Hypoxia causes preservation of labile organic matter and changes seafloor microbial community composition (Black Sea).

PubMed

Jessen, Gerdhard L; Lichtschlag, Anna; Ramette, Alban; Pantoja, Silvio; Rossel, Pamela E; Schubert, Carsten J; Struck, Ulrich; Boetius, Antje

2017-02-01

Bottom-water oxygen supply is a key factor governing the biogeochemistry and community composition of marine sediments. Whether it also determines carbon burial rates remains controversial. We investigated the effect of varying oxygen concentrations (170 to 0 μM O 2 ) on microbial remineralization of organic matter in seafloor sediments and on community diversity of the northwestern Crimean shelf break. This study shows that 50% more organic matter is preserved in surface sediments exposed to hypoxia compared to oxic bottom waters. Hypoxic conditions inhibit bioturbation and decreased remineralization rates even within short periods of a few days. These conditions led to the accumulation of threefold more phytodetritus pigments within 40 years compared to the oxic zone. Bacterial community structure also differed between oxic, hypoxic, and anoxic zones. Functional groups relevant in the degradation of particulate organic matter, such as Flavobacteriia , Gammaproteobacteria , and Deltaproteobacteria , changed with decreasing oxygenation, and the microbial community of the hypoxic zone took longer to degrade similar amounts of deposited reactive matter. We conclude that hypoxic bottom-water conditions-even on short time scales-substantially increase the preservation potential of organic matter because of the negative effects on benthic fauna and particle mixing and by favoring anaerobic processes, including sulfurization of matter.

Hypoxia causes preservation of labile organic matter and changes seafloor microbial community composition (Black Sea)

PubMed Central

Jessen, Gerdhard L.; Lichtschlag, Anna; Ramette, Alban; Pantoja, Silvio; Rossel, Pamela E.; Schubert, Carsten J.; Struck, Ulrich; Boetius, Antje

2017-01-01

Bottom-water oxygen supply is a key factor governing the biogeochemistry and community composition of marine sediments. Whether it also determines carbon burial rates remains controversial. We investigated the effect of varying oxygen concentrations (170 to 0 μM O2) on microbial remineralization of organic matter in seafloor sediments and on community diversity of the northwestern Crimean shelf break. This study shows that 50% more organic matter is preserved in surface sediments exposed to hypoxia compared to oxic bottom waters. Hypoxic conditions inhibit bioturbation and decreased remineralization rates even within short periods of a few days. These conditions led to the accumulation of threefold more phytodetritus pigments within 40 years compared to the oxic zone. Bacterial community structure also differed between oxic, hypoxic, and anoxic zones. Functional groups relevant in the degradation of particulate organic matter, such as Flavobacteriia, Gammaproteobacteria, and Deltaproteobacteria, changed with decreasing oxygenation, and the microbial community of the hypoxic zone took longer to degrade similar amounts of deposited reactive matter. We conclude that hypoxic bottom-water conditions—even on short time scales—substantially increase the preservation potential of organic matter because of the negative effects on benthic fauna and particle mixing and by favoring anaerobic processes, including sulfurization of matter. PMID:28246637

Groundwater and surface-water interaction, water quality, and processes affecting loads of dissolved solids, selenium, and uranium in Fountain Creek near Pueblo, Colorado, 2012–2014

USGS Publications Warehouse

Arnold, L. Rick; Ortiz, Roderick F.; Brown, Christopher R.; Watts, Kenneth R.

2016-11-28

In 2012, the U.S. Geological Survey, in cooperation with the Arkansas River Basin Regional Resource Planning Group, initiated a study of groundwater and surface-water interaction, water quality, and loading of dissolved solids, selenium, and uranium to Fountain Creek near Pueblo, Colorado, to improve understanding of sources and processes affecting loading of these constituents to streams in the Arkansas River Basin. Fourteen monitoring wells were installed in a series of three transects across Fountain Creek near Pueblo, and temporary streamgages were established at each transect to facilitate data collection for the study. Groundwater and surface-water interaction was characterized by using hydrogeologic mapping, groundwater and stream-surface levels, groundwater and stream temperatures, vertical hydraulic-head gradients and ratios of oxygen and hydrogen isotopes in the hyporheic zone, and streamflow mass-balance measurements. Water quality was characterized by collecting periodic samples from groundwater, surface water, and the hyporheic zone for analysis of dissolved solids, selenium, uranium, and other selected constituents and by evaluating the oxidation-reduction condition for each groundwater sample under different hydrologic conditions throughout the study period. Groundwater loads to Fountain Creek and in-stream loads were computed for the study area, and processes affecting loads of dissolved solids, selenium, and uranium were evaluated on the basis of geology, geochemical conditions, land and water use, and evapoconcentration.During the study period, the groundwater-flow system generally contributed flow to Fountain Creek and its hyporheic zone (as a single system) except for the reach between the north and middle transects. However, the direction of flow between the stream, the hyporheic zone, and the near-stream aquifer was variable in response to streamflow and stage. During periods of low streamflow, Fountain Creek generally gained flow from groundwater. However, during periods of high streamflow, the hydraulic gradient between groundwater and the stream temporarily reversed, causing the stream to lose flow to groundwater.Concentrations of dissolved solids, selenium, and uranium in groundwater generally had greater spatial variability than surface water or hyporheic-zone samples, and constituent concentrations in groundwater generally were greater than in surface water. Constituent concentrations in the hyporheic zone typically were similar to or intermediate between concentrations in groundwater and surface water. Concentrations of dissolved solids, selenium, uranium, and other constituents in groundwater samples collected from wells located on the east side of the north monitoring well transect were substantially greater than for other groundwater, surface-water, and hyporheic-zone samples. With one exception, groundwater samples collected from wells on the east side of the north transect exhibited oxic to mixed (oxic-anoxic) conditions, whereas most other groundwater samples exhibited anoxic to suboxic conditions. Concentrations of dissolved solids, selenium, and uranium in surface water generally increased in a downstream direction along Fountain Creek from the north transect to the south transect and exhibited an inverse relation to streamflow with highest concentration occurring during periods of low streamflow and lowest concentrations occurring during periods of high streamflow.Groundwater loads of dissolved solids, selenium, and uranium to Fountain Creek were small because of the small amount of groundwater flowing to the stream under typical low-streamflow conditions. In-stream loads of dissolved solids, selenium, and uranium in Fountain Creek varied by date, primarily in relation to streamflow at each transect and were much larger than computed constituent loads from groundwater. In-stream loads generally decreased with decreases in streamflow and increased as streamflow increased. In-stream loads of dissolved solids and selenium increased between the north and middle transects but generally decreased between the middle and south transects. By contrast, uranium loads generally decreased between the north and middle transects but increased between the middle and south transects. In-stream load differences between transects appear primarily to be related to differences in streamflow. However, because groundwater typically flows to Fountain Creek under low-flow conditions, and groundwater has greater concentrations of dissolved solids, selenium, and uranium than surface water in Fountain Creek, increases in loads between transects likely are affected by inflow of groundwater to the stream, which can account for a substantial proportion of the in-stream load difference between transects. When loads decreased between transects, the primary cause likely was decreased streamflow as a result of losses to groundwater and flow through the hyporheic zone. However, localized groundwater inflow likely attenuated the magnitude by which the in-stream loads decreased.The combination of localized soluble geologic sources and oxic conditions likely is the primary reason for the occurrence of high concentrations of dissolved solids, selenium, and uranium in groundwater on the east side of the north monitoring well transect. To evaluate conditions potentially responsible for differences in water quality and redox conditions, physical characteristics such as depth to water, saturated thickness, screen depth below the water table, screen height above bedrock, and aquifer hydraulic conductivity were compared by using Wilcoxon rank-sum tests. Results indicated no significant difference between depth to water, screen height above bedrock, and hydraulic conductivity for groundwater samples collected from wells on the east side of the north transect and groundwater samples from all other wells. However, saturated thickness and screen depth below the water table both were significantly smaller for groundwater samples collected from wells on the east side of the north transect than for groundwater samples from other wells, indicating that these characteristics might be related to the elevated constituent concentrations found at that location. Similarly, saturated thickness and screen depth below the water table were significantly smaller for groundwater samples under oxic or mixed (oxic-anoxic) conditions than for those under anoxic to suboxic conditions.The greater constituent concentrations at wells on the east side of the north transect also could, in part, be related to groundwater discharge from an unnamed alluvial drainage located directly upgradient from that location. Although the quantity and quality of water discharging from the drainage is not known, the drainage appears to collect water from a residential area located upgradient to the east of the wells, and groundwater could become concentrated in nitrate and other dissolved constituents before flowing through the drainage. High levels of nitrate, whether from anthropogenic or natural geologic sources, could promote more soluble forms of selenium and other constituents by affecting the redox condition of groundwater. Whether oxic conditions at wells on the east side of the north transect are the result of physical characteristics or of groundwater inflow from the alluvial drainage, the oxic conditions appear to cause increased dissolution of minerals from the shallow shale bedrock at that location. Because ratios of hydrogen and oxygen isotopes indicate evaporation likely has not had a substantial effect on groundwater, constituent concentrations at that location likely are not the result of evapoconcentration. 

Freshwater bacteria release methane as a byproduct of phosphorus acquisition.

PubMed

Yao, Mengyin; Henny, Cynthia; Maresca, Julia A

2016-09-30

Freshwater lakes emit large amounts of methane, some of which is produced in oxic surface waters. Two potential pathways for aerobic methane production exist: methanogenesis in oxygenated water, which has been observed in some lakes, or demethylation of small organic molecules. Although methane is produced via demethylation in oxic marine environments, this mechanism of methane release has not yet been demonstrated in freshwater systems. Genes related to the C-P lyase pathway, which cleaves C-P bonds in phosphonate compounds, were found in a metagenomic survey of the surface water of Lake Matano, which is chronically P-starved and methane-rich. We demonstrate that four bacterial isolates from Lake Matano obtain P from methylphosphonate and release methane, and that this activity is repressed by phosphate. We further demonstrate that expression of phnJ, which encodes the enzyme that releases methane, is higher in the presence of methylphosphonate and lower when both methylphosphonate and phosphate are added. This gene is also found in most of the metagenomic data sets from freshwater environments. These experiments link methylphosphonate degradation and methane production with gene expression and phosphate availability in freshwater organisms, and suggest that some of the excess methane in the Lake Matano surface water, and in other methane-rich lakes, may be produced by P-starved bacteria. Methane is an important greenhouse gas, and contributes substantially to global warming. Although freshwater environments are known to release methane into the atmosphere, estimates of the amount of methane emitted by freshwater lakes vary from 8 to 73 Tg per year. Methane emissions are difficult to predict in part because the source of the methane can vary: it is the end product of the energy-conserving pathway in methanogenic archaea, which predominantly live in anoxic sediments or waters, but have also been identified in some oxic freshwater environments. More recently, methane release from small organic molecules has been observed in oxic marine environments. Here we show that demethylation of methylphosphonate may also contribute to methane release from lakes, and that phosphate can repress this activity. Since lakes are typically phosphorus-limited, some methane release in these environments may be a byproduct of phosphorus metabolism, rather than carbon or energy metabolism. Methane emissions from lakes are currently predicted using primary production, eutrophication status, extent of anoxia, and the shape and size of the lake; to improve prediction of methane emissions, phosphorus availability and sources may also need to be included in these models. Copyright © 2016, American Society for Microbiology. All Rights Reserved.

Study of phosphate release from Bogor botanical gardens’ sediment into pore water using diffusive gradient in thin film (DGT)

NASA Astrophysics Data System (ADS)

Tirta, A. P.; Saefumillah, A.; Foliatini

2017-04-01

Eutrophication is one of the environmental problems caused by the excessive nutrients in aquatic ecosystems. In most lakes, phosphate is a limiting nutrient for algae photosynthesis. Even though the concentration of phosphate from external loading into the water body has been reduced, eutrophication could still be occured due to internal mobilization of phosphate from the sediment pore water into the overlying water. Therefore, the released phosphate from sediments and their interaction in the pore water must be included in the monitoring of phosphate concentration in aquatic system. The released phosphate from sediment into pore water has been studied by DGT device with ferrihydrite as binding gel and N-N‧-methylenebisacrylamide as crosslinker. The results showed that DGT with 15% acrylamide; 0.1 % N-N‧-methylenebisacrylamide and ferrihydrite as binding gel was suitable for the measurement of the released phosphate from sediment into pore water. The result of the deployed DGT in oxic and anoxic conditions in seven days incubation showed the released phosphate process from the sediment into pore water was affected by incubation time and the existence of oxygen in the environment. The released phosphate from the sediment into pore water in anoxic condition has a higher value than oxic condition. The experimental results of the deployed DGT in natural sediment core at a depth of 1 to 15 cm from the surface of the water for 7 days showed that the sediment has a different phosphate mass profile based on depth. The concentration of phosphate tends to be increased with depth. The maximum CDGT of phosphate released in oxic and anoxic conditions at 7th day period of incubation are 29.23 μg/L at 14 cm depth and 30.19 μg/L at 8 cm depth, respectively.

Aerobic methane production in surface waters of the Gulf of Mexico

NASA Astrophysics Data System (ADS)

Finke, N.; Crespo-Medina, M.; Schweers, J.; Joye, S. B.

2011-12-01

Near surface water of the global oceans often show elevated methane concentrations compared to the water column below with concentrations in supersaturation in regard to the atmosphere (Lamontagne et al. 1973), resulting in a source of this potent greenhouse gas to the atmosphere. The mechanisms leading to methane supersaturation in surface waters remains unclear. Incubations with Trichodesmium-containing Pacific surface water suggested methylphosphonate as potential methane precursor under phosphate limiting conditions (Karl et al. 2008), whereas in phosphate rich Arctic surface waters, DMSP addition stimulated methane production (Damm et al. 2010). Surface waters of the Gulf of Mexico typically exhibit a methane maximum that is conincident with the deep chlorophyll maximum, below the depths where Trichodesmium is abundant. Addition of methylphosphonate, dimethylsulfoniopropionate (DMSP) or methane thiol (MeSH), the proposed methane precursor in DMSP conversion to methane, to oxic sea water did not affect methane production within the chlorophyll maximum at most stations, whereas methyl phosphonate addition stimulated methane production in the surface water and proposed deep Trichodesmium horizon. Pre-filtration of the water through a 10 μm sieve, which eliminated Trichodesmium, or through a 1.2 μm filter, which eliminated additional cyanobacteria such as Synechococcus, did not reduce methane production. Under dark oxic and dark anoxic conditions, however, methane production was reduced 5 and 7-20 fold, respectively, indicating that anerobic methane production in anoxic microniches is not responsible for the methane production. The reduction of methane production under dark conditions suggests that methane production is, in some yet unrecognized way, linked to phototrophic metabolism. Cyanobacteria are likely not responsible for the observed aerobic methane production in the surface waters of the Gulf of Mexico and while methylphosphonate is a potential precursor in the surface waters, the precursor and methanism of methane production within the coincident deep chlorophyll/methane maximum remains unknown. Lamontagne R, Swinnert J, Linnenbo V, Smith WD (1973) Methane concentrations in various marine environments. Journal of Geophysical Research 78, 5317-5324 Karl DM et al. (2008) Aerobic production of methane in the sea. Nature Geosciences 1, 473-478 Damm E et al. (2010) Methane production in aerobic oligotrophic surface water in the central Arctic Ocean. Biogeosciences 7, 1099-1108

Status and understanding of groundwater quality in the Northern Coast Ranges study unit, 2009: California GAMA Priority Basin Project

USGS Publications Warehouse

Mathany, Timothy M.; Belitz, Kenneth

2015-01-01

Chloroform, simazine, and perchlorate were observed in the Interior Basins and Coastal Basins study areas, predominantly at shallow sites with top-of-perforation depths ≤70 feet below land surface, with modern water (post-1950s), and with oxic groundwater conditions.

Evolution of nanoscale zero-valent iron (nZVI) in water: Microscopic and spectroscopic evidence on the formation of nano- and micro-structured iron oxides.

PubMed

Liu, Airong; Liu, Jing; Han, Jinhao; Zhang, Wei-Xian

2017-01-15

Knowledge on the transformation of nanoscale zero-valent iron (nZVI) in water is essential to predict its surface chemistry including surface charge, colloidal stability and aggregation, reduction and sorption of organic contaminants, heavy metal ions and other pollutants in the environment. In this work, transmission electronic microscopy (TEM), X-ray diffraction (XRD) and Raman spectroscopy are applied to study the compositional and structural evolution of nZVI under oxic and anoxic conditions. Under anoxic conditions, the core-shell structure of nZVI is well maintained even after 72h, and the corrosion products usually contain a mixture of wustite (FeO), goethite (α-FeOOH) and akaganeite (β-FeOOH). Under oxic conditions, the core-shell structure quickly collapses to flakes or acicular-shaped structures with crystalline lepidocrocite (γ-FeOOH) as the primary end product. This work provides detailed information and fills an important knowledge gap on the physicochemical characteristics and structural evolution of engineered nanomaterials in the environment. Copyright © 2015 Elsevier B.V. All rights reserved.

Regulation of Methane Oxidation in a Freshwater Wetland by Water Table Changes and Anoxia

NASA Technical Reports Server (NTRS)

Roslev, Peter; King, Gary M.

1996-01-01

The effects of water table fluctuations and anoxia on methane emission and methane oxidation were studied in a freshwater marsh. Seasonal aerobic methane oxidation rates varied between 15% and 76% of the potential diffusive methane flux (diffusive flux in the absence of aerobic oxidation). On an annual basis, approximately 43% of the methane diffusing into the oxic zone was oxidized before reaching the atmosphere. The highest methane oxidation was observed when the water table was below the peat surface. This was confirmed in laboratory experiments where short-term decreases in water table levels increased methane oxidation but also net methane emission. Although methane emission was generally not observed during the winter, stems of soft rush (Juncus effusus) emitted methane when the marsh was ice covered. Indigenous methanotrophic bacteria from the wetiand studied were relatively anoxia tolerant. Surface peat incubated under anoxic conditions maintained 30% of the initial methane oxidation capacity after 32 days of anoxia. Methanotrophs from anoxic peat initiated aerobic methane oxidation relatively quickly after oxygen addition (1-7 hours). These results were supported by culture experiments with the methanotroph Methylosinus trichosporium OB3b. This organism maintained a greater capacity for aerobic methane oxidation when starved under anoxic compared to oxic conditions. Anoxic incubation of M. trichosporium OB3b in the presence of sulfide (2 mM) and a low redox potential (-110 mV) did not decrease the capacity for methane oxidation relative to anoxic cultures incubated without sulfide. The results suggest that aerobic methane oxidation was a major regulator of seasonal methane emission front the investigated wetland. The observed water table fluctuations affected net methane oxidation presumably due to associated changes in oxygen gradients. However, changes from oxic to anoxic conditions in situ had relatively little effect on survival of the methanotrophic bacteria and thus on methane oxidation potential per se.

Survival of the fittest: phosphorus burial in the sulfidic deep Black Sea

NASA Astrophysics Data System (ADS)

Kraal, Peter; Dijkstra, Nikki; Behrends, Thilo; Slomp, Caroline

2016-04-01

The Black Sea is characterized by permanently anoxic and sulfidic deep waters. Studies of the mechanisms of P burial in such a setting can be used to improve our understanding of P cycling in modern coastal systems undergoing eutrophication and ancient oceans during periods of anoxia in Earth's past. Here, we present phosphorus and iron (Fe) pools as determined in surface sediments along a transect from oxic shallow waters to sulfidic deep waters in the northwestern Black Sea, using a combination of bulk chemical analyses and micro-scale X-ray fluorescence (μXRF) and X-ray absorption spectroscopy (μXAS). We show that under oxic bottom water conditions, ferric iron oxides (Fe(III)ox) in surficial sediment efficiently scavenge dissolved phosphate from pore waters. Under these conditions, Fe(III)ox-bound P constitutes the main P pool at the sediment surface, but rapidly declines with depth in the sediment due to anoxic diagenesis. The transition from shallow (oxic) to deep (sulfidic) waters along the depth transect is reflected in a slight increase in the fraction of organic P. We also show evidence for authigenic calcium phosphate formation under sulfidic conditions at relatively low dissolved PO4 concentrations. Furthermore, we provide spectroscopic evidence for the presence of Fe(II)-Mn(II)-Mg-P minerals in sediments of the sulfidic deep basin. We hypothesize that these minerals are formed as a result of input of Fe(III)ox-P from shallower waters and subsequent transformation in either the water column or sediment. This finding suggests an unexpected strength of Fe-P shuttling from the shelf to the deep basin. While the presence of Fe-P species in such a highly sulfidic environment is remarkable, further analysis suggests that this P pool may not be quantitatively significant. In fact, our results indicate that some of the P that is interpreted as Fe-bound P based on chemical extraction may in fact be Ca-associated PO4 consisting of a combination of fish debris and adsorbed P.

TBA biodegradation in surface-water sediments under aerobic and anaerobic conditions.

PubMed

Bradley, Paul M; Landmeyer, James E; Chapelle, Francis H

2002-10-01

The potential for [U-14C] TBA biodegradation was examined in laboratory microcosms under a range of terminal electron accepting conditions. TBA mineralization to CO2 was substantial in surface-water sediments under oxic, denitrifying, or Mn(IV)-reducing conditions and statistically significant but low under SO4-reducing conditions. Thus, anaerobic TBA biodegradation may be a significant natural attenuation mechanism for TBA in the environment, and stimulation of in situ TBA bioremediation by addition of suitable terminal electron acceptors may be feasible. No degradation of [U-14C] TBA was observed under methanogenic or Fe(III)-reducing conditions.

TBA biodegradation in surface-water sediments under aerobic and anaerobic conditions

USGS Publications Warehouse

Bradley, P.M.; Landmeyer, J.E.; Chapelle, F.H.

2002-01-01

The potential for [U-14C] TBA biodegradation was examined in laboratory microcosms under a range of terminal electron accepting conditions. TBA mineralization to CO2 was substantial in surface-water sediments under oxic, denitrifying, or Mn(IV)-reducing conditions and statistically significant but low under SO4-reducing conditions. Thus, anaerobic TBA biodegradation may be a significant natural attenuation mechanism for TBA in the environment, and stimulation of in situ TBA bioremediation by addition of suitable terminal electron acceptors may be feasible. No degradation of [U-14C] TBA was observed under methanogenic or Fe(III)-reducing conditions.

Effects of ecological engineered oxygenation on the bacterial community structure in an anoxic fjord in western Sweden

PubMed Central

Forth, Michael; Liljebladh, Bengt; Stigebrandt, Anders; Hall, Per O J; Treusch, Alexander H

2015-01-01

Oxygen-depleted bodies of water are becoming increasingly common in marine ecosystems. Solutions to reverse this trend are needed and under development, for example, by the Baltic deep-water OXygenation (BOX) project. In the framework of this project, the Swedish Byfjord was chosen for a pilot study, investigating the effects of an engineered oxygenation on long-term anoxic bottom waters. The strong stratification of the water column of the Byfjord was broken up by pumping surface water into the deeper layers, triggering several inflows of oxygen-rich water and increasing oxygen levels in the lower water column and the benthic zone up to 110 μmol l−1.We used molecular ecologic methods to study changes in bacterial community structure in response to the oxygenation in the Byfjord. Water column samples from before, during and after the oxygenation as well as from two nearby control fjords were analyzed. Our results showed a strong shift in bacterial community composition when the bottom water in the Byfjord became oxic. Initially dominant indicator species for oxygen minimum zones such as members of the SUP05 clade declined in abundance during the oxygenation event and nearly vanished after the oxygenation was accomplished. In contrast, aerobic species like SAR11 that initially were restricted to surface waters could later be detected deep into the water column. Overall, the bacterial community in the formerly anoxic bottom waters changed to a community structure similar to those found in oxic waters, showing that an engineered oxygenation of a large body of anoxic marine water is possible and emulates that of a natural oxygenation event. PMID:25238400

Effects of ecological engineered oxygenation on the bacterial community structure in an anoxic fjord in western Sweden.

PubMed

Forth, Michael; Liljebladh, Bengt; Stigebrandt, Anders; Hall, Per O J; Treusch, Alexander H

2015-03-01

Oxygen-depleted bodies of water are becoming increasingly common in marine ecosystems. Solutions to reverse this trend are needed and under development, for example, by the Baltic deep-water OXygenation (BOX) project. In the framework of this project, the Swedish Byfjord was chosen for a pilot study, investigating the effects of an engineered oxygenation on long-term anoxic bottom waters. The strong stratification of the water column of the Byfjord was broken up by pumping surface water into the deeper layers, triggering several inflows of oxygen-rich water and increasing oxygen levels in the lower water column and the benthic zone up to 110 μmol l(-1).We used molecular ecologic methods to study changes in bacterial community structure in response to the oxygenation in the Byfjord. Water column samples from before, during and after the oxygenation as well as from two nearby control fjords were analyzed. Our results showed a strong shift in bacterial community composition when the bottom water in the Byfjord became oxic. Initially dominant indicator species for oxygen minimum zones such as members of the SUP05 clade declined in abundance during the oxygenation event and nearly vanished after the oxygenation was accomplished. In contrast, aerobic species like SAR11 that initially were restricted to surface waters could later be detected deep into the water column. Overall, the bacterial community in the formerly anoxic bottom waters changed to a community structure similar to those found in oxic waters, showing that an engineered oxygenation of a large body of anoxic marine water is possible and emulates that of a natural oxygenation event.

Iron Cycling in Sediment of the North Atlantic: Preliminary Results from R/V Knorr Expedition 223

NASA Astrophysics Data System (ADS)

Anderson, C. H.; Estes, E. R.; Dyar, M. D.; Murray, R. W.; Spivack, A. J.; Sauvage, J.; McKinley, C. C.; Present, T. M.; Homola, K.; Pockalny, R. A.; D'Hondt, S.

2015-12-01

Iron (Fe) in marine sediments is a significant microbial electron acceptor [Fe(III)] in suboxic conditions and is an electron donor [Fe(II)] in oxic conditions. In the transition from oxic to suboxic sediment, a portion of solid Fe is reduced and mobilized as soluble Fe(II) into interstitial water during the oxidation of organic matter. The presence of Fe and its oxidation state in oxic sediment provides insight into an important metabolic and mineral reaction pathway in subseafloor sediment. We recovered bulk sediment and interstitial water at western North Atlantic sites during Expedition 223 on the R/V Knorr in November, 2014. The expedition targeted regions with predominantly oxic sediment and regions with predominantly anoxic sediment, ideal for investigating redox Fe cycling between solid and aqueous phases. At Site 10 (14.4008N, 50.6209W, 4455m water depth), interstitial dissolved oxygen is depleted within the upper few meters of sediment. At Site 12 (29.6767N, 58.3285W, 5637m water depth), interstitial dissolved oxygen is present throughout the cored sediment column (10s of meters). Here we present total solid Fe concentration for 45 bulk sediment samples and total aqueous Fe and Mn concentrations for 50 interstitial water samples analyzed via ICP-ES. We additionally present Fe(II) and Fe(III) speciation results from 10 solid sediment samples determined by Mossbauer spectroscopy. We trace downcore fluctuations in Fe in solid and aqueous phases to understand Fe cycling in oxic, suboxic, and transitional regimes. Our preliminary data indicate that solid Fe concentration ranges from 4-6 wt % at the oxic site; aqueous Fe ranges from below detection to 20μM and aqueous Mn ranges from 1 to 125 μM at the anoxic site. In the anoxic sediment (Site 10), 86-90% of the total Fe is oxidized [Fe(III)] and 10-14% as reduced [Fe(II)], compared to 3-6% as reduced [Fe(II)] at the oxic site (Site 12), even in sediment as old as 25 million years.

Oxic to anoxic transition in bottom waters during formation of the Citronen Fjord sediment-hosted Zn-Pb deposit, North Greenland

USGS Publications Warehouse

Slack, John F.; Rosa, Diogo; Falck, Hendrik

2015-01-01

Bulk geochemical data acquired for host sedimentary rocks to the Late Ordovician Citronen Fjord sediment-hosted Zn-Pb deposit in North Greenland constrain the redox state of bottom waters prior to and during sulphide mineralization. Downhole profiles for one drill core show trends for redox proxies (MnO, Mo, Ce anomalies) that suggest the local basin bottom waters were initially oxic, changing to anoxic and locally sulphidic concurrent with sulphide mineralization. We propose that this major redox change was caused by two broadly coeval processes (1) emplacement of debris-flow conglomerates that sealed off the basin from oxic seawater, and (2) venting of reduced hydrothermal fluids into the basin. Both processes may have increased H2S in bottom waters and thus prevented the oxidation of sulphides on the sea floor.

Oxic microshield and local pH enhancement protects Zostera muelleri from sediment derived hydrogen sulphide.

PubMed

Brodersen, Kasper Elgetti; Nielsen, Daniel Aagren; Ralph, Peter J; Kühl, Michael

2015-02-01

Seagrass is constantly challenged with transporting sufficient O₂ from above- to belowground tissue via aerenchyma in order to maintain aerobic metabolism and provide protection against phytotoxins. Electrochemical microsensors were used in combination with a custom-made experimental chamber to analyse the belowground biogeochemical microenvironment of Zostera muelleri under changing environmental conditions. Measurements revealed high radial O₂ release of up to 500 nmol O2 cm(-2) h(-1) from the base of the leaf sheath, maintaining a c. 300-μm-wide plant-mediated oxic microzone and thus protecting the vital meristematic regions of the rhizome from reduced phytotoxic metabolites such as hydrogen sulphide (H₂S). H₂S intrusion was prevented through passive diffusion of O₂ to belowground tissue from leaf photosynthesis in light, as well as from the surrounding water column into the flow-exposed plant parts during darkness. Under water column hypoxia, high belowground H₂S concentrations at the tissue surface correlated with the inability to sustain the protecting oxic microshield around the meristematic regions of the rhizome. We also found increased pH levels in the immediate rhizosphere of Z. muelleri, which may contribute to further detoxification of H₂S through shifts in the chemical speciation of sulphide. Zostera muelleri can modify the geochemical conditions in its immediate rhizosphere, thereby reducing its exposure to H₂S. © 2014 The Authors. New Phytologist © 2014 New Phytologist Trust.

Processes affecting geochemistry and contaminant movement in the middle Claiborne aquifer of the Mississippi embayment aquifer system

USGS Publications Warehouse

Katz, Brian G.; Kingsbury, James A.; Welch, Heather L.; Tollett, Roland W.

2012-01-01

Groundwater chemistry and tracer-based age data were used to assess contaminant movement and geochemical processes in the middle Claiborne aquifer (MCA) of the Mississippi embayment aquifer system. Water samples were collected from 30 drinking-water wells (mostly domestic and public supply) and analyzed for nutrients, major ions, pesticides, volatile organic compounds (VOCs), and transient age tracers (chlorofluorocarbons, tritium and helium-3, and sulfur hexafluoride). Redox conditions are highly variable throughout the MCA. However, mostly oxic groundwater with low dissolved solids is more vulnerable to nitrate contamination in the outcrop areas east of the Mississippi River in Mississippi and west Tennessee than in mostly anoxic groundwater in downgradient areas in western parts of the study area. Groundwater in the outcrop area was relatively young (apparent age of less than 40 years) with significantly (p 50 m depth) indicated contaminant movement from shallow parts of the aquifer into deeper oxic zones. Given the persistence of nitrate in young oxic groundwater that was recharged several decades ago, and the lack of a confining unit, the downward movement of young contaminated water may result in higher nitrate concentrations over time in deeper parts of the aquifer containing older oxic water.

Profiling bacterial communities associated with sediment-based aquaculture bioremediation systems under contrasting redox regimes

NASA Astrophysics Data System (ADS)

Robinson, Georgina; Caldwell, Gary S.; Wade, Matthew J.; Free, Andrew; Jones, Clifford L. W.; Stead, Selina M.

2016-12-01

Deposit-feeding invertebrates are proposed bioremediators in microbial-driven sediment-based aquaculture effluent treatment systems. We elucidate the role of the sediment reduction-oxidation (redox) regime in structuring benthic bacterial communities, having direct implications for bioremediation potential and deposit-feeder nutrition. The sea cucumber Holothuria scabra was cultured on sediments under contrasting redox regimes; fully oxygenated (oxic) and redox stratified (oxic-anoxic). Taxonomically, metabolically and functionally distinct bacterial communities developed between the redox treatments with the oxic treatment supporting the greater diversity; redox regime and dissolved oxygen levels were the main environmental drivers. Oxic sediments were colonised by nitrifying bacteria with the potential to remediate nitrogenous wastes. Percolation of oxygenated water prevented the proliferation of anaerobic sulphate-reducing bacteria, which were prevalent in the oxic-anoxic sediments. At the predictive functional level, bacteria within the oxic treatment were enriched with genes associated with xenobiotics metabolism. Oxic sediments showed the greater bioremediation potential; however, the oxic-anoxic sediments supported a greater sea cucumber biomass. Overall, the results indicate that bacterial communities present in fully oxic sediments may enhance the metabolic capacity and bioremediation potential of deposit-feeder microbial systems. This study highlights the benefits of incorporating deposit-feeding invertebrates into effluent treatment systems, particularly when the sediment is oxygenated.

Profiling bacterial communities associated with sediment-based aquaculture bioremediation systems under contrasting redox regimes

PubMed Central

Robinson, Georgina; Caldwell, Gary S.; Wade, Matthew J.; Free, Andrew; Jones, Clifford L. W.; Stead, Selina M.

2016-01-01

Deposit-feeding invertebrates are proposed bioremediators in microbial-driven sediment-based aquaculture effluent treatment systems. We elucidate the role of the sediment reduction-oxidation (redox) regime in structuring benthic bacterial communities, having direct implications for bioremediation potential and deposit-feeder nutrition. The sea cucumber Holothuria scabra was cultured on sediments under contrasting redox regimes; fully oxygenated (oxic) and redox stratified (oxic-anoxic). Taxonomically, metabolically and functionally distinct bacterial communities developed between the redox treatments with the oxic treatment supporting the greater diversity; redox regime and dissolved oxygen levels were the main environmental drivers. Oxic sediments were colonised by nitrifying bacteria with the potential to remediate nitrogenous wastes. Percolation of oxygenated water prevented the proliferation of anaerobic sulphate-reducing bacteria, which were prevalent in the oxic-anoxic sediments. At the predictive functional level, bacteria within the oxic treatment were enriched with genes associated with xenobiotics metabolism. Oxic sediments showed the greater bioremediation potential; however, the oxic-anoxic sediments supported a greater sea cucumber biomass. Overall, the results indicate that bacterial communities present in fully oxic sediments may enhance the metabolic capacity and bioremediation potential of deposit-feeder microbial systems. This study highlights the benefits of incorporating deposit-feeding invertebrates into effluent treatment systems, particularly when the sediment is oxygenated. PMID:27941918

Selenium and trace element mobility affected by periodic displacement of stratification in the Great Salt Lake, Utah

USGS Publications Warehouse

Beisner, K.; Naftz, D.L.; Johnson, W.P.; Diaz, X.

2009-01-01

The Great Salt Lake (GSL) is a unique ecosystem in which trace element activity cannot be characterized by standard geochemical parameters due to the high salinity. Movement of selenium and other trace elements present in the lake bed sediments of GSL may occur due to periodic stratification displacement events or lake bed exposure. The water column of GSL is complicated by the presence of a chemocline persistent over annual to decadal time scales. The water below the chemocline is referred to as the deep brine layer (DBL), has a high salinity (16.5 to 22.9%) and is anoxic. The upper brine layer (UBL) resides above the chemocline, has lower salinity (12.6 to 14.7%) and is oxic. Displacement of the DBL may involve trace element movement within the water column due to changes in redox potential. Evidence of stratification displacement in the water column has been observed at two fixed stations on the lake by monitoring vertical water temperature profiles with horizontal and vertical velocity profiles. Stratification displacement events occur over periods of 12 to 24 h and are associated with strong wind events that can produce seiches within the water column. In addition to displacement events, the DBL shrinks and expands in response to changes in the lake surface area over a period of months. Laboratory tests simulating the observed sediment re-suspension were conducted over daily, weekly and monthly time scales to understand the effect of placing anoxic bottom sediments in contact with oxic water, and the associated effect of trace element desorption and (or) dissolution. Results from the laboratory simulations indicate that a small percentage (1%) of selenium associated with anoxic bottom sediments is periodically solubilized into the UBL where it potentially can be incorporated into the biota utilizing the oxic part of GSL.

A geochemical model of the Peru Basin deep-sea floor—and the response of the system to technical impacts

NASA Astrophysics Data System (ADS)

König, Iris; Haeckel, Matthias; Lougear, André; Suess, Erwin; Trautwein, Alfred X.

A geochemical model of the Peru Basin deep-sea floor, based on an extensive set of field data as well as on numerical simulations, is presented. The model takes into account the vertical oscillations of the redox zonation that occur in response to both long-term (glacial/interglacial) and short-term (El Niño Southern Oscillation (ENSO) time scale) variations in the depositional flux of organic matter. Field evidence of reaction between the pore water NO 3- and an oxidizable fraction of the structural Fe(II) in the clay mineral content of the deep-sea sediments is provided. The conditions of formation and destruction of reactive clay Fe(II) layers in the sea floor are defined, whereby a new paleo-redox proxy is established. Transitional NO 3- profile shapes are explained by periodic contractions and expansions of the oxic zone (ocean bottom respiration) on the ENSO time scale. The near-surface oscillations of the oxic-suboxic boundary constitute a redox pump mechanism of major importance with respect to diagenetic trace metal enrichments and manganese nodule formation, which may account for the particularly high nodule growth rates in this ocean basin. These conditions are due to the similar depth ranges of both the O 2 penetration in the sea floor and the bioturbated high reactivity surface layer (HRSL), all against the background of ENSO-related large variations in depositional C org flux. Removal of the HRSL in the course of deep-sea mining would result in a massive expansion of the oxic surface layer and, thus, the shut down of the near-surface redox pump for centuries, which is demonstrated by numerical modeling.

Predicting redox conditions in groundwater at a regional scale

USGS Publications Warehouse

Tesoriero, Anthony J.; Terziotti, Silvia; Abrams, Daniel B.

2015-01-01

Defining the oxic-suboxic interface is often critical for determining pathways for nitrate transport in groundwater and to streams at the local scale. Defining this interface on a regional scale is complicated by the spatial variability of reaction rates. The probability of oxic groundwater in the Chesapeake Bay watershed was predicted by relating dissolved O2 concentrations in groundwater samples to indicators of residence time and/or electron donor availability using logistic regression. Variables that describe surficial geology, position in the flow system, and soil drainage were important predictors of oxic water. The probability of encountering oxic groundwater at a 30 m depth and the depth to the bottom of the oxic layer were predicted for the Chesapeake Bay watershed. The influence of depth to the bottom of the oxic layer on stream nitrate concentrations and time lags (i.e., time period between land application of nitrogen and its effect on streams) are illustrated using model simulations for hypothetical basins. Regional maps of the probability of oxic groundwater should prove useful as indicators of groundwater susceptibility and stream susceptibility to contaminant sources derived from groundwater.

The Dynamics of sediment oxygenation in Spartina anglica Rhizospheres - a Planar Optode Study

NASA Astrophysics Data System (ADS)

Koop-Jakobsen, Ketil

2013-04-01

The salt marsh grass Spartina anglica have well-developed aerenthyma tissue facilitating a rapid transport of oxygen from the atmosphere to belowground roots and rhizomes, where oxygen can leak out of the root system and oxygenate the surrounding sediment. In this way, oxic microzones are distributed vertically in marsh sediments promoting aerobic microbial activity at depth. In this study, the dynamics of sediment oxygenation in Spartina anglica rhizospheres was investigated, visualizing the belowground oxygen content using planar optode technology. Oxic microzones around roots and rhizomes were monitored in the laboratory under different light conditions and during tidal inundations of the aboveground biomass. Oxic microzones were restricted to the root tips extending up to16mm along the root and 1.5mm into the anoxic bulk sediment from the root surface. The oxygen concentration was highest at the root-surface ranging from 58-85μM. The volume of the oxic microzones did not change significantly with decreasing light availability of the aboveground biomass showing that the atmosphere is the primary source for oxygen transported below ground. Consequently, tidal inundations cutting off the access to atmospheric oxygen resulted in a complete collapse of the oxic microzones after 3 hours of inundation in the light as well as in the dark. However, monitoring oxic microzones during a 24h tidal cycle with diurnal tidal inundations lasting 90min showed a 36% reduction of the oxic microzones in the light in contrast to a complete collapse of the oxic microzones in the dark. Hence, light availability and photosynthetic oxygen production of the aboveground biomass does influence the kinetics of oxic microzone develupment. Belowground sediment oxygenation is of significant importance for the biogeochemical cycles in salt marsh sediment, in particular coupled nitrification-denitrification occurring at depth associated with oxic microzones can account for a significant proportion of the gaseous export of nitrogen from Spartina spp.-dominated marshes. This study shows that tidal inundations have significant impact on belowground biogeochemical conditions and must be taken into account when monitoring tidal marsh processes on a daily basis.

Effects of oxygen and redox oscillation on degradation of cell-associated lipids in surficial marine sediments

NASA Astrophysics Data System (ADS)

Sun, Ming-Y. i.; Aller, Robert C.; Lee, Cindy; Wakeham, Stuart G.

2002-06-01

Degradation patterns of sedimentary algal lipids were tracked with time under variable redox treatments designed to mimic conditions in organic-rich, bioturbated deposits. Uniformly 13C-labeled algae were mixed with Long Island Sound surface muddy sediments and exposed to different redox regimes, including continuously oxic and anoxic, and oscillated oxic: anoxic conditions. Concentrations of several 13C-labeled algal fatty acids (16:1, 16:0 and 18:1), phytol and an alkene were measured serially. Results showed a large difference (∼10×) in first-order degradation rate constants of cell-associated lipids between continuously oxic and anoxic conditions. Exposure to oxic conditions increased the degradation of cell-associated lipids, and degradation rate constants were positive functions (linear or nonlinear) of the fraction of time sediments were oxic. Production of two new 13C-labeled compounds (iso-15:0 fatty acid and hexadecanol) further indicated that redox conditions and oxic: anoxic oscillations strongly affect microbial degradation of algal lipids and net synthesis of bacterial biomass. Production of 13C-labeled iso-15:0 fatty acid (a bacterial biomarker) was inversely proportional to the fraction of time sediments were oxic, rapidly decreasing after 10 days of incubation under oxic and frequently oscillated conditions. Turnover of bacterial biomass was faster under continuously or occasionally oxic conditions than under continuously anoxic conditions. 13C-labeled hexadecanol, an intermediate degradation product, accumulated under anoxic conditions but not under oxic or periodically oxic conditions. The frequency of oxic: anoxic oscillation clearly alters both the rate and pathways of lipid degradation in surficial sediments. Terminal degradation efficiency and lipid products from degradation of algal material depend on specific patterns of redox fluctuations.

Staphylococcus aureus Strain Newman Photoinactivation and Cellular Response to Sunlight Exposure.

PubMed

McClary, Jill S; Sassoubre, Lauren M; Boehm, Alexandria B

2017-09-01

Sunlight influences microbial water quality of surface waters. Previous studies have investigated photoinactivation mechanisms and cellular photostress responses of fecal indicator bacteria (FIB), including Escherichia coli and enterococci, but further work is needed to characterize photostress responses of bacterial pathogens. Here we investigate the photoinactivation of Staphylococcus aureus (strain Newman), a pigmented, waterborne pathogen of emerging concern. We measured photodecay using standard culture-based assays and cellular membrane integrity and investigated photostress response by measuring the relative number of mRNA transcripts of select oxidative stress, DNA repair, and metabolism genes. Photoinactivation experiments were performed in both oxic and anoxic systems to further investigate the role of oxygen-mediated and non-oxygen-mediated photoinactivation mechanisms. S. aureus lost culturability much faster in oxic systems than in anoxic systems, indicating an important role for oxygen in photodecay mechanisms. S. aureus cell membranes were damaged by sunlight exposure in anoxic systems but not in oxic systems, as measured by cell membrane permeability to propidium iodide. After sunlight exposure, S. aureus increased expression of a gene coding for methionine sulfoxide reductase after 12 h of sunlight exposure in the oxic system and after 6 h of sunlight exposure in the anoxic system, suggesting that methionine sulfoxide reductase is an important enzyme for defense against both oxygen-dependent and oxygen-independent photostresses. This research highlights the importance of oxygen in bacterial photoinactivation in environmentally relevant systems and the complexity of the bacterial photostress response with respect to cell structure and transcriptional regulation. IMPORTANCE Staphylococcus aureus is a pathogenic bacterium that causes gastrointestinal, respiratory, and skin infections. In severe cases, S. aureus infection can lead to life-threatening diseases, including pneumonia and sepsis. Cases of community-acquired S. aureus infection have been increasing in recent years, pointing to the importance of considering S. aureus transmission pathways outside the hospital environment. Associations have been observed between recreational water contact and staphylococcal skin infections, suggesting that recreational waters may be an important environmental transmission pathway for S. aureus However, prediction of human health risk in recreational waters is hindered by incomplete knowledge of pathogen sources, fate, and transport in this environment. This study is an in-depth investigation of the inactivation of a representative strain of S. aureus by sunlight exposure, one of the most important factors controlling the fate of microbial contaminants in clear waters, which will improve our ability to predict water quality changes and human health risk in recreational waters. Copyright © 2017 American Society for Microbiology.

Enhanced nitrogen loss from rivers through coupled nitrification-denitrification caused by suspended sediment.

PubMed

Xia, Xinghui; Liu, Ting; Yang, Zhifeng; Michalski, Greg; Liu, Shaoda; Jia, Zhimei; Zhang, Sibo

2017-02-01

Present-day estimations of global nitrogen loss (N-loss) are underestimated. Commonly, N-loss from rivers is thought to be caused by denitrification only in bed-sediments. However, coupled nitrification-denitrification occurring in overlying water with suspended sediments (SPS) where oxic and anoxic/low oxygen zones may coexist is ignored for N-loss in rivers. Here the Yellow and Yangtze Rivers were taken as examples to investigate the effect of SPS, which exists in many rivers of the world, on N loss through coupled nitrification-denitrification with nitrogen stable ( 15 N) isotopic tracer simulation experiments and in-situ investigation. The results showed even when SPS was surrounded by oxic waters, there were redox conditions that transitioned from an oxic surface layer to anoxic layer near the particle center, enabling coupled nitrification-denitrification to occur around SPS. The production rate of 15 N 2 from 15 NH 4 + -N (R 15N2-production ) increased with increasing SPS concentration ([SPS]) as a power function (R 15N2-production =a·[SPS] b ) for both the SPS-water and bed sediment-SPS-water systems. The power-functional increase of nitrifying and denitrifying bacteria population with [SPS] accounted for the enhanced coupled nitrification-denitrification rate in overlying water. SPS also accelerated denitrification in bed-sediment due to increased NO 3 - concentration caused by SPS-mediated nitrification. For these two rivers, 1gL -1 SPS will lead to N-loss enhancement by approximately 25-120%, and the enhancement increased with organic carbon content of SPS. Thus, we conclude that SPS in overlying water is a hot spot for nitrogen loss in river systems and current estimates of in-stream N-loss are underestimated without consideration of SPS; this may partially compensate for the current imbalance of global nitrogen inputs and sinks. Copyright © 2016 Elsevier B.V. All rights reserved.

Evidence for methane production by the marine algae Emiliania huxleyi

NASA Astrophysics Data System (ADS)

Lenhart, Katharina; Klintzsch, Thomas; Langer, Gerald; Nehrke, Gernot; Bunge, Michael; Schnell, Sylvia; Keppler, Frank

2016-06-01

Methane (CH4), an important greenhouse gas that affects radiation balance and consequently the earth's climate, still has uncertainties in its sinks and sources. The world's oceans are considered to be a source of CH4 to the atmosphere, although the biogeochemical processes involved in its formation are not fully understood. Several recent studies provided strong evidence of CH4 production in oxic marine and freshwaters, but its source is still a topic of debate. Studies of CH4 dynamics in surface waters of oceans and large lakes have concluded that pelagic CH4 supersaturation cannot be sustained either by lateral inputs from littoral or benthic inputs alone. However, regional and temporal oversaturation of surface waters occurs frequently. This comprises the observation of a CH4 oversaturating state within the surface mixed layer, sometimes also termed the "oceanic methane paradox". In this study we considered marine algae as a possible direct source of CH4. Therefore, the coccolithophore Emiliania huxleyi was grown under controlled laboratory conditions and supplemented with two 13C-labeled carbon substrates, namely bicarbonate and a position-specific 13C-labeled methionine (R-S-13CH3). The CH4 production was 0.7 µg particular organic carbon (POC) g-1 d-1, or 30 ng g-1 POC h-1. After supplementation of the cultures with the 13C-labeled substrate, the isotope label was observed in headspace CH4. Moreover, the absence of methanogenic archaea within the algal culture and the oxic conditions during CH4 formation suggest that the widespread marine algae Emiliania huxleyi might contribute to the observed spatially and temporally restricted CH4 oversaturation in ocean surface waters.

In Situ Mo Isotope Fractionation in the Water Columns of Euxinic Basins

NASA Astrophysics Data System (ADS)

Neubert, N.; Nägler, T. F.; Böttcher, M. E.

2007-12-01

The present study investigates for the first time the overall process of molybdenum (Mo) scavenging in modern euxinic systems using Mo concentration and stable isotope measurements. We analyzed samples from three different sites: The Black Sea, the largest permanently euxinic basin, and two anoxic basins of the Baltic Sea, the Gotland Deep and the Landsort Deep which have maximum water depths of 247 m and 459 m, respectively. Water column profiles, as well as surface sediment samples, were recovered from different water depths. Mo is a redox-sensitive trace metal which is soluble as the molybdate oxyanion in oxic seawater with a residence time of about 800 ka. The isotope signature of Mo is a relatively new proxy used to reconstruct the paleo-redox conditions of the Earth's atmosphere and the oceanic system. The Mo isotope composition in seawater is homogeneous (Siebert et al. 2003). Scavenging of Mo under euxinic conditions is related to the amount of free sulfide in the water column. Near total removal of Mo from the water column is reached at aquatic sulfide concentration of c. 11 μM (Erickson and Helz 2000). In the Black Sea this corresponds to a water depth of about 400 m. Sediment samples of the Black Sea from more then 400 m water depth show seawater isotopic composition, in line with the assumption of bulk Mo removal. However, shallower sediments deposited under lower aquatic sulfide concentrations show significant Mo isotope fractionation. The Baltic Sea oceanographic conditions, including temporary bottom water oxygenation due to sporadic North Sea water inflows, are more complex than in the Black Sea. The aquatic sulfide concentration in the water column is less than 5 μM in the two anoxic troughs. As expected from this lower sulfidity, the surface sediments show Mo fractionation similar to the oxic to slightly euxinic sediments of the Black Sea. Our new results on the Mo isotopic composition in euxinic water columns clearly indicate in situ fractionation of Mo isotopes. All euxinic water samples from the three settings are shifted towards heavier Mo isotope signatures, thus complementing the lighter values in the surface sediments (Nagler et al. 2005).

Just Around the Riverbend: Seasonal hydrologic controls on dynamic hyporheic zone redox biogeochemistry

NASA Astrophysics Data System (ADS)

Saup, C. M.; Sawyer, A. H.; Williams, K. H.; Wilkins, M.

2017-12-01

Upland rivers host exceptionally strong linkages between the terrestrial and aquatic elemental cycles. The weathering of mineral phases, coupled with degradation of organic matter and anthropogenic influences can result in the export of carbon, metals, and nutrients in upland fluvial systems, often decreasing downstream water quality with negative impacts on both human usage and ecosystem functioning. Within these fluvial networks, zones of hyporheic mixing—regions within the riverbed where surface water and groundwater mix—are thought to represent hotspots of biogeochemical activity, thus exerting significant control over elemental cycling and solute export. To investigate how the deeper exchange of oxic river water into the riverbed during snowmelt-driven peak discharge affects microbial degradation (oxidation) of carbon pools, depth resolved pore water samples were recovered from multiple locations around a representative meander on the East River near Crested Butte, CO. At each location, a series of temperature and redox probes were installed in the riverbed to track the extent of hyporheic mixing and the impact of this process on riverbed biogeochemistry. We complemented this real-time data with discrete samples collected during peak flow, intermediate flow, and base flow at a 10 cm resolution over 70 cm vertical profiles for a suite of microbiological and geochemical analyses. Results revealed elevated pore fluid concentrations of dissolved metals and recalcitrant DOC species under reducing conditions induced by base flow, while regions that were more influenced by down-welling oxic surface water hosted distinct microbial communities and lower metal concentrations. Overall, our results indicate that mixing-driven vertical redox gradients exert a strong control on biogeochemical processing in riverbeds, with implications for downstream water quality and solute export from watersheds.

Mobility of 137Cs in freshwater lakes: A mass balance and diffusion study of Lake St. Clair, Southeast Michigan, USA

NASA Astrophysics Data System (ADS)

Wang, Jinlong; Baskaran, Mark; Niedermiller, John

2017-12-01

Cesium-137 is one of the most widely utilized anthropogenic radionuclides, both as a tracer and chronometer in the environment. Its application as an effective chronometer requires a thorough understanding of its geochemical behavior in aqueous systems. In this study, we collected and analyzed a suite of time-series water samples over a period of 8 months (April - November 2015), for particulate and dissolved 137Cs activities from a watershed in southeast Michigan, USA, using Cu2Fe(CN)6-coated cartridges developed to pre-concentrate dissolved 137Cs. We also conducted a series of laboratory experiments with the natural freshwater sediment samples and water with different chemical composition. There were seasonal variations of both particulate and dissolved 137Cs activities in the watersheds of Lake St. Clair. The distribution coefficients of 137Cs determined over a period of 8 months varied between 0.14 × 105 and 6.1 × 105 mL g-1 (mean: 2.9 × 105 mL g-1). The annual input and export flux of total 137Cs activity via rivers into and out of Lake St. Clair were calculated to be 3.6 × 1010 Bq and 1.6 × 1010 Bq, respectively. The amount of 137Cs derived by diffusion from interstitial pore water to the water column was estimated to be 0.30 × 1010 Bq (8.3% of the total input flux) which is similar to the percentage of 137Cs desorption (13%-20%) from sediment placed in oxic soft water system over a period of 30-106 days. For the same concentrations of NH4+, Mn2+, K+, Mg2+, Ca2+, Na+ and Sr2+ in a distilled water, our lab work showed that the sediment-sorbed 137Cs is displaced by ions in the order NH4+ > Mn2+ > K+ > Mg2+ ≈ Ca2+ > Na+ > Sr2+. In laboratory studies, 137Cs sorbed onto sediment was found to be less mobile in oxic soft water (Kd: 2.0 × 103 mL g-1) and more mobile in anoxic soft water (Kd: 0.2 × 103 mL g-1). In a hard water system, however, there is no significant difference in Kd values for both oxic and anoxic conditions. The sequence of Kd values is: oxic soft water > oxic hard water > anoxic hard water > anoxic soft water. The desorption experiments with 137Cs-sorbed sediments also confirmed that 137Cs is much more mobile in soft water than hard water. This mobility of 137Cs under oxic hard water system makes sedimentation rate estimation by 137Cs (based on the time the introduction of 137Cs) problematic in some soft water lakes, and estuarine and coastal waters.

Underground structure pattern and multi AO reaction with step feed concept for upgrading an large wastewater treatment plant

NASA Astrophysics Data System (ADS)

Peng, Yi; Zhang, Jie; Li, Dong

2018-03-01

A large wastewater treatment plant (WWTP) could not meet the new demand of urban environment and the need of reclaimed water in China, using a US treatment technology. Thus a multi AO reaction process (Anaerobic/oxic/anoxic/oxic/anoxic/oxic) WWTP with underground structure was proposed to carry out the upgrade project. Four main new technologies were applied: (1) multi AO reaction with step feed technology; (2) deodorization; (3) new energy-saving technology such as water resource heat pump and optical fiber lighting system; (4) dependable old WWTP’s water quality support measurement during new WWTP’s construction. After construction, upgrading WWTP had saved two thirds land occupation, increased 80% treatment capacity and improved effluent standard by more than two times. Moreover, it had become a benchmark of an ecological negative capital changing to a positive capital.

Biodegradation of MTBE by indigenous aquifer microorganisms under artificial oxic conditions

USGS Publications Warehouse

Landmeyer, J.E.; Bradley, P.M.

2001-01-01

Oxygen in the form of a metal peroxide slurry (MgO2 and water) was added to an anoxic part of a gasoline-contaminated aquifer in South Carolina to test the hypothesis that artificial oxic conditions will lead to MTBE biodegradation by indigenous microorganisms in anoxic, gasoline-contaminated aquifers. The slurry slowly released dissolved oxygen upon hydrolysis with groundwater, and was a proprietary mixture consisting of ??? 25-35 wt % MgO2. Significant natural attenuation of MTBE could occur if the oxygen limitations naturally associated with gasoline releases could be removed, either under natural conditions where discharging anoxic groundwater comes into contact with oxygen, or artificial conditions where oxygen could be added to aquifers containing milligram per liter concentrations of MTBE. This final solution might be an effective strategy for intercepting characteristically long MTBE plumes, particularly at those sites not characterized by groundwater discharge to land surface.

Phosphorus storage and mobilization in coastal Phragmites wetlands: Influence of local-scale hydrodynamics

NASA Astrophysics Data System (ADS)

Karstens, Svenja; Buczko, Uwe; Glatzel, Stephan

2016-04-01

Coastal Phragmites wetlands are at the interface between terrestrial and aquatic ecosystems and are of paramount importance for nutrient regulation. They can act both as sinks and sources for phosphorus, depending on environmental conditions, sediment properties as well as on antecedent nutrient loading and sorption capacity of the sediments. The Darss-Zingst Bodden Chain is a shallow lagoon system at the German Baltic Sea coast with a long eutrophication history. It is lined almost at its entire length by reed wetlands. In order to elucidate under which conditions these wetlands act as sources or sinks for phosphorus, in-situ data of chemo-physical characteristics of water and sediment samples were combined with hydrodynamic measurements and laboratory experiments. Small-scale basin structures within the wetland serve as sinks for fine-grained particles rich in phosphorus, iron, manganese and organic matter. Without turbulent mixing the bottom water and the sediment surface lack replenishment of oxygen. During stagnant periods with low water level, low turbulence and thus low-oxygen conditions phosphorus from the sediments is released. But the sediments are capable of becoming sinks again once oxygen is resupplied. A thin oxic sediment surface layer rich in iron and manganese adsorbs phosphorus quickly. We demonstrate that sediments in coastal Phragmites wetlands can serve both as sources and sinks of soluble reactive phosphorus on a very short time-scale, depending on local-scale hydrodynamics and the state of the oxic-anoxic sediment interface.

Ferromanganese nodules from MANOP Sites H, S, and R-Control of mineralogical and chemical composition by multiple accretionary processes

USGS Publications Warehouse

Dymond, J.; Lyle, M.; Finney, B.; Piper, D.Z.; Murphy, K.; Conard, R.; Pisias, N.

1984-01-01

The chemical composition of ferromanganese nodules from the three nodule-bearing MANOP sites in the Pacific can be accounted for in a qualitative way by variable contributions of distinct accretionary processes. These accretionary modes are: 1. (1) hydrogenous, i.e., direct precipitation or accumulation of colloidal metal oxides in seawater, 2. (2) oxic diagenesis which refers to a variety of ferromanganese accretion processes occurring in oxic sediments; and 3. (3) suboxic diagenesis which results from reduction of Mn+4 by oxidation of organic matter in the sediments. Geochemical evidence suggests processes (1) and (2) occur at all three MANOP nodule-bearing sites, and process (3) occurs only at the hemipelagic site, H, which underlies the relatively productive waters of the eastern tropical Pacific. A normative model quantitatively accounts for the variability observed in nearly all elements. Zn and Na, however, are not well explained by the three end-member model, and we suggest that an additional accretionary process results in greater variability in the abundances of these elements. Variable contributions from the three accretionary processes result in distinct top-bottom compositional differences at the three sites. Nodule tops from H are enriched in Ni, Cu, and Zn, instead of the more typical enrichments of these elements in nodule bottoms. In addition, elemental correlations typical of most pelagic nodules are reversed at site H. The three accretionary processes result in distinct mineralogies. Hydrogenous precipitation produces ??MnO2. Oxic diagenesis, however, produces Cu-Ni-rich todorokite, and suboxic diagenesis results in an unstable todorokite which transforms to a 7 A?? phase ("birnessite") upon dehydration. The presence of Cu and Ni as charge-balancing cations influence the stability of the todorokite structure. In the bottoms of H nodules, which accrete dominantly by suboxic diagenesis, Na+ and possibly Mn+2 provide much of the charge balance for the todorokite structure. Limited growth rate data for H nodules suggest suboxic accretion is the fastest of the three processes, with rates at least 200 mm/106 yr. Oxic accretion is probably 10 times slower and hydrogenous 100 times slower. Since these rates predict more suboxic component in bulk nodules than is calculated by the normative analysis, we propose that suboxic accretion is a non-steady-state process. Variations in surface water productivity cause pulses of particulate flux to the sea floor which result in transient Mn reduction in the surface sediments and reprecipitation on nodule surfaces. ?? 1984.

Ferromanganese nodules from MANOP Sites H, S, and R - Control of mineralogical and chemical composition by multiple accretionary processes

NASA Astrophysics Data System (ADS)

Dymond, Jack; Lyle, Mitchell; Finney, Bruce; Piper, David Z.; Murphy, Kim; Conard, Roberta; Pisias, Nicklas

1984-05-01

The chemical composition of ferromanganese nodules from the three nodule-bearing MANOP sites in the Pacific can be accounted for in a qualitative way by variable contributions of distinct accretionary processes. These accretionary modes are: (1) hydrogenous, i.e., direct precipitation or accumulation of colloidal metal oxides in seawater, (2) oxic diagenesis which refers to a variety of ferromanganese accretion processes occurring in oxic sediments; and (3) suboxic diagenesis which results from reduction of Mn +4 by oxidation of organic matter in the sediments. Geochemical evidence suggests processes (1) and (2) occur at all three MANOP nodule-bearing sites, and process (3) occurs only at the hemipelagic site, H, which underlies the relatively productive waters of the eastern tropical Pacific. A normative model quantitatively accounts for the variability observed in nearly all elements. Zn and Na, however, are not well explained by the three end-member model, and we suggest that an additional accretionary process results in greater variability in the abundances of these elements. Variable contributions from the three accretionary processes result in distinct top-bottom compositional differences at the three sites. Nodule tops from H are enriched in Ni, Cu, and Zn, instead of the more typical enrichments of these elements in nodule bottoms. In addition, elemental correlations typical of most pelagic nodules are reversed at site H. The three accretionary processes result in distinct mineralogies. Hydrogenous precipitation produces δMnO 2. Oxic diagenesis, however, produces Cu-Ni-rich todorokite, and suboxic diagenesis results in an unstable todorokite which transforms to a 7 Å phase ("birnessite") upon dehydration. The presence of Cu and Ni as charge-balancing cations influence the stability of the todorokite structure. In the bottoms of H nodules, which accrete dominantly by suboxic diagenesis, Na + and possibly Mn +2 provide much of the charge balance for the todorokite structure. Limited growth rate data for H nodules suggest suboxic accretion is the fastest of the three processes, with rates at least 200 mm/10 6 yr. Oxic accretion is probably 10 times slower and hydrogenous 100 times slower. Since these rates predict more suboxic component in bulk nodules than is calculated by the normative analysis, we propose that suboxic accretion is a non-steady-state process. Variations in surface water productivity cause pulses of particulate flux to the sea floor which result in transient Mn reduction in the surface sediments and reprecipitation on nodule surfaces.

Influence of sea level rise on iron diagenesis in an east Florida subterranean estuary

USGS Publications Warehouse

Roy, M.; Martin, J.B.; Cherrier, J.; Cable, J.E.; Smith, C.G.

2010-01-01

Subterranean estuary occupies the transition zone between hypoxic fresh groundwater and oxic seawater, and between terrestrial and marine sediment deposits. Consequently, we hypothesize, in a subterranean estuary, biogeochemical reactions of Fe respond to submarine groundwater discharge (SGD) and sea level rise. Porewater and sediment samples were collected across a 30-m wide freshwater discharge zone of the Indian River Lagoon (Florida, USA) subterranean estuary, and at a site 250. m offshore. Porewater Fe concentrations range from 0.5 ??M at the shoreline and 250. m offshore to about 286 ??M at the freshwater-saltwater boundary. Sediment sulfur and porewater sulfide maxima occur in near-surface OC-rich black sediments of marine origin, and dissolved Fe maxima occur in underlying OC-poor orange sediments of terrestrial origin. Freshwater SGD flow rates decrease offshore from around 1 to 0.1. cm/day, while bioirrigation exchange deepens with distance from about 10. cm at the shoreline to about 40. cm at the freshwater-saltwater boundary. DOC concentrations increase from around 75 ??M at the shoreline to as much as 700 ??M at the freshwater-saltwater boundary as a result of labile marine carbon inputs from marine SGD. This labile DOC reduces Fe-oxides, which in conjunction with slow discharge of SGD at the boundary, allows dissolved Fe to accumulate. Upward advection of fresh SGD carries dissolved Fe from the Fe-oxide reduction zone to the sulfate reduction zone, where dissolved Fe precipitates as Fe-sulfides. Saturation models of Fe-sulfides indicate some fractions of these Fe-sulfides get dissolved near the sediment-water interface, where bioirrigation exchanges oxic surface water. The estimated dissolved Fe flux is approximately 0.84 ??M Fe/day per meter of shoreline to lagoon surface waters. Accelerated sea level rise predictions are thus likely to increase the Fe flux to surface waters and local primary productivity, particularly along coastlines where groundwater discharges through sediments. ?? 2010 Elsevier Ltd.

Population structure and abundance of arsenite-oxidizing bacteria along an arsenic pollution gradient in waters of the upper isle River Basin, France.

PubMed

Quéméneur, Marianne; Cébron, Aurélie; Billard, Patrick; Battaglia-Brunet, Fabienne; Garrido, Francis; Leyval, Corinne; Joulian, Catherine

2010-07-01

Denaturing gradient gel electrophoresis (DGGE) and quantitative real-time PCR (qPCR) were successfully developed to monitor functional aoxB genes as markers of aerobic arsenite oxidizers. DGGE profiles showed a shift in the structure of the aoxB-carrying bacterial population, composed of members of the Alpha-, Beta- and Gammaproteobacteria, depending on arsenic (As) and E(h) levels in Upper Isle River Basin waters. The highest aoxB gene densities were found in the most As-polluted oxic surface waters but without any significant correlation with environmental factors. Arsenite oxidizers seem to play a key role in As mobility in As-impacted waters.

A photoautotrophic source for lycopane in marine water columns

NASA Technical Reports Server (NTRS)

Wakeham, Stuart G.; Freeman, Katherine H.; Pease, Tamara K.; Hayes, J. M.

1993-01-01

Suspended particulate matter and recent sediments from diverse oceanic sites have been investigated for their contents of lycopane. Lycopane was present in all samples, including both oxic and anoxic water column and sediments. The highest concentrations in the water column were found in surface waters of the central Pacific gyre (1.5 ng/L) and in the anoxic waters of the Cariaco Trench (1.1 ng/L) and the Black Sea (0.3 ng/L). Vertical concentration profiles suggest that lycopane is probably algal in origin. Moreover, biogeochemical conditions in anoxic zones apparently result in a secondary production of lycopane from an as yet unidentified precursor. Compound-specific carbon isotopic analyses have been carried out on lycopane from water column and sediment samples. Isotopic compositions of lycopane range between -23.6 and -32.9 percent and are consistent with a photoautotrophic origin. We postulate that some lycopane is produced in surface waters of the ocean, while additional lycopane is produced in anoxic zones by anaerobic microbial action on an algal precursor.

The influence of oxic degradation on the sedimentary biomarker record II. Evidence from Arabian Sea sediments

NASA Astrophysics Data System (ADS)

Sinninghe Damsté, Jaap S.; Rijpstra, W. Irene C.; Reichart, Gert-jan

2002-09-01

Biomarker accumulation rates in nine different time slices in three cores on and at the foot of a submarine high in the northern Arabian Sea (the Murray Ridge) were measured to investigate the influence of oxygen exposure time on the preservation of biomarker signals in the sedimentary record. All three sites experienced the same history of surface water productivity and sediment supply but had different bottom-water redox conditions due to their different positions (in, just below, well below) relative to the present location of the intense oxygen minimum zone (OMZ). Past variations in the intensity and position of the OMZ, known from a wide variety of proxies (TOC content, distribution and abundance of planktonic and benthic foraminifera and pteropods, trace metals, and δ 15N), enabled specific biomarker (i.e., n-alkanes, steroids, alkenones, alkyldiols, C 26 fatty acid, loliolide, biphytane diols, and archaeal tetraether lipids) accumulation rates at contrasting oxygen exposure times to be compared. The results indicate that these accumulation rates can vary by more than an order of magnitude for marine biomarkers. In addition, there are significant differences in the degree of oxic degradation of different types of biomarkers: Terrestrial n-alkanes are much more resistant than alkenones and n-alkyl diols, which are more refractory than steroids and biphytane diols. These differences in degree of oxic degradation indicate that biomarker distributions will change on increasing exposure to oxygen. These findings have a significant impact on the application of biomarkers to sedimentary settings in which oxygen exposure time is likely to change significantly.

Inorganic nitrogen transformations in the bed of the Shingobee River, Minnesota: Integrating hydrologic and biological processes using sediment perfusion cores

USGS Publications Warehouse

Sheibley, R.W.; Duff, J.H.; Jackman, A.P.; Triska, F.J.

2003-01-01

Inorganic N transformations were examined in streambed sediments from the Shingobee River using sediment perfusion cores. The experimental design simulated groundwater-stream water mixing within sediment cores, which provided a well-defined one-dimensional representation of in situ hydrologic conditions. Two distinct hydrologic and chemical settings were preserved in the sediment cores: the lowermost sediments, perfused with groundwater, remained anaerobic during the incubations, whereas the uppermost sediments, perfused with oxic water pumped from the overlying water column, simulated stream water penetration into the bed. The maintenance of oxic and anoxic zones formed a biologically active aerobic-anaerobic interface. Ammonium (NH4+) dissolved in groundwater was transported conservatively through the lower core zone but was removed as it mixed with aerated recycle water. Concurrently, a small quantity of nitrate (NO3-) equaling ???25% of the NH4+ loss was produced in the upper sediments. The NH4+ and NO3- profiles in the uppermost sediments resulted from coupled nitrification-denitrification, because assimilation and sorption were negligible. We hypothesize that anaerobic microsites within the aerated upper sediments supported denitrification. Rates of nitrification and denitrification in the perfusion cores ranged 42-209 and 53-160 mg N m-2 day-1, respectively. The use of modified perfusion cores permitted the identification and quantification of N transformations and verified process control by surface water exchange into the shallow hyporheic zone of the Shingobee River.

Evidence for abiotic sulfurization of marine dissolved organic matter in sulfidic environments

NASA Astrophysics Data System (ADS)

Pohlabeln, A. M.; Niggemann, J.; Dittmar, T.

2016-02-01

Sedimentary organic matter abiotically sulfurizes in sulfidic marine environments. Here we hypothesize that sulfurization also affects dissolved organic matter (DOM), and that sulfidic marine environments are sources of dissolved organic sulfur (DOS) to the ocean. To test these hypotheses we studied solid-phase extractable (SPE) DOS in the Black Sea at various water column depths (oxic and anoxic) and in sediment porewaters from the German Wadden Sea. The concentration and molecular composition of SPE-DOS from these sites and from the oxic water columns of the North Sea (Germany) and of the North Pacific were compared. In support of our hypotheses, SPE-DOS concentrations were elevated in sulfidic waters compared to oxic waters. For a detailed molecular characterization of SPE-DOS, selective wet-chemical alteration experiments targeting different sulfur-containing functional groups were applied prior to Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). These experiments included harsh hydrolysis, selective derivatization of thiols, oxidation, and deoxygenation to test for thioesters, sulfonic acid esters, alkylsulfates, thiols, non-aromatic thioethers, and sulfoxides. Additionally, collision-induced fragmentation experiments were applied to test for sulfonic acids. The tests revealed that the sulfonic acid group was the main structural feature in SPE-DOS, independent of the environmental conditions of the sampling site. Only in Wadden Sea anoxic porewater also non-aromatic thioethers were found which are presumably not stable in oxic waters. The findings from our field studies were confirmed in laboratory experiments, where we abiotically sulfurized marine and algal-derived DOM under conditions similar to that in anoxic marine sediments.

Ground water stratification and delivery of nitrate to an incised stream under varying flow conditions.

PubMed

Böhlke, J K; O'Connell, Michael E; Prestegaard, Karen L

2007-01-01

Ground water processes affecting seasonal variations of surface water nitrate concentrations were investigated in an incised first-order stream in an agricultural watershed with a riparian forest in the coastal plain of Maryland. Aquifer characteristics including sediment stratigraphy, geochemistry, and hydraulic properties were examined in combination with chemical and isotopic analyses of ground water, macropore discharge, and stream water. The ground water flow system exhibits vertical stratification of hydraulic properties and redox conditions, with sub-horizontal boundaries that extend beneath the field and adjacent riparian forest. Below the minimum water table position, ground water age gradients indicate low recharge rates (2-5 cm yr(-1)) and long residence times (years to decades), whereas the transient ground water wedge between the maximum and minimum water table positions has a relatively short residence time (months to years), partly because of an upward increase in hydraulic conductivity. Oxygen reduction and denitrification in recharging ground waters are coupled with pyrite oxidation near the minimum water table elevation in a mottled weathering zone in Tertiary marine glauconitic sediments. The incised stream had high nitrate concentrations during high flow conditions when much of the ground water was transmitted rapidly across the riparian zone in a shallow oxic aquifer wedge with abundant outflow macropores, and low nitrate concentrations during low flow conditions when the oxic wedge was smaller and stream discharge was dominated by upwelling from the deeper denitrified parts of the aquifer. Results from this and similar studies illustrate the importance of near-stream geomorphology and subsurface geology as controls of riparian zone function and delivery of nitrate to streams in agricultural watersheds.

Ground water stratification and delivery of nitrate to an incised stream under varying flow conditions

USGS Publications Warehouse

Böhlke, J.K.; O'Connell, M. E.; Prestegaard, K.L.

2007-01-01

Ground water processes affecting seasonal variations of surface water nitrate concentrations were investigated in an incised first-order stream in an agricultural watershed with a riparian forest in the coastal plain of Maryland. Aquifer characteristics including sediment stratigraphy, geochemistry, and hydraulic properties were examined in combination with chemical and isotopic analyses of ground water, macropore discharge, and stream water. The ground water flow system exhibits vertical stratification of hydraulic properties and redox conditions, with sub-horizontal boundaries that extend beneath the field and adjacent riparian forest. Below the minimum water table position, ground water age gradients indicate low recharge rates (2-5 cm yr-1) and long residence times (years to decades), whereas the transient ground water wedge between the maximum and minimum water table positions has a relatively short residence time (months to years), partly because of an upward increase in hydraulic conductivity. Oxygen reduction and denitrification in recharging ground waters are coupled with pyrite oxidation near the minimum water table elevation in a mottled weathering zone in Tertiary marine glauconitic sediments. The incised stream had high nitrate concentrations during high flow conditions when much of the ground water was transmitted rapidly across the riparian zone in a shallow oxic aquifer wedge with abundant outflow macropores, and low nitrate concentrations during low flow conditions when the oxic wedge was smaller and stream discharge was dominated by upwelling from the deeper denitrified parts of the aquifer. Results from this and similar studies illustrate the importance of near-stream geomorphology and subsurface geology as controls of riparian zone function and delivery of nitrate to streams in agricultural watersheds. ?? ASA, CSSA, SSSA.

Solid-Phase Fe Speciation along the Vertical Redox Gradients in Floodplains using XAS and Mössbauer Spectroscopies.

PubMed

Chen, Chunmei; Kukkadapu, Ravi K; Lazareva, Olesya; Sparks, Donald L

2017-07-18

Properties of Fe minerals are poorly understood in natural soils and sediments with variable redox conditions. In this study, we combined 57 Fe Mössbauer and Fe K-edge X-ray absorption spectroscopic (XAS) techniques to assess solid-phase Fe speciation along the vertical redox gradients of floodplains, which exhibited a succession of oxic, anoxic, and suboxic-oxic zones with increasing depth along the vertical profiles. The incised stream channel is bounded on the east by a narrow floodplain and a steep hillslope, and on the west by a broad floodplain. In the eastern floodplain, the anoxic conditions at the intermediate horizon (55-80 cm) coincided with lower Fe(III)-oxides (particularly ferrihydrite), in concurrence with a greater reduction of phyllosilicates(PS)-Fe(III) to PS-Fe(II), relative to the oxic near-surface and sandy gravel layers. In addition, the anoxic conditions in the eastern floodplain coincided with increased crystallinity of goethite, relative to the oxic layers. In the most reduced intermediate sediments at 80-120 cm of the western floodplain, no Fe(III)-oxides were detected, concurrent with the greatest PS-Fe(III) reduction (PS-Fe(II)/Fe(III) ratio ≈ 1.2 (Mössbauer) or 0.8 (XAS)). In both oxic near-surface horizon and oxic-suboxic gravel aquifers beneath the soil horizons, Fe(III)-oxides were mainly present as ferrihydrite with a much less amount of goethite, which preferentially occurred as nanogoethite or Al/Si-substituted goethite. Ferrihydrite with varying crystallinity or impurities such as organic matter, Al or Si, persisted under suboxic-oxic conditions in the floodplain. This study indicates that vertical redox gradients exert a major control on the quantity and speciation of Fe(III) oxides as well as the oxidation state of structural Fe in PS, which could significantly affect nutrient cycling and carbon (de)stabilization.

Removal of H 2S via an iron catalytic cycle and iron sulfide precipitation in the water column of dead end tributaries

NASA Astrophysics Data System (ADS)

Ma, Shufen; Noble, Abigail; Butcher, Derek; Trouwborst, Robert E.; Luther, George W., III

2006-11-01

The oxidation and precipitation of H 2S were investigated in Torquay Canal and Bald Eagle Creek, two tributaries of northern Rehoboth Bay, one of the Delaware Inland Bays. These man-made dead end canals develop seasonal anoxia and have been the site of past fish kills and harmful algal blooms. The canals have multiple holes over 5.5 m deep compared to an average low tide depth of 2 m. In situ determination for dissolved O 2, H 2S and other Fe and S redox species were conducted with a solid-state Au/Hg microelectrode in 2003 and 2004. Laboratory analyses of discrete samples were also performed to measure dissolved and particulate Fe, Mn, and S 8 to follow the seasonal dynamics of O, S, Fe and Mn redox species. Our results indicate that the water in the holes becomes stratified with O 2 decreasing with depth and H 2S increasing with depth. Dissolved Fe was as high as 30 μM whereas dissolved Mn was only 0.2 μM in the water column, indicating that Fe is the dominant metal involved in S redox cycling and precipitation. In surface oxic waters, the dominant form of Fe was particulate Fe(III) (oxy)hydroxides. When seasonal anoxia developed, Fe(III) (oxy)hydroxides were reduced by H 2S to Fe(II) at the oxic-anoxic interface. The Fe(II) reduced from particulate Fe can be re-oxidized to Fe(III) by O 2 above and at the interface to form a catalytic cycle to oxidize H 2S. Elemental S is the predominant oxidation product and was as high as 30 μM level (as S 0) at the interface. When the system was stable, the Fe catalytic cycle prevented H 2S from being released into surface waters during seasonal anoxia. However, when storms came, the water column was overturned and H 2S was released to the surface water. The reaction rates for the Fe catalytic cycle are not fast enough and the concentration of Fe was not high enough to regulate the high concentration of H 2S in surface waters during storm and mixing events.

Determination of physical and dynamic properties of suspended particles in water column with ultrasonic scanning in between the water surface and stable sediment layer.

NASA Astrophysics Data System (ADS)

Acar, Dursun; Alpar, Bedri; Ozeren, Sinan; Cagatay, Namık; Sari, Erol; Vardar, Denizhan; Eris, Kadir

2015-04-01

The behavior of seafloor sediment with its water column should be known against any occurrences of anoxic or oxic conditions. The most important ones of these conditions are possible leakage of natural gas or escape of liquids from sediment. On the basis of combined solid/liquid flow dynamics in sedimentation, such kind of events can change, even in an effective manner, the dynamic movements of molecules and their cumulative mass of particules, i.e. the suspended materials. The deployment of suitable sediment traps or ultrasonic transducers somewhere in the water column are not easy attempts in order to obtain useful information about the state of suspended materials during sedimentation. These are usually bulky instruments; therefore they may behave like an anti-move suppresser on the particles moving in the float direction, in oxic and anoxic manner. These instruments, on the other hand, may cover the effects of diffusive flow or bubble formed gas and fluid escape from the sediment surface into the water column. Ultrasonic scanners, however, are able to make observations in a remote manner, without affecting such artificial events. Our field trials were successfully completed at the historical estuary called Halic of Marmara sea . The physical properties; such as the velocity of particles, their travel directions, their dimensions and the ability to observe anti-compositor crushes of shock waves of the bubbles are only a few of these observations in natural ambience. The most important problem solved about water pressure during 3 atmosphere . The sensor has been tested successfully few times. We used the ''High voltage electric isolator oil filling'' to the inside of the scanner for pressure equalization between outer side and inner body of probe at a depth of (20 meters) beneath the sea surface . The transmitted signals by the planar crystal of the transducer become weaker under the pressure of overlying water column in depths. Our efforts are now focused on the improved performance of transducer at higher than over 3 atm pressure. Keywords: ultrasonic , flow , particle , Sediment , Cumulative mass

Population Structure and Abundance of Arsenite-Oxidizing Bacteria along an Arsenic Pollution Gradient in Waters of the Upper Isle River Basin, France▿ †

PubMed Central

Quéméneur, Marianne; Cébron, Aurélie; Billard, Patrick; Battaglia-Brunet, Fabienne; Garrido, Francis; Leyval, Corinne; Joulian, Catherine

2010-01-01

Denaturing gradient gel electrophoresis (DGGE) and quantitative real-time PCR (qPCR) were successfully developed to monitor functional aoxB genes as markers of aerobic arsenite oxidizers. DGGE profiles showed a shift in the structure of the aoxB-carrying bacterial population, composed of members of the Alpha-, Beta- and Gammaproteobacteria, depending on arsenic (As) and Eh levels in Upper Isle River Basin waters. The highest aoxB gene densities were found in the most As-polluted oxic surface waters but without any significant correlation with environmental factors. Arsenite oxidizers seem to play a key role in As mobility in As-impacted waters. PMID:20453153

Microbial control of mineral–groundwater equilibria:Macroscale to microscale

USGS Publications Warehouse

Bennett, Philip C.; Hiebert, Franz K.; Roger, Jennifer Roberts

2000-01-01

macroscaleprocesses that perturb general groundwater chemistry and therefore mineral–water equilibria; and microscale interactions, where attached organisms locally perturb mineral–water equilibria, potentially releasing limiting trace nutrients from the dissolving mineral.In the contaminated unconfined glacio-fluvial aquifer near Bemidji, Minnesota, USA, carbonate chemistry is influenced primarily at the macroscale. Under oxic conditions, respiration by native aerobic heterotrophs produces excess carbon dioxide that promotes calcite and dolomite dissolution. Aerobic microorganisms do not colonize dolomite surfaces and few occur on calcite. Within the anoxic groundwater, calcite overgrowths form on uncolonized calcite cleavage surfaces, possibly due to the consumption of acidity by dissimilatory iron-reducing bacteria. As molecular oxygen concentration increases downgradient of the oil pool, aerobes again dominate and residual hydrocarbons and ferrous iron are oxidized, resulting in macroscale carbonate-mineral dissolution and iron precipitation.

The Nitrogen Cycle During the Transition to Euxinia

NASA Astrophysics Data System (ADS)

Meyer, K. M.; Kump, L. R.; Ridgwell, A.

2008-12-01

Nitrogen and phosphorous are essential to life, and their biological availability is hypothesized to regulate marine productivity on short and geologic timescales. The nature of primary production during recurrent intervals of Phanerozoic anoxia is of particular interest because of the redox control of nutrient and trace metal availability. Dissolved phosphate likely increased during transitions from oxic to euxinic marine conditions, while nitrogen availability may have decreased due to extensive denitrification as low-oxygen waters spread. Because nitrogen fixation is both metabolically and trace-metal intensive, a key question in the transition to euxinia is whether nitrogen fixation can "keep pace" with denitrification. If denitrification exceeds nitrogen fixation, diminished export production and oxygen demand in an N-limited ocean would pose a negative feedback that may prevent euxinia altogether or initiate the shift back to oxic conditions. Here we use the GENIE-1 Earth system model to address the biogeochemistry of the oxic-euxinic transition characteristic of some Phanerozoic oceanic anoxic events. As previously demonstrated with box models, phosphate accumulation stimulates both nitrogen fixation and denitrification. While there is an initial transient loss of total fixed nitrogen from the ocean, nitrogen inputs eventually exceed losses, and the marine nitrogen reservoir grows with that of phosphate to significantly exceed its modern value. Nitrogen buildup also corresponds with a shift in ecology of the surface ocean and the unexpected initiation of non-Redfieldian stoichiometry in the chemistry of the deep ocean.

Exploring the dynamic links between microbial ecology and redox state of the hyporheic zone: insight from flume experiments

NASA Astrophysics Data System (ADS)

Kaufman, M.; Cardenas, M. B.; Stegen, J.; Graham, E.; Cook, P. L. M.; Kessler, A. J.

2016-12-01

The hyporheic zone (HZ) provides key ecosystem services such as heavy metal sequestration, nutrient uptake and consumption, and habitat for a diverse collection of ecologically and commercially important species. Microbes are responsible for many of the chemical transformations in the HZ. These microbe populations are intimately linked to redox conditions, and recent work has shown that redox conditions in the HZ can be highly dynamic. Here we investigate the dynamic coupling between surface flow conditions, hyporheic redox conditions, and the hyporheic microbiome. Our window into this world is a large experimental flume (5m x 0.7m x 0.3m), prepared and incubated in a way that is relatively common to hyporheic zone research, without a strong attempt to impose a specific microbial community structure. We use computer-controlled flow combined with sand bedforms within the flume to generate a pattern of oxic and anoxic sediment zones, from which we collected sediment and water samples. Dissolved oxygen was mapped with a large planar optode. The samples were analyzed for microbial community composition through 16S rRNA gene sequencing. We compare the population structure between oxic and anoxic zones, showing that the presence of oxygen in the HZ is a strong predictor of microbial composition. Additionally, we compare both the oxic and anoxic community structure from the flume to those of samples taken from natural environments, showing both interesting similarities and differences. In the future, we plan to use time-series sampling to observe the response times of microbial communities subjected to dynamic surface channel flow and redox conditions. This work will yield greater understanding of the role that dynamic rivers play in microbe-provided ecosystem services.

Exploring the dynamic links between microbial ecology and redox state of the hyporheic zone: insight from flume experiments

NASA Astrophysics Data System (ADS)

Kaufman, M.; Cardenas, M. B.; Stegen, J.; Graham, E.; Cook, P. L. M.; Kessler, A. J.

2017-12-01

The hyporheic zone (HZ) provides key ecosystem services such as heavy metal sequestration, nutrient uptake and consumption, and habitat for a diverse collection of ecologically and commercially important species. Microbes are responsible for many of the chemical transformations in the HZ. These microbe populations are intimately linked to redox conditions, and recent work has shown that redox conditions in the HZ can be highly dynamic. Here we investigate the dynamic coupling between surface flow conditions, hyporheic redox conditions, and the hyporheic microbiome. Our window into this world is a large experimental flume (5m x 0.7m x 0.3m), prepared and incubated in a way that is relatively common to hyporheic zone research, without a strong attempt to impose a specific microbial community structure. We use computer-controlled flow combined with sand bedforms within the flume to generate a pattern of oxic and anoxic sediment zones, from which we collected sediment and water samples. Dissolved oxygen was mapped with a large planar optode. The samples were analyzed for microbial community composition through 16S rRNA gene sequencing. We compare the population structure between oxic and anoxic zones, showing that the presence of oxygen in the HZ is a strong predictor of microbial composition. Additionally, we compare both the oxic and anoxic community structure from the flume to those of samples taken from natural environments, showing both interesting similarities and differences. In the future, we plan to use time-series sampling to observe the response times of microbial communities subjected to dynamic surface channel flow and redox conditions. This work will yield greater understanding of the role that dynamic rivers play in microbe-provided ecosystem services.

Sorption and oxic degradation of the explosive CL-20 during transport in subsurface sediments.

PubMed

Szecsody, J E; Girvin, D C; Devary, B J; Campbell, J A

2004-08-01

The abiotic sorption and oxic degradation processes that control the fate of the explosive CL-20, Hexanitrohexaazaisowurtzitane, in the subsurface environment were investigated to determine the potential for vadose and groundwater contamination. Sorption of aqueous CL-20 is relatively small (K(d) = 0.02-3.83 cm3 g(-1) for 7 sediments and 12 minerals), which results in only slight retardation relative to water movement. Thus, CL-20 could move quickly through unsaturated and saturated sediments of comparable composition to groundwater, similar to the subsurface behavior of RDX. CL-20 sorption was mainly to mineral surfaces of the sediments, and the resulting isotherm was nonlinear. CL-20 abiotically degrades in oxic environments at slow rates (i.e., 10s to 100s of hours) with a wide variety of minerals, but at fast rates (i.e., minutes) in the presence of 2:1 phyllosilicate clays (hectorite, montmorillonite, nontronite), micas (biotite, illite), and specific oxides (MnO2 and the ferrous-ferric iron oxide magnetite). High concentrations of surface ferrous iron in a dithionite reduced sediment degraded CL-20 the fastest (half-life < 0.05 h), but 2:1 clays containing no structural or adsorbed ferrous iron (hectorite) could also quickly degrade CL-20 (half-life < 0.2 h). CL-20 degradation rates were slower in natural sediments (half-life 3-800 h) compared to minerals. Sediments with slow degradation rates and small sorption would exhibit the highest potential for deep subsurface migration. Products of CL-20 oxic degradation included three high molecular weight compounds and anions (nitrite and formate). The 2-3.5 moles of nitrite produced suggest CL-20 nitro-groups are degraded, and the amount of formate produced (0.2-1.2 moles) suggests the CL-20 cage structure is broken in some sediments. Identification of further degradation products and CL-20 mineralization rates is needed to fully assess the impact of these CL-20 transformation rates on the risk of CL-20 (and degradation product) subsurface movement.

Vulnerability of bank filtration systems to climate change.

PubMed

Sprenger, C; Lorenzen, G; Hülshoff, I; Grützmacher, G; Ronghang, M; Pekdeger, A

2011-01-15

Bank filtration (BF) is a well established and proven natural water treatment technology, where surface water is infiltrated to an aquifer through river or lake banks. Improvement of water quality is achieved by a series of chemical, biological and physical processes during subsurface passage. This paper aims at identifying climate sensitive factors affecting bank filtration performance and assesses their relevance based on hypothetical 'drought' and 'flood' climate scenarios. The climate sensitive factors influencing water quantity and quality also have influence on substance removal parameters such as redox conditions and travel time. Droughts are found to promote anaerobic conditions during bank filtration passage, while flood events can drastically shorten travel time and cause breakthrough of pathogens, metals, suspended solids, DOC and organic micropollutants. The study revealed that only BF systems comprising an oxic to anoxic redox sequence ensure maximum removal efficiency. The storage capacity of the banks and availability of two source waters renders BF for drinking water supply less vulnerable than surface water or groundwater abstraction alone. Overall, BF is vulnerable to climate change although anthropogenic impacts are at least as important. Copyright © 2010 Elsevier B.V. All rights reserved.

Exploring Microbial Life in Oxic Sediments Underlying Oligotrophic Ocean Gyres

NASA Astrophysics Data System (ADS)

Ziebis, W.; Orcutt, B.; Wankel, S. D.; D'Hondt, S.; Szubin, R.; Kim, J. N.; Zengler, K.

2015-12-01

Oxygen, carbon and nutrient availability are defining parameters for microbial life. In contrast to organic-rich sediments of the continental margins, where high respiration rates lead to a depletion of O2 within a thin layer at the sediment surface, it was discovered that O2 penetrates several tens of meters into organic-poor sediments underlying oligotrophic ocean gyres. In addition, nitrate, another important oxidant, which usually disappears rapidly with depth in anoxic sediments, tends to accumulate above seawater concentrations in the oxic subsurface, reflecting the importance of nitrogen cycling processes, including both nitrification and denitrification. Two IODP drilling expeditions were vital for exploring the nature of the deep subsurface beneath oligotrophic ocean gyres, expedition 329 to the South Pacific Gyre (SPG) and expedition 336 to North Pond, located on the western flank of the Mid-Atlantic ridge beneath the North Atlantic Gyre. Within the ultra-oligotrophic SPG O2 penetrates the entire sediment column from the sediment-water interface to the underlying basement to depths of > 75 m. At North Pond, a topographic depression filled with sediment and surrounded by steep basaltic outcrops, O2 penetrates deeply into the sediment (~ 30 m) until it eventually becomes depleted. O2 also diffuses upward into the sediment from seawater circulating within the young crust underlying the sediment, resulting in a deep oxic layer several meters above the basalt. Despite low organic carbon contents microbial cells persist throughout the entire sediment column within the SPG (> 75 m) and at North Pond, albeit at low abundances. We explored the nature of the subsurface microbial communities by extracting intact cells from large volumes of sediment obtained from drill cores of the two expeditions. By using CARD-FiSH, amplicon (16s rRNA) and metagenome sequencing we shed light on the phylogenetic and functional diversity of the elusive communities residing in the deep oxic sediments of these two different areas. Given the global extent of this oxic subsurface studies of the diversity and metabolic potential of its biome, together with the analyses of porewater geochemical and isotopic composition, are beginning to reveal its role in global biogeochemical cycles.

Effect of Redox Conditions on Bacterial Community Structure in Baltic Sea Sediments with Contrasting Phosphorus Fluxes

PubMed Central

Steenbergh, Anne K.; Bodelier, Paul L. E.; Slomp, Caroline P.; Laanbroek, Hendrikus J.

2014-01-01

Phosphorus release from sediments can exacerbate the effect of eutrophication in coastal marine ecosystems. The flux of phosphorus from marine sediments to the overlying water is highly dependent on the redox conditions at the sediment-water interface. Bacteria are key players in the biological processes that release or retain phosphorus in marine sediments. To gain more insight in the role of bacteria in phosphorus release from sediments, we assessed the effect of redox conditions on the structure of bacterial communities. To do so, we incubated surface sediments from four sampling sites in the Baltic Sea under oxic and anoxic conditions and analyzed the fingerprints of the bacterial community structures in these incubations and the original sediments. This paper describes the effects of redox conditions, sampling station, and sample type (DNA, RNA, or whole-cell sample) on bacterial community structure in sediments. Redox conditions explained only 5% of the variance in community structure, and bacterial communities from contrasting redox conditions showed considerable overlap. We conclude that benthic bacterial communities cannot be classified as being typical for oxic or anoxic conditions based on community structure fingerprints. Our results suggest that the overall structure of the benthic bacterial community has only a limited impact on benthic phosphate fluxes in the Baltic Sea. PMID:24667801

Effect of redox conditions on bacterial community structure in Baltic Sea sediments with contrasting phosphorus fluxes.

PubMed

Steenbergh, Anne K; Bodelier, Paul L E; Slomp, Caroline P; Laanbroek, Hendrikus J

2014-01-01

Phosphorus release from sediments can exacerbate the effect of eutrophication in coastal marine ecosystems. The flux of phosphorus from marine sediments to the overlying water is highly dependent on the redox conditions at the sediment-water interface. Bacteria are key players in the biological processes that release or retain phosphorus in marine sediments. To gain more insight in the role of bacteria in phosphorus release from sediments, we assessed the effect of redox conditions on the structure of bacterial communities. To do so, we incubated surface sediments from four sampling sites in the Baltic Sea under oxic and anoxic conditions and analyzed the fingerprints of the bacterial community structures in these incubations and the original sediments. This paper describes the effects of redox conditions, sampling station, and sample type (DNA, RNA, or whole-cell sample) on bacterial community structure in sediments. Redox conditions explained only 5% of the variance in community structure, and bacterial communities from contrasting redox conditions showed considerable overlap. We conclude that benthic bacterial communities cannot be classified as being typical for oxic or anoxic conditions based on community structure fingerprints. Our results suggest that the overall structure of the benthic bacterial community has only a limited impact on benthic phosphate fluxes in the Baltic Sea.

Hydrothermal sediments are a source of water column Fe and Mn in the Bransfield Strait, Antarctica

NASA Astrophysics Data System (ADS)

Aquilina, Alfred; Homoky, William B.; Hawkes, Jeffrey A.; Lyons, Timothy W.; Mills, Rachel A.

2014-07-01

Short sediment cores were collected from ∼1100 m water depth at the top of Hook Ridge, a submarine volcanic edifice in the Central Basin of the Bransfield Strait, Antarctica, to assess Fe and Mn supply to the water column. Low-temperature hydrothermal fluids advect through these sediments and, in places, subsurface H2S is present at high enough concentrations to support abundant Sclerolinum sp., an infaunal tubeworm that hosts symbiotic thiotrophic bacteria. The water column is fully oxic, and oxygen penetration depths at all sites are 2-5 cmbsf. Pore water Fe and Mn content is high within the subsurface ferruginous zone (max. 565 μmol Fe L-1, >3-7 cmbsf)-14-18 times higher than values measured at a nearby, background site of equivalent water depth. Diffusion and advection of pore waters supply significant Fe and Mn to the surface sediment. Sequential extraction of the sediment demonstrates that there is a significant enrichment in a suite of reactive, authigenic Fe minerals in the upper 0-5 cm of sediment at one site characterised by weathered crusts at the seafloor. At a site with only minor authigenic mineral surface enrichment we infer that leakage of pore water Fe and Mn from the sediment leads to enriched total dissolvable Fe and Mn in bottom waters. An Eh sensor mounted on a towed package mapped a distinct Eh signature above this coring site which is dispersed over several km at the depth of Hook Ridge. We hypothesise that the main mechanism for Fe and Mn efflux from the sediment is breach of the surface oxic layer by the abundant Sclerolinum sp., along with episodic enhancements by physical mixing and resuspension of sediment in this dynamic volcanic environment. We propose that Hook Ridge sediments are an important source of Fe and Mn to the deep waters of the Central Basin in the Bransfield Strait, where concentrations are sustained by the benthic flux, and Fe is stabilised in the water column as either colloidal phases or ligand-bound dissolved species. Entrainment of this water mass into the Drake Passage and thereby the Antarctic Circumpolar Current could provide a significant metal source to this HNLC region of the Southern Ocean if mixing and upwelling occurs before removal of this metal pool to underlying sediments. Sediment-covered volcanic ridges are common within rifted margins and may play a previously overlooked role in the global Fe cycle.

Sulfate-reducing bacteria and their activities in cyanobacterial mats of Solar Lake (Sinai, Egypt)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Teske, A.; Ramsing, N.B.; Habicht, K.

1998-08-01

The sulfate-reducing bacteria within the surface layer of the hypersaline cyanobacterial mat of Solar Lake (Sinai, Egypt) were investigated with combined microbiological, molecular, and biogeochemical approaches. The diurnally oxic surface layer contained between 10{sup 6} and 10{sup 7} cultivable sulfate-reducing bacteria ml{sup {minus}1} day{sup {minus}1}, both in the same range as and sometimes higher than those in anaerobic deeper mat layers. In the oxic surface layer and in the mat layers below, filamentous sulfate-reducing Desulfonema bacteria were found in variable densities of 10{sup 4} and 10{sup 6} cells ml{sup {minus}1}. A Desulfonema-related, diurnally migrating bacterium was detected with PCR andmore » denaturing gradient gel electrophoresis within and below the oxic surface layer. Facultative aerobic respiration, filamentous morphology, motility, diurnal migration, and aggregate formation were the most conspicuous adaptations of Solar Lake sulfate-reducing bacteria to the mat matrix and to diurnal oxygen stress. A comparison of sulfate reduction rates within the mat and previously published photosynthesis rates showed that CO{sub 2} from sulfate reduction in the upper 5 mm accounted for 7 to 8% of the total photosynthetic CO{sub 2} demand of the mat.« less

Metal Oxides in Surface Sediment Control Nickel Bioavailability to Benthic Macroinvertebrates.

PubMed

Mendonca, Raissa M; Daley, Jennifer M; Hudson, Michelle L; Schlekat, Christian E; Burton, G Allen; Costello, David M

2017-11-21

In aquatic ecosystems, the cycling and toxicity of nickel (Ni) are coupled to other elemental cycles that can limit its bioavailability. Current sediment risk assessment approaches consider acid-volatile sulfide (AVS) as the major binding phase for Ni, but have not yet incorporated ligands that are present in oxic sediments. Our study aimed to assess how metal oxides play a role in Ni bioavailability in surficial sediments exposed to effluent from two mine sites. We coupled spatially explicit sediment geochemistry (i.e., separate oxic and suboxic) to the indigenous macroinvertebrate community structure. Effluent-exposed sites contained high concentrations of sediment Ni and AVS, though roughly 80% less AVS was observed in surface sediments. Iron (Fe) oxide mineral concentrations were elevated in surface sediments and bound a substantial proportion of Ni. Redundancy analysis of the invertebrate community showed surface sediment geochemistry significantly explained shifts in community abundances. Relative abundance of the dominant mayfly (Ephemeridae) was reduced in sites with greater bioavailable Ni, but accounting for Fe oxide-bound Ni greatly decreased variation in effect thresholds between the two mine sites. Our results provide field-based evidence that solid-phase ligands in oxic sediment, most notably Fe oxides, may have a critical role in controlling nickel bioavailability.

More than just one Methane Paradox? - Methane Production in Oxic Waters and Aerobic Methane Oxidation under Oxygen-Depleted Conditions

NASA Astrophysics Data System (ADS)

Lehmann, M. F.; Niemann, H.; Bartosiewicz, M.; Blees, J.; Steinle, L.; Su, G.; Zopfi, J.

2016-12-01

The standing paradigm is that methane (CH4) production through methanogenesis occurs exclusively under anoxic conditions and that at least in freshwater environments most of the biogenic CH4 is oxidized by aerobic methanotrophic bacteria (MOB) under oxic conditions. However, subsurface CH4 accumulation in oxic waters, a phenomenon referred to as the "CH4 paradox", has been observed both in the ocean and in lakes, and suggests in-situ CH4 production or a remarkable tolerance of at least some methanogens to O2. Analogously, MOB seem to thrive also under micro-oxic conditions, i.e., they may be responsible for significant CH4 turnover at extremely low O2 concentrations. O2 availability particularly within the sub-micromolar range is likely one of the key factors controlling the balance between CH4 production and consumption in redox-transition zones of aquatic environments, yet threshold O2 concentrations are poorly constrained. Here we provide multiple lines of evidence for apparent "methanogenesis" in well-oxygenated waters and discuss the potential mechanisms that lead to CH4 accumulation in the oxic epilimnia of two south-alpine lakes. On the other end, we present data from a deep meromictic lake, which indicate aerobic CH4 oxidation (MOx) at O2 concentrations below the detection limit of common O2 sensors. A strong MOx potential throughout the anoxic hyplimnion of the studied lake implies that the MOB community is able to survive prolonged periods of O2 starvation and is capable to rapidly resume microaerobic MOx upon introduction of low levels of O2. This conclusion is qualitatively consistent with field data from a coastal shelf environment in the Baltic Sea, where we observed maximum MOx rates during the summer stratification period when O2 concentrations were lowest, implying that in both environments MOx bacteria are adapted to trace levels of O2. Indeed, laboratory experiments at different manipulated O2 concentration levels suggest a nanomolar O2 optimum for MOx in both environments. The very low O2 requirements may reflect the adaption of water column MOB at the organismic level to O2-limited conditions, with several ecological advantages: it allows them to escape grazing pressure and to avoid the detrimental effects of oxidative stress and/or CH4 starvation in more oxygenated waters.

Chemical activation of bituminous coal for hampering oligomerization of organic contaminants.

PubMed

Yan, Liang; Sorial, George A

2011-12-15

Activated carbons prepared by KOH activation of bituminous coal were studied for hampering oligomerization of phenolic compounds on its surface. A total of 24 activated carbons with different microporosity and BET surface area were created. The effect of the different variables of the activation process (KOH/bituminous coal ratio, heating temperature, activation time, and flow rate of nitrogen gas) on critical carbon parameters was analyzed. The impact of activated carbon on oligomerization was examined by conducting isotherm experiments at a neutral pH on Carbon(exp) produced with optimal characteristics and granular activated carbon (GAC) F400 for phenol, 2-methylphenol and 2-ethylphenol. These isotherms were collected under anoxic (absence of molecular oxygen) and oxic (presence of molecular oxygen) conditions. The single solute adsorption of phenol, 2-methylphenol and 2-ethylphenol on Carbon(exp) showed no obvious differences between oxic and anoxic environment, which indicated that the Carbon(exp) sample is very effective in hampering the oligomerization of phenolic compounds under oxic conditions. On the other hand, F400, which have lower micropore percentage and BET surface area, significant increases in the adsorptive capacity had been observed when molecular oxygen was present. Copyright © 2011 Elsevier B.V. All rights reserved.

Total Mercury and Methylmercury Response in Water, Sediment, and Biota to Destratification of the Great Salt Lake, Utah, United States.

PubMed

Valdes, Carla; Black, Frank J; Stringham, Blair; Collins, Jeffrey N; Goodman, James R; Saxton, Heidi J; Mansfield, Christopher R; Schmidt, Joshua N; Yang, Shu; Johnson, William P

2017-05-02

Measurements of chemical and physical parameters made before and after sealing of culverts in the railroad causeway spanning the Great Salt Lake in late 2013 documented dramatic alterations in the system in response to the elimination of flow between the Great Salt Lake's north and south arms. The flow of denser, more-saline water through the culverts from the north arm (Gunnison Bay) to the south arm (Gilbert Bay) previously drove the perennial stratification of the south arm and the existence of oxic shallow brine and anoxic deep brine layers. Closure of the causeway culverts occurred concurrently with a multiyear drought that resulted in a decrease in the lake elevation and a concomitant increase in top-down erosion of the upper surface of the deep brine layer by wind-forced mixing. The combination of these events resulted in the replacement of the formerly stratified water column in the south arm with one that was vertically homogeneous and oxic. Total mercury concentrations in the deep waters of the south arm decreased by approximately 81% and methylmercury concentrations in deep waters decreased by roughly 86% due to destratification. Methylmercury concentrations decreased by 77% in underlying surficial sediment, whereas there was no change observed in total mercury. The dramatic mercury loss from deep waters and methylmercury loss from underlying sediment in response to causeway sealing provides new understanding of the potential role of the deep brine layer in the accumulation and persistence of methylmercury in the Great Salt Lake. Additional mercury measurements in biota appear to contradict the previously implied connection between elevated methylmercury concentrations in the deep brine layer and elevated mercury in avian species reported prior to causeway sealing.

Oxygen distribution and aerobic respiration in the north and south eastern tropical Pacific oxygen minimum zones

NASA Astrophysics Data System (ADS)

Tiano, Laura; Garcia-Robledo, Emilio; Dalsgaard, Tage; Devol, Allan H.; Ward, Bess B.; Ulloa, Osvaldo; Canfield, Donald E.; Peter Revsbech, Niels

2014-12-01

Highly sensitive STOX O2 sensors were used for determination of in situ O2 distribution in the eastern tropical north and south Pacific oxygen minimum zones (ETN/SP OMZs), as well as for laboratory determination of O2 uptake rates of water masses at various depths within these OMZs. Oxygen was generally below the detection limit (few nmol L-1) in the core of both OMZs, suggesting the presence of vast volumes of functionally anoxic waters in the eastern Pacific Ocean. Oxygen was often not detectable in the deep secondary chlorophyll maximum found at some locations, but other secondary maxima contained up to 0.4 μmol L-1. Directly measured respiration rates were high in surface and subsurface oxic layers of the coastal waters, reaching values up to 85 nmol L-1 O2 h-1. Substantially lower values were found at the depths of the upper oxycline, where values varied from 2 to 33 nmol L-1 O2 h-1. Where secondary chlorophyll maxima were found the rates were higher than in the oxic water just above. Incubation times longer than 20 h, in the all-glass containers, resulted in highly increased respiration rates. Addition of amino acids to the water from the upper oxycline did not lead to a significant initial rise in respiration rate within the first 20 h, indicating that the measurement of respiration rates in oligotrophic Ocean water may not be severely affected by low levels of organic contamination during sampling. Our measurements indicate that aerobic metabolism proceeds efficiently at extremely low oxygen concentrations with apparent half-saturation concentrations (Km values) ranging from about 10 to about 200 nmol L-1.

Anaerobic/oxic/anoxic granular sludge process as an effective nutrient removal process utilizing denitrifying polyphosphate-accumulating organisms.

PubMed

Kishida, Naohiro; Kim, Juhyun; Tsuneda, Satoshi; Sudo, Ryuichi

2006-07-01

In a biological nutrient removal (BNR) process, the utilization of denitrifying polyphosphate-accumulating organisms (DNPAOs) has many advantages such as effective use of organic carbon substrates and low sludge production. As a suitable process for the utilization of DNPAOs in BNR, an anaerobic/oxic/anoxic granular sludge (AOAGS) process was proposed in this study. In spite of performing aeration for nitrifying bacteria, the AOAGS process can create anaerobic/anoxic conditions suitable for the cultivation of DNPAOs because anoxic zones exist inside the granular sludge in the oxic phase. Thus, DNPAOs can coexist with nitrifying bacteria in a single reactor. In addition, the usability of DNPAOs in the reactor can be improved by adding the anoxic phase after the oxic phase. These characteristics enable the AOAGS process to attain effective removal of both nitrogen and phosphorus. When acetate-based synthetic wastewater (COD: 600 mg/L, NH4-N: 60 mg/L, PO(4)-P: 10 mg/L) was supplied to a laboratory-scale sequencing batch reactor under the operation of anaerobic/oxic/anoxic cycles, granular sludge with a diameter of 500 microm was successfully formed within 1 month. Although the removal of both nitrogen and phosphorus was almost complete at the end of the oxic phase, a short anoxic period subsequent to the oxic phase was necessary for further removal of nitrogen and phosphorus. As a result, effluent concentrations of NH(4)-N, NO(x)-N and PO(4)-P were always lower than 1 mg/L. It was found that penetration depth of oxygen inside the granular sludge was approximately 100 microm by microsensor measurements. In addition, from the microbiological analysis by fluorescence in situ hybridization, existence depth of polyphosphate-accumulating organisms was further than the maximum oxygen penetration depth. The water quality data, oxygen profiles and microbial community structure demonstrated that DNPAOs inside the granular sludge may be responsible for denitrification in the oxic phase, which enables effective nutrient removal in the AOAGS process.

Opposite effects of dissolved oxygen on the removal of As(III) and As(V) by carbonate structural Fe(II).

PubMed

Tian, Zeyuan; Feng, Yong; Guan, Yiyi; Shao, Binbin; Zhang, Yalei; Wu, Deli

2017-12-05

Freshly prepared carbonate structural Fe(II) (CSF) was used to immobilize As(III) and As(V) in wastewater under oxic and anoxic conditions. Dissolved oxygen was found to exert opposite effects on these two arsenic species. The sorption density of As(III) was higher under oxic conditions, whereas that of As(V) was higher under anoxic conditions. X-ray diffraction and infrared spectroscopic analyses indicated that crystalline parasymplesite (Fe(II) 3 (AsO 4 ) 2 ·8H 2 O) was formed when As(V) was removed under anoxic conditions, while an amorphous Fe-As-containing precipitate was formed when As(III) was removed under oxic conditions. The distribution of arsenic and iron between the solution and sediments suggested that the oxidation of structural Fe(II) promoted coprecipitation process and inhibited surface complexation. X-ray photoelectron spectroscopic analyses revealed that more As(III) was oxidized under oxic condition, which contributed to a higher sorption capacity for As(III). The formation of parasymplesite through surface complexation/precipitation was proposed to be more effective for the removal of As(V) by CSF, while As(III) was more efficiently removed through coprecipitation. Together, the results suggest that CSF may be an effective material for sequestering both As(III) and As(V). In addition, attention should be paid to the dissolved oxygen content when remediating different arsenic species.

Relations of hydrogeologic factors, groundwater reduction-oxidation conditions, and temporal and spatial distributions of nitrate, Central-Eastside San Joaquin Valley, California, USA

USGS Publications Warehouse

Landon, Matthew K.; Green, Christopher T.; Belitz, Kenneth; Singleton, Michael J.; Esser, Bradley K.

2011-01-01

In a 2,700-km2 area in the eastern San Joaquin Valley, California (USA), data from multiple sources were used to determine interrelations among hydrogeologic factors, reduction-oxidation (redox) conditions, and temporal and spatial distributions of nitrate (NO3), a widely detected groundwater contaminant. Groundwater is predominantly modern, or mixtures of modern water, with detectable NO3 and oxic redox conditions, but some zones have anoxic or mixed redox conditions. Anoxic conditions were associated with long residence times that occurred near the valley trough and in areas of historical groundwater discharge with shallow depth to water. Anoxic conditions also were associated with interactions of shallow, modern groundwater with soils. NO3 concentrations were significantly lower in anoxic than oxic or mixed redox groundwater, primarily because residence times of anoxic waters exceed the duration of increased pumping and fertilizer use associated with modern agriculture. Effects of redox reactions on NO3 concentrations were relatively minor. Dissolved N2 gas data indicated that denitrification has eliminated >5 mg/L NO3–N in about 10% of 39 wells. Increasing NO3 concentrations over time were slightly less prevalent in anoxic than oxic or mixed redox groundwater. Spatial and temporal trends of NO3 are primarily controlled by water and NO3 fluxes of modern land use.

Relations of hydrogeologic factors, groundwater reduction-oxidation conditions, and temporal and spatial distributions of nitrate, Central-Eastside San Joaquin Valley, California, USA

USGS Publications Warehouse

Landon, M.K.; Green, C.T.; Belitz, K.; Singleton, M.J.; Esser, B.K.

2011-01-01

In a 2,700-km2 area in the eastern San Joaquin Valley, California (USA), data from multiple sources were used to determine interrelations among hydrogeologic factors, reduction-oxidation (redox) conditions, and temporal and spatial distributions of nitrate (NO3), a widely detected groundwater contaminant. Groundwater is predominantly modern, or mixtures of modern water, with detectable NO3 and oxic redox conditions, but some zones have anoxic or mixed redox conditions. Anoxic conditions were associated with long residence times that occurred near the valley trough and in areas of historical groundwater discharge with shallow depth to water. Anoxic conditions also were associated with interactions of shallow, modern groundwater with soils. NO3 concentrations were significantly lower in anoxic than oxic or mixed redox groundwater, primarily because residence times of anoxic waters exceed the duration of increased pumping and fertilizer use associated with modern agriculture. Effects of redox reactions on NO3 concentrations were relatively minor. Dissolved N2 gas data indicated that denitrification has eliminated gt;5 mg/L NO3-N in about 10% of 39 wells. Increasing NO3 concentrations over time were slightly less prevalent in anoxic than oxic or mixed redox groundwater. Spatial and temporal trends of NO3 are primarily controlled by water and NO3 fluxes of modern land use. ?? 2011 Springer-Verlag (outside the USA).

Geochemical evolution of acidic ground water at a reclaimed surface coal mine in western Pennsylvania

USGS Publications Warehouse

Cravotta,, Charles A.

1991-01-01

Concentrations of dissolved sulfate and acidity in ground water increase downflow in mine spoil and underlying bedrock at a reclaimed surface coal mine in the bituminous field of western Pennsylvania. Elevated dissolved sulfate and negligible oxygen in ground water from bedrock about 100 feet below the water table suggest that pyritic sulfur is oxidized below the water table, in a system closed to oxygen. Geochemical models for the oxidation of pyrite (FeS2) and production of sulfate (SO42-) and acid (H+) are presented to explain the potential role of oxygen (O2) and ferric iron (Fe3+) as oxidants. Oxidation of pyrite by O2 and Fe3+ can occur under oxic conditions above the water table, whereas oxidation by Fe3+ also can occur under anoxic conditions below the water table. The hydrated ferric-sulfate minerals roemerite [Fe2+Fe43+(SO4)4·14H2O], copiapite [Fe2+Fe43+(SO4)6(OH)2·20H20], and coquimbite [Fe2(SO4)3·9H2O] were identified with FeS2 in coal samples, and form on the oxidizing surface of pyrite in an oxic system above the water table. These soluble ferric-sulfate 11 salts11 can dissolve with recharge waters or a rising water table releasing Fe3+, SO42-. and H+, which can be transported along closed-system ground-water flow paths to pyrite reaction sites where O2 may be absent. The Fe3+ transported to these sites can oxidize pyritic sulfur. The computer programs WATEQ4F and NEWBAL were used to compute chemical speciation and mass transfer, respectively, considering mineral dissolution and precipitation reactions plus mixing of waters from different upflow zones. Alternative mass-balance models indicate that (a) extremely large quantities of O2, over 100 times its aqueous solubility, can generate the observed concentrations of dissolved SO42- from FeS2, or (b) under anoxic conditions, Fe3+ from dissolved ferric-sulfate minerals can oxidize FeS2 along closed-system ground-water flow paths. In a system open to O2, such as in the unsaturated zone, the aqueous solubility of O2 is not limiting, and oxidation of pyrite by O2 and Fe3+ accounts for most SO42- and Fe2+ observed in acidic ground water. However, in a system closed to O2, such as in the saturated zone, O2 solubility is limiting; hence, ferric oxidation of pyrite is a reasonable explanation for the observed elevated SO42- with increasing depth below the water table.

Influence of anoxia on the induction of mutations by phenylalanine radicals during gamma-irradiation of plasmid DNA in aqueous solution.

PubMed

Kuipers, Gitta K; Slotman, Ben J; Reitsma-Wijker, Carola A; van Andel, Rob J; Poldervaart, Hester A; Lafleur, M Vincent M

2004-12-21

When DNA is irradiated in aqueous solution, most of the damage is inflicted by water-derived radicals. This is called the indirect effect of ionizing radiation. However in whole cells not only the primary formed water radicals play a role, because some cellular compounds form secondary radicals which can also damage DNA. It is known that the amino acid phenylalanine is able to react with water radicals, resulting in the production of secondary phenylalanine radicals which can damage and inactivate DNA. In a previous study the influence of the presence of phenylalanine during gamma-irradiation of DNA in aqueous solution under oxic conditions was studied. Under anoxic irradiation conditions different amounts and types of reactive water-derived radicals are formed compared to oxic conditions and also different phenylalanine radicals are formed. Therefore, this study examines the influence of the presence of phenylalanine under anoxic conditions on the gamma-radiation-induced mutation spectrum. The results indicate that phenylalanine radicals are damaging to DNA, but less effective compared to primary water radicals. On the mutational level, in the presence of phenylalanine radicals under anoxic conditions, the amount of mutations on G:C base pairs was significantly decreased as compared to oxic conditions. Furthermore, the results of this study indicate that nucleotide excision repair is involved in repair of both inactivating and mutagenic damage induced by phenylalanine radicals under anoxic conditions.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, Chunmei; Kukkadapu, Ravi K.; Lazareva, Olesya

Properties of Fe minerals are poorly understood in natural soils and sediments with variable redox conditions. In this study, we combined 57Fe Mössbauer and Fe K-edge X-ray absorption spectroscopic techniques to assess solid-phase Fe speciation along the vertical redox gradients of floodplain profiles, which exhibited a succession of oxic, anoxic and suboxic-oxic zones with increasing depth along the vertical profiles. The anoxic conditions at the intermediate horizon (55-80 cm) of the eastern floodplain resulted in extensive depletion of Fe(III)-oxides including both ferrihydrite and goethite, concurrent with a corresponding reduction of phyllosilicates(PS)-Fe(III) to PS-Fe(II). In addition, the anoxic conditions increased themore » crystallinity of Fe(III)-oxides in this reduced zone, relative to the oxic zones. In the most reduced intermediate sediments at 80-120cm of the western floodplain, the anoxic conditions drove the complete reductive dissolution of Fe(III) oxides, as well as the greatest reduction (48-55%) in PS-Fe(III). In both oxic near-surface horizon and oxic-suboxic gravel aquifers beneath the soil horizons, Fe(III)-oxides were mainly present as ferrihydrite with a less amount of goethite, which preferentially occurred as nanogoethite or Al/Si-substituted goethite. Ferrihydrite with varying crystallinity or impurities such as organic matter, Al or Si, persisted under suboxic-oxic conditions in the floodplain. This study indicates that vertical redox gradients exert a major control on the quantity and speciation of Fe(III) oxides as well as the oxidation state of structural Fe in PS, which could significantly affect nutrient cycling and carbon (de)stabilization.« less

Pseudomonas aeruginosa facilitates Campylobacter jejuni growth in biofilms under oxic flow conditions.

PubMed

Culotti, Alessandro; Packman, Aaron I

2015-12-01

We investigated the growth of Campylobacter jejuni in biofilms with Pseudomonas aeruginosa under oxic flow conditions. We observed the growth of C. jejuni in mono-culture, deposited on pre-established P. aeruginosa biofilms, and co-inoculated with P. aeruginosa. In mono-culture, C. jejuni was unable to form biofilms. However, deposited C. jejuni continuously grew on pre-established P. aeruginosa biofilms for a period of 3 days. The growth of scattered C. jejuni clusters was strictly limited to the P. aeruginosa biofilm surface, and no intergrowth was observed. Co-culturing of C. jejuni and P. aeruginosa also enabled the growth of both organisms in biofilms, with C. jejuni clusters developing on the surface of the P. aeruginosa biofilm. Dissolved oxygen (DO) measurements in the medium showed that P. aeruginosa biofilms depleted the effluent DO from 9.0 to 0.5 mg L(-1) 24 hours after inoculation. The localized microaerophilic environment generated by P. aeruginosa promoted the persistence and growth of C. jejuni. Our findings show that P. aeruginosa not only prolongs the survival of C. jejuni under oxic conditions, but also enables the growth of C. jejuni on the surface of P. aeruginosa biofilms. © FEMS 2015. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

Nitrate in groundwater of the United States, 1991-2003

USGS Publications Warehouse

Burow, Karen R.; Nolan, Bernard T.; Rupert, Michael G.; Dubrovsky, Neil M.

2010-01-01

An assessment of nitrate concentrations in groundwater in the United States indicates that concentrations are highest in shallow, oxic groundwater beneath areas with high N inputs. During 1991-2003, 5101 wells were sampled in 51 study areas throughout the U.S. as part of the U.S. Geological Survey National Water-Quality Assessment (NAWQA) program. The well networks reflect the existing used resource represented by domestic wells in major aquifers (major aquifer studies), and recently recharged groundwater beneath dominant land-surface activities (land-use studies). Nitrate concentrations were highest in shallow groundwater beneath agricultural land use in areas with well-drained soils and oxic geochemical conditions. Nitrate concentrations were lowest in deep groundwater where groundwater is reduced, or where groundwater is older and hence concentrations reflect historically low N application rates. Classification and regression tree analysis was used to identify the relative importance of N inputs, biogeochemical processes, and physical aquifer properties in explaining nitrate concentrations in groundwater. Factors ranked by reduction in sum of squares indicate that dissolved iron concentrations explained most of the variation in groundwater nitrate concentration, followed by manganese, calcium, farm N fertilizer inputs, percent well-drained soils, and dissolved oxygen. Overall, nitrate concentrations in groundwater are most significantly affected by redox conditions, followed by nonpoint-source N inputs. Other water-quality indicators and physical variables had a secondary influence on nitrate concentrations.

Methane production as key to the greenhouse gas budget of thawing permafrost on climate relevant time scales

NASA Astrophysics Data System (ADS)

Knoblauch, C.; Beer, C.; Liebner, S.; Schütt, A.; Grigoriev, M.; Pfeiffer, E. M.

2017-12-01

Permafrost in circum-arctic soils stores as much carbon as the global atmosphere. Permafrost thaw liberates organic matter, which is mineralized by microorganisms to carbon dioxide (CO2) and methane (CH4). The release of these greenhouse gases (GHGs) may form a positive feedback to atmospheric CO2 and CH4 concentrations and accelerate climate change. The microbial formation of CH4, which has 28 to 45 times the global warming potential (GWP) of CO2 (100 years time scale), requires anoxic conditions. Current studies indicate that permafrost thaw at the bottom of well drained (oxic) soils cause a higher formation of GHGs than in water saturated (anoxic) soils since more CO2 is formed under oxic conditions and only small amounts of CH4 are formed from permafrost organic matter under anoxic conditions. Here we show through 7-year laboratory incubations and molecular analysis of Siberian permafrost that low CH4 production from permafrost organic matter is due to the lack of active methanogens. Equal amounts of permafrost organic carbon are mineralized to CO2 and CH4 under anoxic conditions after an active methanogenic community has established. Field measurements demonstrate that recently thawed permafrost organic matter is a substantial source for CH4 if primed with surface soil. An organic carbon decomposition model, calibrated with the collected long-term incubation data, predicts a higher loss of permafrost carbon under oxic conditions but a twice as high production of CO2-C equivalents under anoxic conditions when considering a GWP of 28 for CH4. Combining these model results with observed permafrost carbon profile data, up-scaled carbon stocks and thaw depth projections suggests a global formation of 3 - 10 Pg CO2-C from thawing permafrost in oxic soils compared to 0.2 - 0.6 Pg CO2-C and 0.2- 0.8 Pg CH4-C in anoxic soils until 2100. However, based on CO2-C equivalents the GHG production in anoxic soils (2 - 9 Pg CO2-C equivalents) is similar to those in oxic soils. These findings challenge the view of a stronger permafrost carbon-climate feedback from drained soils and emphasize the importance of CH4 production in thawing permafrost.

Methane cycling in alpine wetlands - an interplay of microbial communities and vascular plants

NASA Astrophysics Data System (ADS)

Henneberger, Ruth; Cheema, Simrita; Zeyer, Josef

2014-05-01

Wetland environments play an important role for the global climate, as they represent a major terrestrial carbon store. These environments are potential sinks for atmospheric carbon due to reduced decomposition rates of plant material in the waterlogged, anoxic subsurface. In contrast, wetlands are also a major source of the highly potent greenhouse gas methane (CH4), which is produced in the anoxic zones through methanogenic archaea (methanogens) degrading organic matter. The CH4 emitted into the pore water diffuses upwards towards the surface, and is partially oxidized in the oxic zones by aerobic methanotrophic bacteria (methanotrophs) before reaching the atmosphere. Nonetheless, global emissions of atmospheric CH4 from natural wetlands are estimated to range from 100 to 230 Tg a-1. Natural wetlands can be found around the globe, and are also common in temperate-cold climates in the Northern hemisphere. Methane release from these environments is influenced by many factors (e.g., vegetation, water table, temperature, pH) and shows high seasonal and spatial variability. To comprehend these variations and further predict potential responses to climate change, the biotic and abiotic processes involved in CH4 turnover need to be understood in detail. Many research projects focus on (sub-)arctic wetland areas, while studies on CH4 emissions from alpine wetlands are scarce, despite similar processes occurring in these different regions. Recently, we conducted a survey of 14 wetlands (i.e., fens vegetated with vascular plants) located in the Swiss Alps, showing CH4 emissions between 74 ± 43 and 711 ± 212 mg CH4 m-2 d-1 (Franchini et al., in press). A detailed study of one fen also revealed that CH4 emission was highest immediately after snowmelt, followed by a decrease in CH4 emission throughout the snow-free period (Liebner et al., 2012). Even though the CH4 cycle is largely driven by microbially mediated processes, vascular plants also play a crucial role in CH4 emissions from wetlands, as CH4 generated in the deeper layers can bypass the oxic, methanotrophic zones through the plant aerenchyma. In addition, O2 transported to the root system facilitates CH4 oxidation in the rhizosphere. To further comprehend these complex processes, the present study focused on selected fens dominated by different plants (i.e., Carex spp. or Eriophorum spp.). We combined field-measurements of overall CH4 emissions, CH4 and O2 pore water concentrations and plant-mediated bypass with molecular biological analyses of methanogenic and methanotrophic subpopulations at different soil depths. Methane emissions and pore water concentrations varied with location and dominating plant species. Nevertheless, in all fens we observed the presence of active methanogens and methanotrophs throughout the depth profile, independently of O2 and CH4 concentrations, with active methanogens being highly abundant even in the oxic layers indicating the presence of microniches. The often described spatial separation of methanogenic activity in anoxic zones and methanotrophic activity in oxic zones and oxic-anoxic interfaces could not be observed. The composition of the methanogenic and methanotrophic subpopulations that are active at different depths is currently analyzed in detail, providing new insights into the complex processes involved in CH4 turnover in alpine regions.

The Dynamics of Sediment Oxygenation in Marsh Rhizospheres

NASA Astrophysics Data System (ADS)

Koop-Jakobsen, K.

2014-12-01

Many marsh grasses are capable of internal oxygen transport from aboveground sources to belowground roots and rhizomes, where oxygen may leak across the rhizodermis and oxygenate the surrounding sediment. In the field, the extent of sediment oxygenation in marshes was assessed in the rhizosphere of the marsh grass; Spartina anglica, inserting 70 optical fiber oxygen sensors into the rhizosphere. Two locations with S. anglica growing in different sediment types were investigated. No oxygen was detected in the rhizospheres indicating that belowground sediment oxygenation in S. anglica has a limited effect on the bulk anoxic sediment and is restricted to sediment in the immediate vicinity of the roots. In the laboratory, the presence of 1.5mm wide and 16mm long oxic root zones was demonstrated around root tips of S. anglica growing in permeable sandy sediment using planar optodes recording 2D-images of the oxygen distribution. Oxic root zones in S. anglica growing in tidal flat deposits were significantly smaller. The size of oxic roots zones was highly dynamic and affected by tidal inundations as well as light availability. Atmospheric air was the primary oxygen source for belowground sediment oxygenation, whereas photosynthetic oxygen production only played a minor role for the size of the oxic root zones during air-exposure of the aboveground biomass. During tidal inundations (1.5 h) completely submerging the aboveground biomass cutting off access to atmospheric oxygen, the size of oxic root zones were reduced significantly in the light and oxic root zones were completely eliminated in darkness. Sediment oxygenation in the rhizospheres of marsh grasses is of significant importance for marshes ability to retain inorganic nitrogen before it reaches the coastal waters. The presence of oxic roots zones promotes coupled nitrification-denitrification at depth in the sediment, which can account for more than 80% of the total denitrification in marshes.

The Association of Arsenic With Redox Conditions, Depth, and Ground-Water Age in the Glacial Aquifer System of the Northern United States

USGS Publications Warehouse

Thomas, Mary Ann

2007-01-01

More than 800 wells in the glacial aquifer system of the Northern United States were sampled for arsenic as part of U.S. Geological Survey National Water-Quality Assessment (NAWQA) studies during 1991-2003. Elevated arsenic concentrations (greater than or equal to 10 micrograms per liter) were detected in 9 percent of samples. Elevated arsenic concentrations were associated with strongly reducing conditions. Of the samples classified as iron reducing or sulfate reducing, arsenic concentrations were elevated in 19 percent. Of the methanogenic samples, arsenic concentrations were elevated in 45 percent. In contrast, concentrations of arsenic were elevated in only 1 percent of oxic samples. Arsenic concentrations were also related to ground-water age. Elevated arsenic concentrations were detected in 34 percent of old waters (recharged before 1953) as compared to 4 percent of young waters (recharged since 1953). For samples classified as both old and methanogenic, elevated arsenic concentrations were detected in 62 percent of samples, as compared to 1 percent for samples classified as young and oxic. Arsenic concentrations were also correlated with well depth and concentrations of several chemical constituents, including (1) constituents linked to redox processes and (2) anions or oxyanions that sorb to iron oxides. Observations from the glacial aquifer system are consistent with the idea that the predominant source of arsenic is iron oxides and the predominant mechanism for releasing arsenic to the ground water is reductive desorption or reductive dissolution. Arsenic is also released from iron oxides under oxic conditions, but on a more limited basis and at lower concentrations. Logistic regression was used to investigate the relative significance of redox, ground-water age, depth, and other water-quality constituents as indicators of elevated arsenic concentrations in the glacial aquifer system. The single variable that explained the greatest amount of variation in the data was redox. Multivariate models that included a redox variable overestimated the percentage of samples with elevated arsenic concentrations because, even though elevated arsenic concentrations were associated with strongly reducing samples, not all strongly reducing samples had elevated arsenic concentrations. Arsenic concentrations and redox conditions differed among four broad areas of the glacial aquifer system. For the East, Central, and West-Central north areas, there was a trend of increasing arsenic concentrations that corresponded to an increase in reducing conditions. For the West-Central south area, arsenic concentrations in oxic samples were higher than for the other areas, possibly because of high concentrations of orthophosphate, which is linked to desorption of arsenic from iron oxides under oxic conditions. The observed differences in arsenic concentrations among broad areas of the glacial aquifer system were generally consistent with a conceptual model developed by Smedley and Kinniburg, who studied or reviewed studies of widespread arsenic contamination in Bangladesh, India, China, Vietnam, Hungary, Argentina, northern Chile and the Southwestern United States.

Subsurface microbial diversity in deep-granitic-fracture water in Colorado

USGS Publications Warehouse

Sahl, J.W.; Schmidt, R.; Swanner, E.D.; Mandernack, K.W.; Templeton, A.S.; Kieft, Thomas L.; Smith, R.L.; Sanford, W.E.; Callaghan, R.L.; Mitton, J.B.; Spear, J.R.

2008-01-01

A microbial community analysis using 16S rRNA gene sequencing was performed on borehole water and a granite rock core from Henderson Mine, a >1,000-meter-deep molybdenum mine near Empire, CO. Chemical analysis of borehole water at two separate depths (1,044 m and 1,004 m below the mine entrance) suggests that a sharp chemical gradient exists, likely from the mixing of two distinct subsurface fluids, one metal rich and one relatively dilute; this has created unique niches for microorganisms. The microbial community analyzed from filtered, oxic borehole water indicated an abundance of sequences from iron-oxidizing bacteria (Gallionella spp.) and was compared to the community from the same borehole after 2 weeks of being plugged with an expandable packer. Statistical analyses with UniFrac revealed a significant shift in community structure following the addition of the packer. Phospholipid fatty acid (PLFA) analysis suggested that Nitrosomonadales dominated the oxic borehole, while PLFAs indicative of anaerobic bacteria were most abundant in the samples from the plugged borehole. Microbial sequences were represented primarily by Firmicutes, Proteobacteria, and a lineage of sequences which did not group with any identified bacterial division; phylogenetic analyses confirmed the presence of a novel candidate division. This "Henderson candidate division" dominated the clone libraries from the dilute anoxic fluids. Sequences obtained from the granitic rock core (1,740 m below the surface) were represented by the divisions Proteobacteria (primarily the family Ralstoniaceae) and Firmicutes. Sequences grouping within Ralstoniaceae were also found in the clone libraries from metal-rich fluids yet were absent in more dilute fluids. Lineage-specific comparisons, combined with phylogenetic statistical analyses, show that geochemical variance has an important effect on microbial community structure in deep, subsurface systems. Copyright ?? 2008, American Society for Microbiology. All Rights Reserved.

Subsurface Microbial Diversity in Deep-Granitic-Fracture Water in Colorado▿

PubMed Central

Sahl, Jason W.; Schmidt, Raleigh; Swanner, Elizabeth D.; Mandernack, Kevin W.; Templeton, Alexis S.; Kieft, Thomas L.; Smith, Richard L.; Sanford, William E.; Callaghan, Robert L.; Mitton, Jeffry B.; Spear, John R.

2008-01-01

A microbial community analysis using 16S rRNA gene sequencing was performed on borehole water and a granite rock core from Henderson Mine, a >1,000-meter-deep molybdenum mine near Empire, CO. Chemical analysis of borehole water at two separate depths (1,044 m and 1,004 m below the mine entrance) suggests that a sharp chemical gradient exists, likely from the mixing of two distinct subsurface fluids, one metal rich and one relatively dilute; this has created unique niches for microorganisms. The microbial community analyzed from filtered, oxic borehole water indicated an abundance of sequences from iron-oxidizing bacteria (Gallionella spp.) and was compared to the community from the same borehole after 2 weeks of being plugged with an expandable packer. Statistical analyses with UniFrac revealed a significant shift in community structure following the addition of the packer. Phospholipid fatty acid (PLFA) analysis suggested that Nitrosomonadales dominated the oxic borehole, while PLFAs indicative of anaerobic bacteria were most abundant in the samples from the plugged borehole. Microbial sequences were represented primarily by Firmicutes, Proteobacteria, and a lineage of sequences which did not group with any identified bacterial division; phylogenetic analyses confirmed the presence of a novel candidate division. This “Henderson candidate division” dominated the clone libraries from the dilute anoxic fluids. Sequences obtained from the granitic rock core (1,740 m below the surface) were represented by the divisions Proteobacteria (primarily the family Ralstoniaceae) and Firmicutes. Sequences grouping within Ralstoniaceae were also found in the clone libraries from metal-rich fluids yet were absent in more dilute fluids. Lineage-specific comparisons, combined with phylogenetic statistical analyses, show that geochemical variance has an important effect on microbial community structure in deep, subsurface systems. PMID:17981950

Sulfur speciation and sulfide oxidation in the water column of the Black Sea

NASA Astrophysics Data System (ADS)

Luther, George W., III; Church, Thomas M.; Powell, David

We have applied sulfur speciation techniques to understand the chemistry and cycling of sulfur in Black Sea waters. The only reduced dissolved inorganic sulfur species detected (above the low minimum detection limits of the voltammetric methods employed) in the water column was hydrogen sulfide. The maximum concentration of sulfide (423 μM) is similar to previous reports. Using a cathodic stripping square wave voltammetry (CSSWV) method for nanomolar levels of sulfide, we determined the precise boundary between the "free" hydrogen sulfide (sulfidic) zone and the upper (oxic/suboxic) water column at the two stations studied. This boundary has apparently moved up by about 50 m in the past 20 years. Our results help demonstrate three chemically distinct zones of water in the central basin of the Black Sea: (1) the oxic [0-65 m], (2) the anoxic/nonsulfidic [65-100 m] and (3) the sulfidic [>100 m]. Sulfide bound to metals ("complexed" sulfide) is observed in both the oxic and anoxic/nonsulfidic zones of the water column. This supports previous studies on metal sulfide forms. From the electrochemical data, it is possible to estimate the strength of the complexation of sulfide to metals (log K = 10 to 11). Thiosulfate and sulfite were below our minimum detectable limit (MDL) of 50 nM using CSSWV. Elemental sulfur (MDL 5 nM) was detected below the onset of the hydrogen sulfide zone (90-100 m) with a maximum of 30-60 nM near 120 m. The sulfur speciation results for the Black Sea are lower by one order of magnitude or more than other marine systems such as the Cariaco Trench and salt marshes. New HPLC techniques were applied to detect thiols at submicromolar levels. The presence of thiols (2-mercaptoethylamine, 2-mercaptoethanol, N-acetylcysteine and glutathione) is correlated with the remineralization of organic matter at the oxic and anoxic/nonsulfidic interface. Water samples collected from the upper 50 m of the sulfidic zone showed significant sulfide oxidation on storage onboard ship even though they were filtered (0.2 μm) and handled to exclude oxygen contamination. Chemical additives such as formaldehyde, glutaraldehyde, hydroxylamine and ascorbic acid prevented or retarded the sulfide loss. Thiosulfate and azide did not inhibit sulfide loss. These studies suggest an anaerobic chemical oxidation of sulfide rather than a biological oxidation on stored and filtered samples.

Seasonal Variation in Abundance and Diversity of Bacterial Methanotrophs in Five Temperate Lakes

PubMed Central

Samad, Md Sainur; Bertilsson, Stefan

2017-01-01

Lakes are significant sources of methane (CH4) to the atmosphere. Within these systems, methanotrophs consume CH4 and act as a potential biofilter mitigating the emission of this potent greenhouse gas. However, it is still not well understood how spatial and temporal variation in environmental parameters influence the abundance, diversity, and community structure of methanotrophs in lakes. To address this gap in knowledge, we collected water samples from three depths (surface, middle, and bottom) representing oxic to suboxic or anoxic zones of five different Swedish lakes in winter (ice-covered) and summer. Methanotroph abundance was determined by quantitative real time polymerase chain reaction and a comparison to environmental variables showed that temperature, season as well as depth, phosphate concentration, dissolved oxygen, and CH4 explained the observed variation in methanotroph abundance. Due to minimal differences in methane concentrations (0.19 and 0.29 μM for summer and winter, respectively), only a weak and even negative correlation was observed between CH4 and methanotrophs, which was possibly due to usage of CH4. Methanotrophs were present at concentrations ranging from 105 to 106 copies/l throughout the oxic (surface) and suboxic/anoxic (bottom) water mass of the lakes, but always contributed less than 1.3% to the total microbial community. Relative methanotroph abundance was significantly higher in winter than in summer and consistently increased with depth in the lakes. Phylogenetic analysis of pmoA genes in two clone libraries from two of the ice-covered lakes (Ekoln and Ramsen) separated the methanotrophs into five distinct clusters of Methylobacter sp. (Type I). Terminal restriction fragment length polymorphism analysis of the pmoA gene further revealed significant differences in methanotrophic communities between lakes as well as between winter and summer while there were no significant differences between water layers. The study provides new insights into diversity, abundance, community composition and spatial as well as temporal distribution of freshwater methanotrophs in low-methane dimictic lakes. PMID:28217121

COMPETITIVE ADSORPTION OF VOCS AND BOM-OXIC AND ANOXIC ENVIRONMENTS

EPA Science Inventory

The effect of the presence of molecular oxygen on the adsorption of volatile organic compounds (VOCs) in distilled Milli-Q water and in water supplemented with background organic matter (BOM) is evaluated. Experiments are conducted under conditions where molecular oxygen is prese...

Lignin decomposition and microbial community in paddy soils: effects of alternating redox conditions

NASA Astrophysics Data System (ADS)

Cerli, Chiara; Liu, Qin; Hanke, Alexander; Kaiser, Klaus; Kalbitz, Karsten

2013-04-01

Paddy soils are characterised by interchanging cycles of anaerobic and aerobic conditions. Such fluctuations cause continuous changes in soil solution chemistry as well as in the composition and physiological responses of the microbial community. Temporary deficiency in oxygen creates conditions favourable to facultative or obligates anaerobic bacteria, while aerobic communities can thrive in the period of water absence. These alterations can strongly affect soil processes, in particular organic matter (OM) accumulation and mineralization. In submerged soils, lignin generally constitutes a major portion of the total OM because of hampered degradation under anoxic conditions. The alternating redox cycles resulting from paddy soil management might promote both degradation and preservation of lignin, affecting the overall composition and reactivity of total and dissolved OM. We sampled soils subjected to cycles of anoxic (rice growing period) and oxic (harvest and growth of other crops) conditions since 700 and 2000 years. We incubated suspended Ap material, sampled from the two paddy plus two corresponding non-paddy control soils under oxic and anoxic condition, for 3 months, interrupted by a short period of three weeks (from day 21 to day 43) with reversed redox conditions. At each sampling time (day 2, 21, 42, 63, 84), we determined lignin-derived phenols (by CuO oxidation) as well as phospholipids fatty acids contents and composition. We aimed to highlight changes in lignin decomposition as related to the potential rapid changes in microbial community composition. Since the studied paddy soils had a long history of wet rice cultivation, the microbial community should be well adapted to interchanging oxic and anoxic cycles, therefore fully expressing its activity at both conditions. In non-paddy soil changes in redox conditions caused modification of quantity and composition of the microbial community. On the contrary, in well-established paddy soils the microbial community appeared to be affected by alternating redox conditions more in quantity that in quality. Bacteria represented the largest portion of the living microorganisms, responding promptly to changes in soil redox status. However we did not detect any sign of lignin biodegradation. Relative short (3 weeks) changes in redox conditions had no effect on lignin decomposition or oxidation state. Also, lignin was not altered during oxic incubation. Since fungi represented only small portion of the microbial biomass in the studied soils, they were obviously not capable to cause much degradation, even under favourable conditions. On the contrary, changes in redox conditions strongly affected lignin extractability, regardless of the initial content and direction of change in both paddy and non-paddy soils. This was likely a result of (partial) dissolution and/or pH-induced changes of the surface properties of Fe and Mn hydrous oxides causing the release of mineral-associated lignin-derived phenols. Thus, we speculate that oxidised lignin fragments produced during the (oxic) dry period do not remain in the soils but percolate with water drainage during the flooding period.

Abundance and δ13C values of fatty acids in lacustrine surface sediments: Relationships with in-lake methane concentrations

NASA Astrophysics Data System (ADS)

Stötter, Tabea; Bastviken, David; Bodelier, Paul L. E.; van Hardenbroek, Maarten; Rinta, Päivi; Schilder, Jos; Schubert, Carsten J.; Heiri, Oliver

2018-07-01

Proxy-indicators in lake sediments provide the only approach by which the dynamics of in-lake methane cycling can be examined on multi-decadal to centennial time scales. This information is necessary to constrain how lacustrine methane production, oxidation and emissions are expected to respond to global change drivers. Several of the available proxies for reconstructing methane cycle changes of lakes rely on interpreting past changes in the abundance or relevance of methane oxidizing bacteria (MOB), either directly (e.g. via analysis of bacterial lipids) or indirectly (e.g. via reconstructions of the past relevance of MOB in invertebrate diet). However, only limited information is available about the extent to which, at the ecosystem scale, variations in abundance and availability of MOB reflect past changes in in-lake methane concentrations. We present a study examining the abundances of fatty acids (FAs), particularly of 13C-depleted FAs known to be produced by MOB, relative to methane concentrations in 29 small European lakes. 39 surface sediment samples were obtained from these lakes and FA abundances were compared with methane concentrations measured at the lake surface, 10 cm above the sediments and 10 cm within the sediments. Three of the FAs in the surface sediment samples, C16:1ω7c, C16:1ω5c/t, and C18:1ω7c were characterized by lower δ13C values than the remaining FAs. We show that abundances of these FAs, relative to other short-chain FAs produced in lake ecosystems, are related with sedimentary MOB concentrations assessed by quantitative polymerase chain reaction (qPCR). We observed positive relationships between methane concentrations and relative abundances of C16:1ω7c, C16:1ω5c/t, and C18:1ω7c and the sum of these FAs. For the full dataset these relationships were relatively weak (Spearman's rank correlation (rs) of 0.34-0.43) and not significant if corrected for multiple testing. However, noticeably stronger and statistically significant relationships were observed when sediments from near-shore and deep-water oxic environments (rs = 0.57 to 0.62) and those from anoxic deep-water environment (rs = 0.55 to 0.65) were examined separately. Our results confirm that robust relationships exist between in-lake CH4 concentrations and 13C-depleted groups of FAs in the examined sediments, agreeing with earlier suggestions that the availability of MOB-derived, 13C-depleted organic matter for aquatic invertebrates increases with increasing methane concentrations. However, we also show that these relationships are complex, with different relationships observed for oxic and anoxic sediments and highest values measured in sediments deposited in oxic environments overlain with relatively methane-rich water. Furthermore, although all three 13C-depleted FA groups identified in our survey are known to be produced by MOB, they also receive contributions by other organism groups, and this will have influenced their distribution in our dataset.

Distribution and Rate of Methane Oxidation in Sediments of the Florida Everglades †

PubMed Central

King, Gary M.; Roslev, Peter; Skovgaard, Henrik

1990-01-01

Rates of methane emission from intact cores were measured during anoxic dark and oxic light and dark incubations. Rates of methane oxidation were calculated on the basis of oxic incubations by using the anoxic emissions as an estimate of the maximum potential flux. This technique indicated that methane oxidation consumed up to 91% of the maximum potential flux in peat sediments but that oxidation was negligible in marl sediments. Oxygen microprofiles determined for intact cores were comparable to profiles measured in situ. Thus, the laboratory incubations appeared to provide a reasonable approximation of in situ activities. This was further supported by the agreement between measured methane fluxes and fluxes predicted on the basis of methane profiles determined by in situ sampling of pore water. Methane emissions from peat sediments, oxygen concentrations and penetration depths, and methane concentration profiles were all sensitive to light-dark shifts as determined by a combination of field and laboratory analyses. Methane emissions were lower and oxygen concentrations and penetration depths were higher under illuminated than under dark conditions; the profiles of methane concentration changed in correspondence to the changes in oxygen profiles, but the estimated flux of methane into the oxic zone changed negligibly. Sediment-free, root-associated methane oxidation showed a pattern similar to that for methane oxidation in the core analyses: no oxidation was detected for roots growing in marl sediment, even for roots of Cladium jamaicense, which had the highest activity for samples from peat sediments. The magnitude of the root-associated oxidation rates indicated that belowground plant surfaces may not markedly increase the total capacity for methane consumption. However, the data collectively support the notion that the distribution and activity of methane oxidation have a major impact on the magnitude of atmospheric fluxes from the Everglades. PMID:16348299

A highly redox-heterogeneous ocean in South China during the early Cambrian (˜529-514 Ma): Implications for biota-environment co-evolution

NASA Astrophysics Data System (ADS)

Jin, Chengsheng; Li, Chao; Algeo, Thomas J.; Planavsky, Noah J.; Cui, Hao; Yang, Xinglian; Zhao, Yuanlong; Zhang, Xingliang; Xie, Shucheng

2016-05-01

The ;Cambrian Explosion; is known for rapid increases in the morphological disparity and taxonomic diversity of metazoans. It has been widely proposed that this biological event was a consequence of oxygenation of the global ocean, but this hypothesis is still under debate. Here, we present high-resolution Fe-S-C-Al-trace element geochemical records from the Jinsha (outer shelf) and Weng'an (outer shelf) sections of the early Cambrian Yangtze Platform, integrating these results with previously published data from six correlative sections representing a range of water depths (Xiaotan, Shatan, Dingtai, Yangjiaping, Songtao, and Longbizui). The integrated iron chemistry and redox-sensitive trace element data suggest that euxinic mid-depth waters dynamically coexisted with oxic surface waters and ferruginous deep waters during the earliest Cambrian, but that stepwise expansion of oxic waters commenced during Cambrian Stage 3 (∼ 521- 514 Ma). Combined with data from lower Cambrian sections elsewhere, including Oman, Iran and Canada, we infer that the global ocean exhibited a high degree of redox heterogeneity during the early Cambrian, consistent with low atmospheric oxygen levels (∼ 10- 40% of present atmospheric level, or PAL). A large spatial gradient in pyrite sulfur isotopic compositions (δ34Spy), which vary from a mean of - 12.0 ‰ in nearshore areas to + 22.5 ‰ in distal deepwater sections in lower Cambrian marine units of South China imply low concentrations and spatial heterogeneity of seawater sulfate, which is consistent with a limited oceanic sulfate reservoir globally. By comparing our reconstructed redox chemistry with fossil records from the lower Cambrian of South China, we infer that a stepwise oxygenation of shelf and slope environments occurred concurrently with a gradual increase in ecosystem complexity. However, deep waters remained anoxic and ferruginous even as macrozooplankton and suspension-feeding mesozooplankton appeared during Cambrian Stage 3. These findings suggest that the ;Cambrian Explosion; in South China may have been primarily a consequence of locally improved oxygenation of the ocean-surface layer rather than of the full global ocean. Our observations are inconsistent with predicted changes in ocean chemistry driven by early Cambrian animals, suggesting that the influence of early Cambrian animals on contemporaneous ocean chemistry, as proposed in previous studies, may be overly exaggerated.

The Impact of the Major Baltic Inflow of December 2014 on the Mercury Species Distribution in the Baltic Sea.

PubMed

Kuss, Joachim; Cordes, Florian; Mohrholz, Volker; Nausch, Günther; Naumann, Michael; Krüger, Siegfried; Schulz-Bull, Detlef E

2017-10-17

The Baltic Sea is a marginal sea characterized by stagnation periods of several years. Oxygen consumption in its deep waters leads to the buildup of sulfide from sulfate reduction. Some of the microorganisms responsible for these processes also transform reactive ionic mercury to neurotoxic methylmercury. Episodic inflows of oxygenated saline water from the North Sea temporally re-establish oxic life in deep waters of the Baltic Sea. Thus, this sea is an especially important region to better understand mercury species distributions in connection with variable redox conditions. Mercury species were measured on three Baltic Sea campaigns, during the preinflow, ongoing inflow, and subsiding inflow of water, respectively, to the central basin. The inflowing water caused the removal of total mercury by 600 nmol m -2 and of methylmercury by 214 nmol m -2 in the Gotland Deep, probably via attachment of the mercury compounds to sinking particles. It appears likely that the consequences of the oxygenation of Baltic Sea deep waters, which are the coprecipitation of mercury species and the resettlement of the oxic deep waters, could lead to the enhanced transfer of accumulated mercury and methylmercury to the planktonic food chain and finally to fish.

Evaluation Of Selected Sorption Materials For Capping Mercury-Contaminated Fresh Water Sediments

EPA Science Inventory

Fate and transport of mercury (Hg) and methylmercury (MeHg) within the aquatic environment involves many complex and interconnected pathways. MeHg is formed mainly at the sediment-water interface, just below which there is a transition from oxic to anoxic conditions. The format...

MEASURING METAL SULFIDE COMPLEXES IN OXIC RIVER WATERS WITH SQUARE WAVE VOLTAMMETRY. (R825395)

EPA Science Inventory

A sulfide identification protocol was developed to quantify specific metal
sulfides that could exist in river water. Using a series of acid additions,
nitrogen purges, and voltammetric analyses, metal sulfides were identified and
semiquantified in three specific gr...

Assessing the role of bed sediments in the persistence of red mud pollution in a shallow lake (Kinghorn Loch, UK).

PubMed

Olszewska, Justyna P; Heal, Kate V; Winfield, Ian J; Eades, Lorna J; Spears, Bryan M

2017-10-15

Red mud is a by-product of alumina production. Little is known about the long-term fate of red mud constituents in fresh waters or of the processes regulating recovery of fresh waters following pollution control. In 1983, red mud leachate was diverted away from Kinghorn Loch, UK, after many years of polluting this shallow and monomictic lake. We hypothesised that the redox-sensitive constituents of red mud leachate, phosphorus (P), arsenic (As) and vanadium (V), would persist in the Kinghorn Loch for many years following pollution control as a result of cycling between the lake bed sediment and the overlying water column. To test this hypothesis, we conducted a 12-month field campaign in Kinghorn Loch between May 2012 and April 2013 to quantify the seasonal cycling of P, As, and V in relation to environmental conditions (e.g., dissolved oxygen (DO) concentration, pH, redox chemistry and temperature) in the lake surface and bottom waters. To confirm the mechanisms for P, As and V release, a sediment core incubation experiment was conducted using lake sediment sampled in July 2012, in which DO concentrations were manipulated to create either oxic or anoxic conditions similar to the bed conditions found in the lake. The effects on P, As, and V concentrations and species in the water column were measured daily over an eight-day incubation period. Phosphate (PO 4 -P) and dissolved As concentrations were significantly higher in the bottom waters (75.9 ± 30.2 μg L -1 and 23.5 ± 1.83 μg L -1 , respectively) than in the surface waters (12.9 ± 1.50 μg L -1 and 14.1 ± 2.20 μg L -1 , respectively) in Kinghorn Loch. Sediment release of As and P under anoxic conditions was confirmed by the incubation experiment and by the significant negative correlations between DO and P and As concentrations in the bottom waters of the lake. In contrast, the highest dissolved V concentrations occurred in the bottom waters of Kinghorn Loch under oxic conditions (15.0 ± 3.35 μg L -1 ), with the release from the bed sediment apparently being controlled by a combination of competitive ion concentrations, pH and redox conditions. Copyright © 2017 The Authors. Published by Elsevier Ltd.. All rights reserved.

Effects of molecular weight of natural organic matter on cadmium mobility in soil environments and its carbon isotope characteristics.

PubMed

Mahara, Y; Kubota, T; Wakayama, R; Nakano-Ohta, T; Nakamura, T

2007-11-15

We investigated the role of natural organic matter in cadmium mobility in soil environments. We collected the dissolved organic matter from two different types of natural waters: pond surface water, which is oxic, and deep anoxic groundwater. The collected organic matter was fractionated into four groups with molecular weights (unit: Da (Daltons)) of <1 x 10(3), 1-10 x 10(3), 10-100 x 10(3), and >100 x 10(3). The organic matter source was land plants, based on the carbon isotope ratios (delta(13)C/(12)C). The organic matter in surface water originated from presently growing land plants, based on (14)C dating, but the organic matter in deep groundwater originated from land plants that grew approximately 4000 years ago. However, some carbon was supplied by the high-molecular-weight fraction of humic substances in soil or sediments. Cadmium interacted in a system of siliceous sand, fractionated organic matter, and water. The lowest molecular weight fraction of organic matter (<1 x 10(3)) bound more cadmium than did the higher molecular weight fractions. Organic matter in deep groundwater was more strongly bound to cadmium than was organic matter in surface water. The binding behaviours of organic matter with cadmium depended on concentration, age, molecular weight, and degradation conditions of the organic matter in natural waters. Consequently, the dissolved, low-molecular-weight fraction in organic matter strongly influences cadmium migration and mobility in the environment.

Understanding the Dynamics of the Oxic-Anoxic Interface in the Black Sea

NASA Astrophysics Data System (ADS)

Stanev, Emil V.; Poulain, Pierre-Marie; Grayek, Sebastian; Johnson, Kenneth S.; Claustre, Hervé; Murray, James W.

2018-01-01

The Black Sea, the largest semienclosed anoxic basin on Earth, can be considered as an excellent natural laboratory for oxic and anoxic biogeochemical processes. The suboxic zone, a thin interface between oxic and anoxic waters, still remains poorly understood because it has been undersampled. This has led to alternative concepts regarding the underlying processes that create it. Existing hypotheses suggest that the interface originates either by isopycnal intrusions that introduce oxygen or the dynamics of manganese redox cycling that are associated with the sinking of particles or chemosynthetic bacteria. Here we reexamine these concepts using high-resolution oxygen, sulfide, nitrate, and particle concentration profiles obtained with sensors deployed on profiling floats. Our results show an extremely stable structure in density space over the entire basin with the exception of areas near the Bosporus plume and in the southern areas dominated by coastal anticyclones. The absence of large-scale horizontal intrusive signatures in the open-sea supports a hypothesis prioritizing the role of biogeochemical processes.

Effects of Hypoxia on the Phylogenetic Composition and Species Distribution of Protists in a Subtropical Harbor.

PubMed

Rocke, Emma; Jing, Hongmei; Xia, Xiaomin; Liu, Hongbin

2016-07-01

Tolo Harbor, a subtropical semi-enclosed coastal water body, is surrounded by an expanding urban community, which contributes to large concentrations of nutrient runoff, leading to algal blooms and localized hypoxic episodes. Present knowledge of protist distributions in subtropical waters during hypoxic conditions is very limited. In this study, therefore, we combined parallel 454 pyrosequencing technology and denaturing gradient gel electrophoresis (DGGE) fingerprint analyses to reveal the protist community shifts before, during, and after a 2-week hypoxic episode during the summer of 2011. Hierarchical clustering for DGGE demonstrated similar grouping of hypoxic samples separately from oxic samples. Dissolved oxygen (DO) concentration and dissolved inorganic nitrogen:phosphate (DIN:PO4) concentrations significantly affected OTU distribution in 454 sequenced samples, and a shift toward a ciliate and marine alveolate clade II (MALV II) species composition occurred as waters shifted from oxic to hypoxic. These results suggest that protist community shifts toward heterotrophic and parasitic tendencies as well as decreased diversity and richness in response to hypoxic outbreaks.

A 26 million year gap in the central Arctic record at the greenhouse-icehouse transition: Looking for clues

USGS Publications Warehouse

Sangiorgi, F.; Brumsack, H.-J.; Willard, D.A.; Schouten, S.; Stickley, C.E.; O'Regan, M.; Reichart, G.-J.; Sinninghe, Damste J.S.; Brinkhuis, H.

2008-01-01

The Cenozoic record of the Lomonosov Ridge (central Arctic Ocean) recovered during Integrated Ocean Drilling Program (IODP) Expedition 302 revealed an unexpected 26 Ma hiatus, separating middle Eocene (???44.4 Ma) from lower Miocene sediments (???18.2 Ma). To elucidate the nature of this unconformity, we performed a multiproxy palynological (dinoflagellate cysts, pollen, and spores), micropaleontological (siliceous microfossils), inorganic, and organic (Tetra Ether Index of lipids with 86 carbon atoms (TEX86) and Branched and Isoprenoid Tetraether (BIT)) geochemical analysis of the sediments from ???5 m below to ???7 m above the hiatus. Four main paleoenvironmental. phases (A-D) are recognized in the sediments encompassing the unconformity, two below (A-B) and two above (C-D): (A) Below the hiatus, proxies show relatively warm temperatures, with Sea Surface Temperatures (TEX86-derived SSTs) of about 8??C and high fresh to brackish water influence. (B) Approaching the hiatus, proxies indicate a cooling trend (TEX86-derived SSTs of ???5??C), increased freshwater influence, and progressive shoaling of the Lomonosov Ridge drilling site, located close to or at sea level. (C) The interval directly above the unconformity contains sparse reworked Cretaceous to Oligocene dinoflagellate cysts. Sediments were deposited in a relatively shallow, restricted marine environment. Proxies show the simultaneous influence of both fresh and marine waters, with alternating oxic and anoxic conditions. Pollen indicates a relatively cold climate. Intriguingly, TEX86-derived SSTs are unexpectedly high, ???15-19??C. Such warm surface waters may be partially explained by the ingression of warmer North Atlantic waters after the opening of the Fram Strait during the early Miocene. (D) Sediments of the uppermost interval indicate a phase of extreme oxic conditions, and a well-ventilated environment, which occurred after the complete opening of the Fram Strait. Importantly, and in contrast with classical postrifting thermal subsidence models for passive margins, our data suggest that sediment erosion and/or nondeposition that generated the hiatus was likely due to a progressive shoaling of the Lomonosov Ridge. A shallow water setting both before and after the hiatus suggests that the Lomonosov Ridge remained at or near sea level for the duration of the gap in the sedimentary record. Interacting sea level changes and/ or tectonic activity (possibly uplift) must be invoked as possible causes for such a long hiatus. Copyright 2008 by the American Geophysical Union.

A NON-STEADY-STATE DIAGENETIC MODEL FOR CHANGES IN SEDIMENT BIOGEOCHEMISTRY IN RESPONSE TO SEASONALLY HYPOXIC/ANOXIC CONDITIONS BENEATH THE MISSISSIPPI RIVER PLUME

EPA Science Inventory

Although the bottom waters of many freshwater and marine environments are either permanently oxic or anoxic, there is a growing appreciation that in many bodies of water near-bottom conditions seasonally oscillate between these extreme. Although observational databases for these ...

Mixing of shallow and deep groundwater as indicated by the chemistry and age of karstic springs

NASA Astrophysics Data System (ADS)

Toth, David J.; Katz, Brian G.

2006-06-01

Large karstic springs in east-central Florida, USA were studied using multi-tracer and geochemical modeling techniques to better understand groundwater flow paths and mixing of shallow and deep groundwater. Spring water types included Ca-HCO3 (six), Na-Cl (four), and mixed (one). The evolution of water chemistry for Ca-HCO3 spring waters was modeled by reactions of rainwater with soil organic matter, calcite, and dolomite under oxic conditions. The Na-Cl and mixed-type springs were modeled by reactions of either rainwater or Upper Floridan aquifer water with soil organic matter, calcite, and dolomite under oxic conditions and mixed with varying proportions of saline Lower Floridan aquifer water, which represented 4-53% of the total spring discharge. Multiple-tracer data—chlorofluorocarbon CFC-113, tritium (3H), helium-3 (3Hetrit), sulfur hexafluoride (SF6)—for four Ca-HCO3 spring waters were consistent with binary mixing curves representing water recharged during 1980 or 1990 mixing with an older (recharged before 1940) tracer-free component. Young-water mixing fractions ranged from 0.3 to 0.7. Tracer concentration data for two Na-Cl spring waters appear to be consistent with binary mixtures of 1990 water with older water recharged in 1965 or 1975. Nitrate-N concentrations are inversely related to apparent ages of spring waters, which indicated that elevated nitrate-N concentrations were likely contributed from recent recharge.

MTBE, TBA, and TAME attenuation in diverse hyporheic zones.

PubMed

Landmeyer, James E; Bradley, Paul M; Trego, Donald A; Hale, Kevin G; Haas, Joseph E

2010-01-01

Groundwater contamination by fuel-related compounds such as the fuel oxygenates methyl tert-butyl ether (MTBE), tert-butyl alcohol (TBA), and tert-amyl methyl ether (TAME) presents a significant issue to managers and consumers of groundwater and surface water that receives groundwater discharge. Four sites were investigated on Long Island, New York, characterized by groundwater contaminated with gasoline and fuel oxygenates that ultimately discharge to fresh, brackish, or saline surface water. For each site, contaminated groundwater discharge zones were delineated using pore water geochemistry data from 15 feet (4.5 m) beneath the bottom of the surface water body in the hyporheic zone and seepage-meter tests were conducted to measure discharge rates. These data when combined indicate that MTBE, TBA, and TAME concentrations in groundwater discharge in a 5-foot (1.5-m) thick section of the hyporheic zone were attenuated between 34% and 95%, in contrast to immeasurable attenuation in the shallow aquifer during contaminant transport between 0.1 and 1.5 miles (0.1 to 2.4 km). The attenuation observed in the hyporheic zone occurred primarily by physical processes such as mixing of groundwater and surface water. Biodegradation also occurred as confirmed in laboratory microcosms by the mineralization of U- (14)C-MTBE and U-(14)C-TBA to (14)CO(2) and the novel biodegradation of U- (14)C-TAME to (14)CO(2) under oxic and anoxic conditions. The implication of fuel oxygenate attenuation observed in diverse hyporheic zones suggests an assessment of the hyporheic zone attenuation potential (HZAP) merits inclusion as part of site assessment strategies associated with monitored or engineered attenuation.

Relationship between peatland hydrology and biogeochemistry

NASA Astrophysics Data System (ADS)

Roulet, N. T.

2012-04-01

The 'boreal forest' landscape is composed of upland forests, peatlands, some of which are treed, lakes, streams, and in North America, beaver ponds. Each of these landscapes present quite different biogeochemical environments due to differences in both abiotic and biotic processes and conditions. A significant amount of the carbon (C) in the boreal landscape is stored in peatlands, in part, due to the effect of the water storage on C cycling. The near saturated conditions affect the plants that can grow in peatlands and over the shorter term moisture variability controls the rate of C input to the peat. In the peat water limits the supply of electron donors and this has a profound effect on the C biogeochemistry. Near peat surface the moisture storage can be quite dynamic and mostly oxic conditions prevail, but redox conditions change significantly within a few tenth of a meter below the surface where water residence times increase orders of magnitude. This limits the supply of electron donors and other substrates that control the rate of C mineralization. Understanding the links among the moisture dynamics, the chemical thermodynamics of temporally variable saturated environments, and the quality of C is critical to determining the sensitivity of the C stored in peatlands to environmental change.

Identification and on-line monitoring of reduced sulphur species (RSS) by voltammetry in oxic waters.

PubMed

Superville, Pierre-Jean; Pižeta, Ivanka; Omanović, Dario; Billon, Gabriel

2013-08-15

Based on automatic on-line measurements on the Deûle River that showed daily variation of a peak around -0.56V (vs Ag|AgCl 3M), identification of Reduced Sulphur Species (RSS) in oxic waters was performed applying cathodic stripping voltammetry (CSV) with the hanging mercury drop electrode (HMDE). Pseudopolarographic studies accompanied with increasing concentrations of copper revealed the presence of elemental sulphur S(0), thioacetamide (TA) and reduced glutathione (GSH) as the main sulphur compounds in the Deûle River. In order to resolve these three species, a simple procedure was developed and integrated in an automatic on-line monitoring system. During one week monitoring with hourly measurements, GSH and S(0) exhibited daily cycles whereas no consequential pattern was observed for TA. Copyright © 2013 Elsevier B.V. All rights reserved.

Soluble Manganese(III) in the Marine Environment

NASA Astrophysics Data System (ADS)

Luther, G. W., III; Oldham, V.; Madison, A.; Tebo, B.; Jones, M.; Jensen, L.; Owings, S.; Mucci, A.; Sundby, B.

2014-12-01

Recent field studies have confirmed the presence of soluble manganese(III), which along with Mn(II) passes through a 0.2 μm filter, in suboxic marine waters. Here we applied a spectrophotometric method using a soluble porphyrin as a competitive ligand to calculate the concentrations and kinetics of Mn(II) and Mn(III) recovery. Data will be presented from the suboxic porewaters of the Saint Lawrence estuary, the suboxic and anoxic waters of the Chesapeake Bay and the oxygenated surface waters of a coastal waterway bordered by wetlands and salt marshes in Delaware. Soluble Mn(III) accounts for up to 100% of the dissolved Mn pool with concentrations ranging from the detection limit of 50 nM to 80 μM at the oxic/anoxic interface of the non-sulfidic porewaters from the hemipelagic sediments of the St. Lawrence Estuary. Data indicate weak-ligand complexation of Mn(III) formed from Mn(II) oxidation as well as reduction of MnO2. Complexation of Mn(III) in the anoxic waters of Chesapeake Bay appears stronger as the porphyrin could not outcompete the natural ligands binding Mn(III). Mn(III) complexes were reduced in the presence of hydroxylamine or hydrogen sulfide and detected as Mn(II). Soluble Mn(III) comprised up to 52 % of total dissolved Mn. Profiles over the course of a five day cruise showed that high Mn(III) concentrations (7.3 μM) were observed at low H2S (4.9 μM) whereas low Mn(III) (1.1 μM) was detected at high H2S (40 μM). The presence of Mn(III) in sulfidic waters indicated that it is kinetically stabilized in situ by strong ligands so reduction to Mn(II) was incomplete. One electron reductive dissolution of solid MnO2 particles formed at the oxic-anoxic interface appear to be the source of Mn(III). Lastly, soluble Mn(III) was detected in the oxygenated surface waters of a coastal waterway (salinity ranging from freshwater to 31) bordered by wetlands and salt marshes in Delaware. Soluble Mn(III) made up 0-49 % of the total dissolved Mn (maximum of 1.92 μM) with the highest concentrations and percentages coming from waters adjacent to salt marsh areas. The porphyrin competitive ligand could not outcompete the natural ligands, which appear to be humic material; thus, a reductant was again needed to convert the Mn(III) complexes to Mn(II) for measurement.

Similar potential ATP-P production and enzymatic activities in the microplankton community off Concepción (Chile) under oxic and suboxic conditions

NASA Astrophysics Data System (ADS)

González, Rodrigo R.; Gutiérrez, Marcelo H.; Quiñones, Renato A.

2007-11-01

The effects of the oxygen minimum zone on the metabolism of the heterotrophic microplankton community (0.22-100 μm) in the Humboldt Current System, as well as the factors controlling its biomass production, remain unknown. Here we compare the effect of four sources of dissolved organic carbon (glucose, oxaloacetate, glycine, leucine) on microbial biomass production (such as ATP-P) and the potential enzymatic activities involved in catabolic pathways under oxic and suboxic conditions. Our results show significant differences ( p < 0.05) in the ATP-P production when induced by the different substrates that are used as dissolved organic carbon herein. The induction of ATP-P production is enhanced from glucose < oxaloacetate < glycine < leucine. Nevertheless, for individual substrates, no significant differences were found between incubation under oxic and suboxic conditions except in the case of leucine. For this amino acid, the induction of ATP-P synthesis was higher under suboxic than oxic conditions. The data sets of all the substrates used showed greater potential ATP-P production under suboxic than oxic conditions. The results of the potential enzymatic activities suggest that malate dehydrogenase has the highest signal of NADH oxidization activity in the microbial assemblage. Furthermore, for all experiments, the malate dehydrogenase activity data set had a significant relationship with ATP-P production. These findings suggest that the microbial community inhabiting the oxygen minimum zone has the same or greater potential growth than the community inhabiting more oxygenated strata of the water column and that malate dehydrogenase is the activity that best represents the metabolic potential of the community.

Ground Water Redox Zonation near La Pine, Oregon: Relation to River Position within the Aquifer-Riparian Zone Continuum

USGS Publications Warehouse

Hinkle, Stephen R.; Morgan, David S.; Orzol, Leonard L.; Polette, Danial J.

2007-01-01

Increasing residential development since in the 1960s has lead to increases in nitrate concentrations in shallow ground water in parts of the 247 square mile study area near La Pine, Oregon. Denitrification is the dominant nitrate-removal process that occurs in suboxic ground water, and suboxic ground water serves as a barrier to transport of most nitrate in the aquifer. Oxic ground water, on the other hand, represents a potential pathway for nitrate transport from terrestrial recharge areas to the Deschutes and Little Deschutes Rivers. The effects of present and potential future discharge of ground-water nitrate into the nitrogen-limited Deschutes and Little Deschutes Rivers are not known. However, additions of nitrogen to nitrogen-limited rivers can lead to increases in primary productivity which, in turn, can increase the magnitudes of dissolved oxygen and pH swings in river water. An understanding of the distribution of oxic ground water in the near-river environment could facilitate understanding the vulnerability of these rivers and could be a useful tool for management of these rivers. In this study, transects of temporary wells were installed in sub-river sediments beneath the Deschutes and Little Deschutes Rivers near La Pine to characterize near-river reduction/oxidation (redox) conditions near the ends of ground-water flow paths. Samples from transects installed near the center of the riparian zone or flood plain were consistently suboxic. Where transects were near edges of riparian zones, most ground-water samples also were suboxic. Oxic ground water (other than hyporheic water) was uncommon, and was only detected near the outside edge of some meander bends. This pattern of occurrence likely reflects geochemical controls throughout the aquifer as well as geochemical processes in the microbiologically active riparian zone near the end of ground-water flow paths. Younger, typically less reduced ground water generally enters near-river environments through peripheral zones, whereas older, typically more reduced ground water tends to discharge closer to the center of the river corridor. Such distributions of redox state reflect ground-water movement and geochemical evolution at the aquifer-scale. Redox state of ground water undergoes additional modification as ground water nears discharge points in or adjacent to rivers, where riparian zone processes can be important. Lateral erosion of river systems away from the center of the flood plain can decrease or even eliminate interactions between ground water and reducing riparian zone sediments. Thus, ground water redox patterns in near-river sediments appear to reflect the position of a river within the riparian zone/aquifer continuum. Spatial heterogeneity of redox conditions near the river/aquifer boundary (that is, near the riverbed) makes it difficult to extrapolate transect-scale findings to a precise delineation of the oxic-suboxic boundary in the near-river environment of the entire study area. However, the understanding of relations between near-river redox state and proximity to riparian zone edges provides a basis for applying these results to the study-area scale, and could help guide management efforts such as nitrogen-reduction actions or establishment of Total Maximum Daily Load criteria. Coupling the ground-water redox-based understanding of river vulnerability with ground-water particle-tracking-based characterization of connections between upgradient recharge areas and receiving rivers demonstrates one means of linking effects of potential nitrate loads at the beginning of ground-water flow paths with river vulnerability.

Patterns of in-soil methane production and atmospheric emission among different land covers of a Lake Erie estuarine wetland

NASA Astrophysics Data System (ADS)

Rey Sanchez, C.; Morin, T. H.; Stefanik, K. C.; Angle, J.; Wrighton, K. C.; Bohrer, G.

2017-12-01

Wetland soils store a great amount of carbon, but also accumulate and emit methane (CH4), a powerful greenhouse gas. To better understand the vertical and horizontal spatial variability of CH4 emissions, we monitored production and fluxes of CH4 in Old Woman Creek, an estuarine wetland of Lake Erie, Ohio, during the growing seasons of 2015 and 2016. Our combined observation methods targeted three different scales: 1) the eddy covariance technique provided continuous high frequency observations integrated over a large spatial footprint; 2) monthly chamber measurements provided sparse point measurements of fluxes in four distinct land-cover types in the wetland: open water, emergent vegetation (Typha spp.), floating vegetation (Nelumbo spp.) and mud flats; and 3) in-situ porewater dialysis samplers, "peepers", provided vertical CH4 concentration data in the soil at the same locations and temporal time steps as the chambers. In addition, we studied gene transcripts to quantify methanogenesis activity along the vertical soil profile. Using integrated chamber and EC measurements, we found an average surface emission rate from Typha, the most abundant vegetated land cover, of 219.4 g CH4-C m-2 y-1, which was much higher than rates reported in similar emergent vegetation types in other wetlands. There was large spatial variation of flux rates, with mud flats having the highest rates of CH4 emission, followed by Nelumbo and Typha patches, and with open water having the lowest emissions. Within the soil column, we applied a numerical model to convert soil methane concentrations to emissions rates. We found that, contrary to current ideas of methane production, most methane was being produced in the well-oxygenated surface soils, probably in anoxic microsites within the oxic layer. Our metatranscriptomic data supported these findings, clearly showing nine times greater methanogenic activity in oxic surface soils relative to deeper anoxic soils. Combined, our results provide important insights for the representation of processes of methane production and consumption in models, which can largely affect the estimates of methane emission from wetlands.

The interaction of natural organic matter with iron in a wetland (Tennessee Park, Colorado) receiving acid mine drainage

USGS Publications Warehouse

Peiffer, Stefan; Walton-Day, Katherine; Macalady, Donald L.

1999-01-01

Pore water from a wetland receiving acid mine drainage was studied for its iron and natural organic matter (NOM) geochemistry on three different sampling dates during summer 1994. Samples were obtained using a new sampling technique that is based on screened pipes of varying length (several centimeters), into which dialysis vessels can be placed and that can be screwed together to allow for vertical pore-water sampling. The iron concentration increased with time (through the summer) and had distinct peaks in the subsurface. Iron was mainly in the ferrous form; however, close to the surface, significant amounts of ferric iron (up to 40% of 2 mmol L-1 total iron concentration) were observed. In all samples studied, iron was strongly associated with NOM. Results from laboratory experiments indicate that the NOM stabilizes the ferric iron as small iron oxide colloids (able to pass a 0.45μm dialysis membrane). We hypothesize that, in the pore water of the wetland, the high NOM concentrations (>100 mg C L-1) allow formation of such colloids at the redoxcline close to the surface and at the contact zone to the adjacent oxic aquifer. Therefore, particle transport along flow paths and resultant export of ferric iron from the wetland into ground water might be possible.

Denitrification of drinking water in a two-stage membrane bioreactor by using immobilized biomass.

PubMed

Ravnjak, Matjaž; Vrtovšek, Janez; Pintar, Albin

2013-01-01

Nitrate removal from polluted groundwater was investigated in a two-stage anoxic/oxic biofilm membrane bioreactor. The process was carried out with ethanol as a carbon source (corresponding C/N ratio of 1.4-2.5) and commercially available Biocontact-N biocarriers (Nisshinbo, Japan) to enable immobilization of highly efficient and long-lasting microbiota. At a residence time of the liquid phase equal to 2.5h, nitrate conversions higher than 99% were obtained without the formation of nitrite and ammonium ions. The concentration of total organic carbon in the reactor discharge was very similar to the content of organic matter in tap water. The biocarriers minimized the occurrence of suspended filamentous bacteria, and the utilization of increased shear force facilitated collisions of floating biocarrier particles with the outer membrane surface, preventing membrane fouling and resulting in stable operation of the system for 40 days. Copyright © 2012 Elsevier Ltd. All rights reserved.

Low-oxygen waters limited habitable space for early animals.

PubMed

Tostevin, R; Wood, R A; Shields, G A; Poulton, S W; Guilbaud, R; Bowyer, F; Penny, A M; He, T; Curtis, A; Hoffmann, K H; Clarkson, M O

2016-09-23

The oceans at the start of the Neoproterozoic Era (1,000-541 million years ago, Ma) were dominantly anoxic, but may have become progressively oxygenated, coincident with the rise of animal life. However, the control that oxygen exerted on the development of early animal ecosystems remains unclear, as previous research has focussed on the identification of fully anoxic or oxic conditions, rather than intermediate redox levels. Here we report anomalous cerium enrichments preserved in carbonate rocks across bathymetric basin transects from nine localities of the Nama Group, Namibia (∼550-541 Ma). In combination with Fe-based redox proxies, these data suggest that low-oxygen conditions occurred in a narrow zone between well-oxygenated surface waters and fully anoxic deep waters. Although abundant in well-oxygenated environments, early skeletal animals did not occupy oxygen impoverished regions of the shelf, demonstrating that oxygen availability (probably >10 μM) was a key requirement for the development of early animal-based ecosystems.

MTBE, TBA, and TAME attenuation in diverse hyporheic zones

USGS Publications Warehouse

Landmeyer, J.E.; Bradley, P.M.; Trego, D.A.; Hale, K.G.; Haas, J.E.

2010-01-01

Groundwater contamination by fuel-related compounds such as the fuel oxygenates methyl tert-butyl ether (MTBE), tert-butyl alcohol (TBA), and tert-amyl methyl ether (TAME) presents a significant issue to managers and consumers of groundwater and surface water that receives groundwater discharge. Four sites were investigated on Long Island, New York, characterized by groundwater contaminated with gasoline and fuel oxygenates that ultimately discharge to fresh, brackish, or saline surface water. For each site, contaminated groundwater discharge zones were delineated using pore water geochemistry data from 15 feet (4.5 m) beneath the bottom of the surface water body in the hyporheic zone and seepage-meter tests were conducted to measure discharge rates. These data when combined indicate that MTBE, TBA, and TAME concentrations in groundwater discharge in a 5-foot (1.5-m) thick section of the hyporheic zone were attenuated between 34% and 95%, in contrast to immeasurable attenuation in the shallow aquifer during contaminant transport between 0.1 and 1.5 miles (0.1 to 2.4 km). The attenuation observed in the hyporheic zone occurred primarily by physical processes such as mixing of groundwater and surface water. Biodegradation also occurred as confirmed in laboratory microcosms by the mineralization of U- 14C-MTBE and U- 14C-TBA to 14CO2 and the novel biodegradation of U- 14C-TAME to 14CO2 under oxic and anoxic conditions. The implication of fuel oxygenate attenuation observed in diverse hyporheic zones suggests an assessment of the hyporheic zone attenuation potential (HZAP) merits inclusion as part of site assessment strategies associated with monitored or engineered attenuation. ?? 2009 National Ground Water Association.

Kinetics and isotherm analysis of 2,4-dichlorophenoxyl acetic acid adsorption onto soil components under oxic and anoxic conditions.

PubMed

Ololade, Isaac A; Alomaja, Folasade; Oladoja, Nurudeen A; Ololade, Oluwaranti O; Oloye, Femi F

2015-01-01

2,4-dichlorophenoxyl acetic acid (2,4-D, pKa = 2.8) is used extensively as a herbicide in agricultural practices. Its sorption behavior on both untreated and soils treated to significantly remove specific components (organic and iron and manganese [Fe-Mn] oxides and hydroxides phases) was investigated under oxic and anoxic conditions. The chemical and structural heterogeneity of the soil components were characterized by elemental analysis and X-ray diffraction (XRD). The coexistence of the various components seems to either mask sorption sites on the untreated soil surfaces or inhibit interlayer diffusion of 2,4-D. All sorption data conform to the Freundlich description and a pseudo-second-order kinetic model. There was a strong positive correlation between sorption capacity K(d), and surface area (r(2) ≤ 0.704), but a negative correlation was uncovered with both pH and organic carbon (r(2) ≤ -0.860). The results indicate that 2,4-D is preferably sorbed under oxic rather than anoxic conditions and it is greater on soils containing a high Fe content. There was incomplete 2,4-D sorption reversibility, with desorption occurring more rapidly under anoxic conditions. The study suggests that stimulation of Fe III reduction could be used for the bioremediation of a 2,4-D-contaminated site.

Persistence of uranium groundwater plumes: contrasting mechanisms at two DOE sites in the groundwater-river interaction zone.

PubMed

Zachara, John M; Long, Philip E; Bargar, John; Davis, James A; Fox, Patricia; Fredrickson, Jim K; Freshley, Mark D; Konopka, Allan E; Liu, Chongxuan; McKinley, James P; Rockhold, Mark L; Williams, Kenneth H; Yabusaki, Steve B

2013-04-01

We examine subsurface uranium (U) plumes at two U.S. Department of Energy sites that are located near large river systems and are influenced by groundwater-river hydrologic interaction. Following surface excavation of contaminated materials, both sites were projected to naturally flush remnant uranium contamination to levels below regulatory limits (e.g., 30 μg/L or 0.126 μmol/L; U.S. EPA drinking water standard), with 10 years projected for the Hanford 300 Area (Columbia River) and 12 years for the Rifle site (Colorado River). The rate of observed uranium decrease was much lower than expected at both sites. While uncertainty remains, a comparison of current understanding suggests that the two sites have common, but also different mechanisms controlling plume persistence. At the Hanford 300 A, the persistent source is adsorbed U(VI) in the vadose zone that is released to the aquifer during spring water table excursions. The release of U(VI) from the vadose zone and its transport within the oxic, coarse-textured aquifer sediments is dominated by kinetically-limited surface complexation. Modeling implies that annual plume discharge volumes to the Columbia River are small (

Persistence of uranium groundwater plumes: Contrasting mechanisms at two DOE sites in the groundwater-river interaction zone

NASA Astrophysics Data System (ADS)

Zachara, John M.; Long, Philip E.; Bargar, John; Davis, James A.; Fox, Patricia; Fredrickson, Jim K.; Freshley, Mark D.; Konopka, Allan E.; Liu, Chongxuan; McKinley, James P.; Rockhold, Mark L.; Williams, Kenneth H.; Yabusaki, Steve B.

2013-04-01

We examine subsurface uranium (U) plumes at two U.S. Department of Energy sites that are located near large river systems and are influenced by groundwater-river hydrologic interaction. Following surface excavation of contaminated materials, both sites were projected to naturally flush remnant uranium contamination to levels below regulatory limits (e.g., 30 μg/L or 0.126 μmol/L; U.S. EPA drinking water standard), with 10 years projected for the Hanford 300 Area (Columbia River) and 12 years for the Rifle site (Colorado River). The rate of observed uranium decrease was much lower than expected at both sites. While uncertainty remains, a comparison of current understanding suggests that the two sites have common, but also different mechanisms controlling plume persistence. At the Hanford 300 A, the persistent source is adsorbed U(VI) in the vadose zone that is released to the aquifer during spring water table excursions. The release of U(VI) from the vadose zone and its transport within the oxic, coarse-textured aquifer sediments is dominated by kinetically-limited surface complexation. Modeling implies that annual plume discharge volumes to the Columbia River are small (< one pore volume). At the Rifle site, slow oxidation of naturally reduced, contaminant U(IV) in the saturated zone and a continuous influx of U(VI) from natural, up-gradient sources influence plume persistence. Rate-limited mass transfer and surface complexation also control U(VI) migration velocity in the sub-oxic Rifle groundwater. Flux of U(VI) from the vadose zone at the Rifle site may be locally important, but it is not the dominant process that sustains the plume. A wide range in microbiologic functional diversity exists at both sites. Strains of Geobacter and other metal reducing bacteria are present at low natural abundance that are capable of enzymatic U(VI) reduction in localized zones of accumulated detrital organic carbon or after organic carbon amendment. Major differences between the sites include the geochemical nature of residual, contaminant U; the rates of current kinetic processes (both biotic and abiotic) influencing U(VI) solid-liquid distribution; the presence of detrital organic matter and the resulting spatial heterogeneity in microbially-driven redox properties; and the magnitude of groundwater hydrologic dynamics controlled by river-stage fluctuations, geologic structures, and aquifer hydraulic properties. The comparative analysis of these sites provides important guidance to the characterization, understanding, modeling, and remediation of groundwater contaminant plumes influenced by surface water interaction that are common world-wide.

Plant-Sediment Interactions in Salt Marshes - An Optode Imaging Study of O2, pH, and CO 2 Gradients in the Rhizosphere.

PubMed

Koop-Jakobsen, Ketil; Mueller, Peter; Meier, Robert J; Liebsch, Gregor; Jensen, Kai

2018-01-01

In many wetland plants, belowground transport of O 2 via aerenchyma tissue and subsequent O 2 loss across root surfaces generates small oxic root zones at depth in the rhizosphere with important consequences for carbon and nutrient cycling. This study demonstrates how roots of the intertidal salt-marsh plant Spartina anglica affect not only O 2 , but also pH and CO 2 dynamics, resulting in distinct gradients of O 2 , pH, and CO 2 in the rhizosphere. A novel planar optode system (VisiSens TD ® , PreSens GmbH) was used for taking high-resolution 2D-images of the O 2 , pH, and CO 2 distribution around roots during alternating light-dark cycles. Belowground sediment oxygenation was detected in the immediate vicinity of the roots, resulting in oxic root zones with a 1.7 mm radius from the root surface. CO 2 accumulated around the roots, reaching a concentration up to threefold higher than the background concentration, and generally affected a larger area within a radius of 12.6 mm from the root surface. This contributed to a lowering of pH by 0.6 units around the roots. The O 2 , pH, and CO 2 distribution was recorded on the same individual roots over diurnal light cycles in order to investigate the interlinkage between sediment oxygenation and CO 2 and pH patterns. In the rhizosphere, oxic root zones showed higher oxygen concentrations during illumination of the aboveground biomass. In darkness, intraspecific differences were observed, where some plants maintained oxic root zones in darkness, while others did not. However, the temporal variation in sediment oxygenation was not reflected in the temporal variations of pH and CO 2 around the roots, which were unaffected by changing light conditions at all times. This demonstrates that plant-mediated sediment oxygenation fueling microbial decomposition and chemical oxidation has limited impact on the dynamics of pH and CO 2 in S. anglica rhizospheres, which may in turn be controlled by other processes such as root respiration and root exudation.

Ocean acidification: One potential driver of phosphorus eutrophication.

PubMed

Ge, Changzi; Chai, Yanchao; Wang, Haiqing; Kan, Manman

2017-02-15

Harmful algal blooms which may be limited by phosphorus outbreak increases currently and ocean acidification worsens presently, which implies that ocean acidification might lead to phosphorus eutrophication. To verify the hypothesis, oxic sediments were exposed to seawater with different pH 30days. If pH was 8.1 and 7.7, the total phosphorus (TP) content in sediments was 1.52±0.50 and 1.29±0.40mg/g. The inorganic phosphorus (IP) content in sediments exposed to seawater with pH8.1 and 7.7 was 1.39±0.10 and 1.06±0.20mg/g, respectively. The exchangeable phosphorus (Ex-P) content in sediments was 4.40±0.45 and 2.82±0.15μg/g, if seawater pH was 8.1 and 7.7. Ex-P and IP contents in oxic sediments were reduced by ocean acidification significantly (p<5%). The reduced phosphorus in sediments diffused into water, which implied that ocean acidification was one potential facilitator of phosphorus eutrophication in oxic conditions. Copyright © 2016 Elsevier Ltd. All rights reserved.

Sediment Microbial Community Dynamics and Geochemistry During Oxic and Hypoxic Periods in the Gulf of Mexico

EPA Science Inventory

Seasonal hypoxia in the benthic waters of the Louisiana Coastal Shelf contributes to the Gulf of Mexico "dead zone" phenomena. Limited information is available on sedimentary biogeochemical interactions during periods of hypoxia.

Mixing of shallow and deep groundwater as indicated by the chemistry and age of karstic springs

USGS Publications Warehouse

Toth, D.J.; Katz, B.G.

2006-01-01

Large karstic springs in east-central Florida, USA were studied using multi-tracer and geochemical modeling techniques to better understand groundwater flow paths and mixing of shallow and deep groundwater. Spring water types included Ca-HCO3 (six), Na-Cl (four), and mixed (one). The evolution of water chemistry for Ca-HCO3 spring waters was modeled by reactions of rainwater with soil organic matter, calcite, and dolomite under oxic conditions. The Na-Cl and mixed-type springs were modeled by reactions of either rainwater or Upper Floridan aquifer water with soil organic matter, calcite, and dolomite under oxic conditions and mixed with varying proportions of saline Lower Floridan aquifer water, which represented 4-53% of the total spring discharge. Multiple-tracer data-chlorofluorocarbon CFC-113, tritium (3H), helium-3 (3Hetrit), sulfur hexafluoride (SF6) - for four Ca-HCO3 spring waters were consistent with binary mixing curves representing water recharged during 1980 or 1990 mixing with an older (recharged before 1940) tracer-free component. Young-water mixing fractions ranged from 0.3 to 0.7. Tracer concentration data for two Na-Cl spring waters appear to be consistent with binary mixtures of 1990 water with older water recharged in 1965 or 1975. Nitrate-N concentrations are inversely related to apparent ages of spring waters, which indicated that elevated nitrate-N concentrations were likely contributed from recent recharge. ?? Springer-Verlag 2006.

Erratum: Mixing of shallow and deep groundwater as indicated by the chemistry and age of karstic springs

NASA Astrophysics Data System (ADS)

Toth, David J.; Katz, Brian G.

2006-09-01

Large karstic springs in east-central Florida, USA were studied using multi-tracer and geochemical modeling techniques to better understand groundwater flow paths and mixing of shallow and deep groundwater. Spring water types included Ca-HCO3 (six), Na-Cl (four), and mixed (one). The evolution of water chemistry for Ca-HCO3 spring waters was modeled by reactions of rainwater with soil organic matter, calcite, and dolomite under oxic conditions. The Na-Cl and mixed-type springs were modeled by reactions of either rainwater or Upper Floridan aquifer water with soil organic matter, calcite, and dolomite under oxic conditions and mixed with varying proportions of saline Lower Floridan aquifer water, which represented 4-53% of the total spring discharge. Multiple-tracer data—chlorofluorocarbon CFC-113, tritium (3H), helium-3 (3Hetrit), sulfur hexafluoride (SF6)—for four Ca-HCO3 spring waters were consistent with binary mixing curves representing water recharged during 1980 or 1990 mixing with an older (recharged before 1940) tracer-free component. Young-water mixing fractions ranged from 0.3 to 0.7. Tracer concentration data for two Na-Cl spring waters appear to be consistent with binary mixtures of 1990 water with older water recharged in 1965 or 1975. Nitrate-N concentrations are inversely related to apparent ages of spring waters, which indicated that elevated nitrate-N concentrations were likely contributed from recent recharge.

Growth response of a deep-water ferromanganese crust to evolution of the Neogene Indian Ocean

USGS Publications Warehouse

Banakar, V.K.; Hein, J.R.

2000-01-01

A deep-water ferromanganese crust from a Central Indian Ocean seamount dated previously by 10Be and 230Th(excess) was studied for compositional and textural variations that occurred throughout its growth history. The 10Be/9Be dated interval (upper 32 mm) yields an uniform growth rate of 2.8 ?? 0.1 mm/Ma [Frank, M., O'Nions, R.K., 1998. Sources of Pb for Indian Ocean ferromanganese crusts: a record of Himalayan erosion. Earth Planet. Sci. Lett., 158, pp. 121-130.] which gives an extrapolated age of ~ 26 Ma for the base of the crust at 72 mm and is comparable to the maximum age derived from the Co-model based growth rate estimates. This study shows that Fe-Mn oxyhydroxide precipitation did not occur from the time of emplacement of the seamount during the Eocene (~ 53 Ma) until the late Oligocene (~ 26 Ma). This paucity probably was the result of a nearly overlapping palaeo-CCD and palaeo-depth of crust formation, increased early Eocene productivity, instability and reworking of the surface rocks on the flanks of the seamount, and lack of oxic deep-water in the nascent Indian Ocean. Crust accretion began (older zone) with the formation of isolated cusps of Fe-Mn oxide during a time of high detritus influx, probably due to the early-Miocene intense erosion associated with maximum exhumation of the Himalayas (op. cit.). This cuspate textured zone extends from 72 mm to 42 mm representing the early-Miocene period. Intense polar cooling and increased mixing of deep and intermediate waters at the close of the Oligocene might have led to the increased oxygenation of the bottom-water in the basin. A considerable expansion in the vertical distance between the seafloor depth and the CCD during the early Miocene in addition to the influx of oxygenated bottom-water likely initiated Fe-Mn crust formation. Pillar structure characterises the younger zone, which extends from 40 mm to the surface of the crust, i.e., ~ 15 Ma to Present. This zone is characterised by > 25% higher content of oxide-bound elements than in the older zone, possibly corresponding to further increased oxygenation of bottom-waters, increased stability of the seamount slope, and gradually reduced input of continental detritus from the erosion of the Himalayas. Middle Miocene Antarctic glaciation, which peaked ~ 12-13 Ma ago, increased the oxic bottom-water influx to the basin resulting in accretion of the crust with low detritus. Therefore, the younger crust started to accrete in response to a shift in bottom-water circulation towards the contemporary pattern, which produced a uniform growth rate and pillar structure up to the present. (C) 2000 Published by Elsevier Science B.V.

Impact of solids residence time on biological nutrient removal performance of membrane bioreactor.

PubMed

Ersu, Cagatayhan Bekir; Ong, Say Kee; Arslankaya, Ertan; Lee, Yong-Woo

2010-05-01

Impact of long solids residence times (SRTs) on nutrient removal was investigated using a submerged plate-frame membrane bioreactor with anaerobic and anoxic tanks. The system was operated at 10, 25, 50 and 75 days SRTs with hydraulic retention times (HRTs) of 2 h each for the anaerobic and anoxic tanks and 8 h for the oxic tank. Recirculation of oxic tank mixed liquor into the anaerobic tank and permeate into the anoxic tank were fixed at 100% each of the influent flow. For all SRTs, percent removals of soluble chemical oxygen demand were more than 93% and nitrification was more than 98.5% but total nitrogen percent removal seemed to peak at 81% at 50 days SRT while total phosphorus (TP) percent removal showed a deterioration from approximately 80% at 50 days SRT to 60% at 75 days SRT. Before calibrating the Biowin((R)) model to the experimental data, a sensitivity analysis of the model was conducted which indicated that heterotrophic anoxic yield, anaerobic hydrolysis factors of heterotrophs, heterotrophic hydrolysis, oxic endogenous decay rate for heterotrophs and oxic endogenous decay rate of PAOs had the most impact on predicted effluent TP concentration. The final values of kinetic parameters obtained in the calibration seemed to imply that nitrogen and phosphorus removal increased with SRT due to an increase in anoxic and anaerobic hydrolysis factors up to 50 days SRT but beyond that removal of phosphorus deteriorated due to high oxic endogenous decay rates. This indirectly imply that the decrease in phosphorus removal at 75 days SRT may be due to an increase in lysis of microbial cells at high SRTs along with the low food/microorganisms ratio as a result of high suspended solids in the oxic tank. Several polynomial correlations relating the various calibrated kinetic parameters with SRTs were derived. The Biowin((R)) model and the kinetic parameters predicted by the polynomial correlations were verified and found to predict well the effluent water quality of the MBR at 35 days SRT.

Global Patterns of Bacterial Beta-Diversity in Seafloor and Seawater Ecosystems

PubMed Central

Zinger, Lucie; Amaral-Zettler, Linda A.; Fuhrman, Jed A.; Horner-Devine, M. Claire; Huse, Susan M.; Welch, David B. Mark; Martiny, Jennifer B. H.; Sogin, Mitchell; Boetius, Antje; Ramette, Alban

2011-01-01

Background Marine microbial communities have been essential contributors to global biomass, nutrient cycling, and biodiversity since the early history of Earth, but so far their community distribution patterns remain unknown in most marine ecosystems. Methodology/Principal Findings The synthesis of 9.6 million bacterial V6-rRNA amplicons for 509 samples that span the global ocean's surface to the deep-sea floor shows that pelagic and benthic communities greatly differ, at all taxonomic levels, and share <10% bacterial types defined at 3% sequence similarity level. Surface and deep water, coastal and open ocean, and anoxic and oxic ecosystems host distinct communities that reflect productivity, land influences and other environmental constraints such as oxygen availability. The high variability of bacterial community composition specific to vent and coastal ecosystems reflects the heterogeneity and dynamic nature of these habitats. Both pelagic and benthic bacterial community distributions correlate with surface water productivity, reflecting the coupling between both realms by particle export. Also, differences in physical mixing may play a fundamental role in the distribution patterns of marine bacteria, as benthic communities showed a higher dissimilarity with increasing distance than pelagic communities. Conclusions/Significance This first synthesis of global bacterial distribution across different ecosystems of the World's oceans shows remarkable horizontal and vertical large-scale patterns in bacterial communities. This opens interesting perspectives for the definition of biogeographical biomes for bacteria of ocean waters and the seabed. PMID:21931760

Factors affecting the movement and persistence of nitrate and pesticides in the surficial and upper Floridan aquifers in two agricultural areas in the southeastern United States

USGS Publications Warehouse

Katz, B.G.; Berndt, M.P.; Crandall, C.A.

2014-01-01

Differences in the degree of confinement, redox conditions, and dissolved organic carbon (DOC) are the main factors that control the persistence of nitrate and pesticides in the Upper Floridan aquifer (UFA) and overlying surficial aquifer beneath two agricultural areas in the southeastern US. Groundwater samples were collected multiple times from 66 wells during 1993–2007 in a study area in southwestern Georgia (ACFB) and from 48 wells in 1997–98 and 2007–08 in a study area in South Carolina (SANT) as part of the US Geological Survey National Water-Quality Assessment Program. In the ACFB study area, where karst features are prevalent, elevated nitrate-N concentrations in the oxic unconfined UFA (median 2.5 mg/L) were significantly (p = 0.03) higher than those in the overlying oxic surficial aquifer (median 1.5 mg/L). Concentrations of atrazine and deethylatrazine (DEA; the most frequently detected pesticide and degradate) were higher in more recent groundwater samples from the ACFB study area than in samples collected prior to 2000. Conversely, in the SANT study area, nitrate-N concentrations in the UFA were mostly <0.06 mg/L, resulting from anoxic conditions and elevated DOC concentrations that favored denitrification. Although most parts of the partially confined UFA in the SANT study area were anoxic or had mixed redox conditions, water from 28 % of the sampled wells was oxic and had low DOC concentrations. Based on the groundwater age information, nitrate concentrations reflect historic fertilizer N usage in both the study areas, but with a lag time of about 15–20 years. Simulated responses to future management scenarios of fertilizer N inputs indicated that elevated nitrate-N concentrations would likely persist in oxic parts of the surficial aquifer and UFA for decades even with substantial decreases in fertilizer N inputs over the next 40 years.

Sulfur speciation and isotope analysis of the 2.7 Ga shallow- and deep-facies black shales from Pilbara, Western Australia

NASA Astrophysics Data System (ADS)

Minami, H.; Yamaguchi, K. E.; Naraoka, H.

2014-12-01

It has been widely believed that Great Oxidation Event (GOE: Holland, 1994) occurred at ~2.4-2.2 Ga ago. However, some previous studies have found evidence for oxic ocean and atmosphere from earlier rock records (e.g., Hoashi et al., 2009). In order to explore if such oxic environment was local or global and if there was redox heterogeneity in a sedimentary basin before the inferred GOE, using the 2.7 Ga pyrite-bearing drillcore black shales (deep-facies WRL1 and shallow-facies RHDH2A drillcores) from Pilbara, Western Australia, we separately quantified abundance of S-bearing species (SAVS (acid-volatile sulfide), Spy (pyrite), SSO4 (sulfate), Sorg (organic-S), and S0 (elemental S) and Fe-bearing species (Fecarb, Feox, and Femag) by using sequential extraction methods. These samples were previously used by Brocks et al. (1999), Yamaguchi (2002), Yamaguchi et al. (2005), and Eigenbrode and Freeman (2006). The shallow samples have high S contents and are interpreted to have deposited in relatively anoxic environment, but most of deep samples with elevated Fe contents deposited in relatively oxic environment. The DOP values and δ34Spy values are relatively higher in shallow samples, suggesting active bacterial sulfate reduction in reducing environment created due to near-complete consumption of dissolved O2by decomposition of organic matter produced by photosynthesizers living in the surface ocean. All of these observations consistently suggest that the shallower part was anoxic and deeper part was oxic in the 2.7 Ga ocean. The surface ocean would have been oxygenated due to activity of oxygenic photosynthesis. Such redox stratification of the ocean, i.e., development of mid-depth (shallow) OMZ in an essentially oxic ocean, is typically seen in highly productive regions in the modern ocean. Modern-style oceanic redox structure could have existed as far back as 2.7 Ga ago, much earlier than the inferred GOE at ~2.4-2.2 Ga. Brocks et al. (1999) Science 285, 1033-1036; Eigenbrode & Freeman (2006) PNAS 103, 15759-15764; Hoashi et al. (2009) Nature Geosc. 2, 301-306; Holland (1994) Early Life on Earth, Columbia Univ. Press; Yamaguchi (2002) Ph.D. dissertation, Penn State Univ.; Yamaguchi et al. (2005) Chem. Geol. 218, 135- 169.

Marine redox stratification during the early Cambrian (ca. 529-509 Ma) and its control on the development of organic-rich shales in Yangtze Platform

NASA Astrophysics Data System (ADS)

Zhang, Yuying; He, Zhiliang; Jiang, Shu; Gao, Bo; Liu, Zhongbao; Han, Bo; Wang, Hu

2017-06-01

High resolution geochemical data from nine sections representing shelf to basinal environments in the Yangtze Platform were analyzed to reconstruct the marine redox environment during early Cambrian. Based on Fe species and Mo/TOC ratios, we have supplemented marine redox stratification during Stage 4 (late Canglangpuian-Longwangmiaoan, ˜514-509 Ma) on basis of the previously studied Stage 2-Stage 3 (Meishucunian-Qiongzhusian, ˜529-514 Ma). A new proposed marine stratified redox model indicates that the middepth "euxinic wedge" developed at the base of slope during ˜514-509 Ma in contrast to that the "euxinic wedge" prevailed at the shelf margin during ˜529-514 Ma, even though these middepth euxinic waters both occurred between the oxic surface waters and ferruginous deep waters. This marine redox stratification resulted in high production and good preservation of organic matter during early Cambrian. TOC values in euxinic waters in the middle are generally higher than in ferruginous waters due to upwelling in slope. Therefore, the lower Cambrian organic-rich shales in the Yangtze Platform are inferred to be deposited under the anoxic-ferruginous and euxinic bottom waters with moderate-strong restriction.

Sources of oxygen flux in groundwater during induced bank filtration at a site in Berlin, Germany

NASA Astrophysics Data System (ADS)

Kohfahl, Claus; Massmann, Gudrun; Pekdeger, Asaf

2009-05-01

The microbial degradation of pharmaceuticals found in surface water used for artificial recharge is strongly dependent on redox conditions of the subsurface. Furthermore the durability of production wells may decrease considerably with the presence of oxygen and ferrous iron due to the precipitation of trivalent iron oxides and subsequent clogging. Field measurements are presented for oxygen at a bank filtration site in Berlin, Germany, along with simplified calculations of different oxygen pathways into the groundwater. For a two-dimensional vertical cross-section, oxygen input has been calculated for six scenarios related to different water management strategies. Calculations were carried out in order to assess the amount of oxygen input due to (1) the infiltration of oxic lake water, (2) air entrapment as a result of water table oscillations, (3) diffusive oxygen flux from soil air and (4) infiltrating rainwater. The results show that air entrapment and infiltrating lake water during winter constitute by far the most important mechanism of oxygen input. Oxygen input by percolating rainwater and by diffusive delivery of oxygen in the gas phase is negligible. The results exemplify the importance of well management as a determining factor for water oscillations and redox conditions during artificial recharge.

Vertical mercury distributions in the oceans

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gill, G.A.; Fitzgerald, W.F.

1988-06-01

The vertical distribution of mercury (Hg) was determined at coastal and open ocean sites in the northwest Atlantic and Pacific Oceans. Reliable and diagnostic Hg distribution were obtained, permitting major processes governing the marine biogeochemistry of Hg to be identified. The northwest Atlantic near Bermuda showed surface water Hg concentrations near 4 pM, a maximum of 10 pM within the main thermocline, and concentrations less than or equal to surface water values below the depth of the maximum. The maximum appears to result from lateral transport of Hg enriched waters from higher latitudes. In the central North Pacific, surface watersmore » (to 940 m) were slightly elevated (1.9 {plus minus} 0.7 pM) compared to deeper waters (1.4 {plus minus} 0.4 pM), but on thermocline Hg maximum was observed. At similar depths, Hg concentrations near Bermuda were elevated compared to the central North Pacific Ocean. The authors hypothesize that the source of this Hg comes from diagenetic reactions in oxic margin sediments, releasing dissolved Hg to overlying water. Geochemical steady-state box modeling arguments predict a relatively short ({approximately}350 years) mean residence time for Hg in the oceans, demonstrating the reactive nature of Hg in seawater and precluding significant involvement in nutrient-type recycling. Mercury's distributional features and reactive nature suggest that interaction of Hg with settling particulate matter and margin sediments play important roles in regulating oceanic Hg concentrations. Oceanic Hg distributions are governed by an external cycling process, in which water column distributions reflect a rapid competition between the magnitude of the input source and the intensity of the (water column) removal process.« less

Reconstruction of early Cambrian ocean chemistry from Mo isotopes

NASA Astrophysics Data System (ADS)

Wen, Hanjie; Fan, Haifeng; Zhang, Yuxu; Cloquet, Christophe; Carignan, Jean

2015-09-01

The Neoproterozoic-Cambrian transition was a key time interval in the history of the Earth, especially for variations in oceanic and atmospheric chemical composition. However, two conflicting views exist concerning the nature of ocean chemistry across the Precambrian-Cambrian boundary. Abundant geochemical evidence suggests that oceanic basins were fully oxygenated by the late Ediacaran, while other studies provide seemingly conflicting evidence for anoxic deep waters, with ferruginous conditions [Fe(II)-enriched] persisting into the Cambrian. Here, two early Cambrian sedimentary platform and shelf-slope sections in South China were investigated to trace early Cambrian ocean chemistry from Mo isotopes. The results reveal that early Cambrian sediments deposited under oxic to anoxic/euxinic conditions have δ98/95Mo values ranging from -0.28‰ to 2.29‰, which suggests that early Cambrian seawater may have had δ98/95Mo values of at least 2.29‰, similar to modern oceans. The heaviest and relatively homogeneous δ98/95Mo values were recorded in siltstone samples formed under completely oxic conditions, which is considered that Mn oxide-free shuttling was responsible for such heavy δ98/95Mo value. Further, combined with Fe species data and the accumulation extent of Mo and U, the variation of δ98/95Mo values in the two studied sections demonstrate a redox-stratified ocean with completely oxic shallow water and predominantly anoxic (even euxinic) deeper water having developed early on, which eventually became completely oxygenated. This suggests that oceanic circulation at the time became reorganized, and such changes in oceanic chemistry may have been responsible for triggering the "Cambrian Explosion" of biological diversity.

Effect of ammonium and oxygen on methane and nitrous oxide fluxes across sediment-water interface in a eutrophic lake.

PubMed

Liikanen, Anu; Martikainen, Pertti J

2003-09-01

Eutrophication has decreased the O(2) content and increased the NH(4)(+) availability in freshwaters. These changes may affect carbon and nitrogen transformation processes and the production of CH(4) and N(2)O, which are important greenhouse gases. We studied release of CH(4) and N(2)O from a eutrophic lake sediment under varying O(2) and NH(4)(+) conditions. Intact sediment cores were incubated in a laboratory microcosm with a continuous anoxic or oxic water flows containing 0, 50, 500, 5,000, or 15000 microM NH(4)(+). With the anoxic flow, the sediment released CH(4), up to 7.9 mmol m(-2)d(-1). With the oxic flow, the CH(4) emissions were small indicating limited CH(4) production and/or effective CH(4) oxidation. Addition of NH(4)(+) did not affect sediment CH(4) release, evidence that the CH(4) oxidizing bacteria were not disturbed by the extra NH(4)(+). The release of N(2)O from the sediment was highest, up to 7.6 micromol m(-2)d(-1), with the oxic flow without NH(4)(+) addition. Oxygen was the key factor regulating the production of NO(3)(-), which enabled denitrification and production of N(2)O. However, the highest NH(4)(+) addition increased nitrification and associated O(2) consumption causing a decrease in sediment O(2) content and in accumulation of NO(3)(-) and N(2)O, which were effectively reduced to N(2) in denitrification. In summary, sediment CH(4) and N(2)O dynamics are regulated more by the availability of O(2) than extra NH(4)(+). Anoxia in eutrophic lakes favouring the CH(4) production, is the major contributor to the atmospheric consequences of water eutrophication.

Physical and chemical consequences of artificially deepened thermocline in a small humic lake - a paired whole-lake climate change experiment

NASA Astrophysics Data System (ADS)

Forsius, M.; Saloranta, T.; Arvola, L.; Salo, S.; Verta, M.; Ala-Opas, P.; Rask, M.; Vuorenmaa, J.

2010-05-01

Climate change with higher air temperatures and changes in cloud cover, radiation and wind speed alters the heat balance and stratification patterns of lakes. A paired whole-lake thermocline manipulation experiment of a small (0.047 km2) shallow dystrophic lake (Halsjärvi) was carried out in southern Finland. A thermodynamic model (MyLake) was used for both predicting the impacts of climate change scenarios and for determining the manipulation target of the experiment. The model simulations assuming several climate change scenarios indicated large increases in the whole-lake monthly mean temperature (+1.4-4.4 °C in April-October for the A2 scenario), and shortening of the length of the ice covered period by 56-89 days. The thermocline manipulation resulted in large changes in the thermodynamic properties of the lake, and those were rather well consistent with the simulated future increases in the heat content during the summer-autumn season. The manipulation also resulted in changes in the oxygen stratification, and the expansion of the oxic water layer increased the spatial extent of the sediment surface oxic-anoxic interfaces. The experiment also affected several other chemical constituents; concentrations of TotN, NH4 and organic carbon showed a statistically significant decrease, likely due to both unusual hydrological conditions during the experiment period and increased decomposition and sedimentation. Changes in mercury processes and in the aquatic food web were also introduced. In comparison with the results of a similar whole-lake manipulation experiment in a deep, oligotrophic, clear-watered lake in Norway, it is evident that shallow dystrophic lakes, common in the boreal region, are more sensitive to physical perturbations. This means that projected climate change may strongly modify their physical and chemical conditions in the future.

Vertical oxygen minimum zone oscillations since 20 ka in Santa Barbara Basin: A benthic foraminiferal community perspective

NASA Astrophysics Data System (ADS)

Moffitt, Sarah E.; Hill, Tessa M.; Ohkushi, Kenichi; Kennett, James P.; Behl, Richard J.

2014-01-01

we present a history of deoxygenation of upper intermediate waters during the last deglaciation from Santa Barbara Basin (SBB), based on quantitative analyses of benthic foraminiferal assemblages, from a new shallow piston core above basin sill depth (MV0811-15JC, 418 m), and previously described sequences in the deeper basin (MD02-2504, 481 m and MD02-2503, 570 m). We document a 152 m depth transect of benthic foraminiferal assemblages to extract changing community structure (density, diversity, and evenness) and improve paleoenvironmental interpretation of late Quaternary vertical oscillations in the upper boundary of the oxygen minimum zone (OMZ). Close interaction between changes in open margin OMZ and that of the restricted SBB is documented using these quantitative techniques. MV0811-15JC, while being unlaminated, contains strongly hypoxic foraminiferal assemblages (including species Bolivina tumida and Nonionella stella), coeval with preserved sediment laminations in the deeper cores. Last Glacial Maximum (LGM) assemblages across this transect contained oxic fauna and high diversity. At 14.7 ka, glacial termination IA, hypoxic benthic fauna appeared across the transect, recording hypoxic waters (<0.5 ml L-1) < 300 m from the ocean surface. Bølling/Allerød (B/A) assemblages uniquely stand out in the record, exhibited by low density, diversity, and evenness, and taxonomic composition reflecting extreme and stressful hypoxia and methane-rich environments. Younger Dryas assemblages were diverse and composed of oxic fauna, similar to LGM assemblages. Termination IB initiated another deoxygenation shift, followed by OMZ-associated faunal and density patterns. This analysis strengthens the quantitative assessment of oxygen concentrations involved in deglacial OMZ change and reveals the unexpected, remarkable shallowness of OMZ influence during the B/A.

Dependence of Bacterial Magnetosome Morphology on Chemical Conditions in Deep-sea Sediments

NASA Astrophysics Data System (ADS)

Yamazaki, T.; Suzuki, Y.; Kawamura, N.

2016-12-01

Magnetotactic bacteria (MTB) should play an important role for biogeochemical cycles of iron. MTB are considered to be microaerophilic and most commonly live near or below the oxic-anoxic transition zone (OATZ). However, common occurrence of magnetofossils in Pacific red clay (Yamazaki & Shimono, 2013), which contains abundant dissolved oxygen and does not have an OATZ, may conflict with the widespread interpretations of the ecology of MTB. For better understanding of the ecology in deep-sea sediments, we conducted rock-magnetic, biogeochemical, and microbiological analyses of Japan Sea surface sediments with an OATZ. Rock magnetic proxies and TEM images indicate that magnetofossils occur throughout the sediment columns regardless of the OATZ, even at the sediment-water interface. The proportion of magnetofossils with teardrop morphology increases near the OATZ. These suggest that some species producing teardrop magnetosomes prefer a chemical condition near the OATZ, whereas other species may live in microaerophilic microenvironments around organic particles near the sediment-water interface. The fact that morphology of magnetofossils in Pacific red clay is >90% octahedral suggests that even some species of MTB that yield octahedral magnetosomes might be aerotolerant and prefer oxic environments. To strengthen the notion above, pyrosequencing of 16S rRNA gene sequences was conducted for the corresponding sediments. Among diverse bacterial lineages known to produce magnetosomes, 16S rRNA gene sequences phylogenetically affiliated within the lineage of Nitrospirae known to produce teardrop magnetosomes were distributed only around the OATZ, whereas those affiliated within the family Rhodospirillaceae (α-Proteobacteria) and known to produce octahedral magnetosomes were distributed in all investigated Japan Sea sediments regardless of the OATZ. It is strongly suggested that the dependency on the OATZ is different among phylogenetically and morphologically diverse MTB.

Community composition of ammonia-oxidizing bacteria and archaea in rice field soil as affected by nitrogen fertilization.

PubMed

Wang, Yanan; Ke, Xiubin; Wu, Liqin; Lu, Yahai

2009-02-01

Little information is available on the ecology of ammonia-oxidizing bacteria (AOB) and archaea (AOA) in flooded rice soils. Consequently, a microcosm experiment was conducted to determine the effect of nitrogen fertilizer on the composition of AOB and AOA communities in rice soil by using molecular analyses of ammonia monooxygenase gene (amoA) fragments. Experimental treatments included three levels of N (urea) fertilizer, i.e. 50, 100 and 150 mgNkg(-1) soil. Soil samples were operationally divided into four fractions: surface soil, bulk soil deep layer, rhizosphere and washed root material. NH(4)(+)-N was the dominant form of N in soil porewater and increased with N fertilization. Cloning and sequencing of amoA gene fragments showed that the AOB community in the rice soil consisted of three major groups, i.e. Nitrosomonas communis cluster, Nitrosospira cluster 3a and cluster 3b. The sequences related to Nitrosomonas were predominant. There was a clear effect of N fertilizer and soil depth on AOB community composition based on terminal restriction fragment length polymorphism fingerprinting. Nitrosomonas appeared to be more abundant in the potentially oxic or micro-oxic fractions, including surface soil, rhizosphere and washed root material, than the deep layer of anoxic bulk soil. Furthermore, Nitrosomonas increased relatively in the partially oxic fractions and that of Nitrosospira decreased with the increasing application of N fertilizer. However, AOA community composition remained unchanged according to the denaturing gradient gel electrophoresis analyses.

A 26 million year gap in the central Arctic record at the greenhouse-icehouse transition: Looking for clues

USGS Publications Warehouse

Sangiorgi, Francesca; Brumsack, Hans-Juergen; Willard, Debra A.; Schouten, Stefan; Stickley, Catherine E.; O'Regan, Matthew; Reichart, Gert-Jan; Damste, Jaap S. Sinninghe; Brinkhuis, Henk

2008-01-01

The Cenozoic record of the Lomonosov Ridge (central Arctic Ocean) recovered during Integrated Ocean Drilling Program (IODP) Expedition 302 revealed an unexpected 26 Ma hiatus, separating middle Eocene (∼44.4 Ma) from lower Miocene sediments (∼18.2 Ma). To elucidate the nature of this unconformity, we performed a multiproxy palynological (dinoflagellate cysts, pollen, and spores), micropaleontological (siliceous microfossils), inorganic, and organic (Tetra Ether Index of lipids with 86 carbon atoms (TEX86) and Branched and Isoprenoid Tetraether (BIT)) geochemical analysis of the sediments from ∼5 m below to ∼7 m above the hiatus. Four main paleoenvironmental phases (A–D) are recognized in the sediments encompassing the unconformity, two below (A–B) and two above (C–D): (A) Below the hiatus, proxies show relatively warm temperatures, with Sea Surface Temperatures (TEX86‐derived SSTs) of about 8°C and high fresh to brackish water influence. (B) Approaching the hiatus, proxies indicate a cooling trend (TEX86‐derived SSTs of ∼5°C), increased freshwater influence, and progressive shoaling of the Lomonosov Ridge drilling site, located close to or at sea level. (C) The interval directly above the unconformity contains sparse reworked Cretaceous to Oligocene dinoflagellate cysts. Sediments were deposited in a relatively shallow, restricted marine environment. Proxies show the simultaneous influence of both fresh and marine waters, with alternating oxic and anoxic conditions. Pollen indicates a relatively cold climate. Intriguingly, TEX86‐derived SSTs are unexpectedly high, ∼15–19°C. Such warm surface waters may be partially explained by the ingression of warmer North Atlantic waters after the opening of the Fram Strait during the early Miocene. (D) Sediments of the uppermost interval indicate a phase of extreme oxic conditions, and a well‐ventilated environment, which occurred after the complete opening of the Fram Strait. Importantly, and in contrast with classical postrifting thermal subsidence models for passive margins, our data suggest that sediment erosion and/or nondeposition that generated the hiatus was likely due to a progressive shoaling of the Lomonosov Ridge. A shallow water setting both before and after the hiatus suggests that the Lomonosov Ridge remained at or near sea level for the duration of the gap in the sedimentary record. Interacting sea level changes and/or tectonic activity (possibly uplift) must be invoked as possible causes for such a long hiatus.

Phylogenetic composition and distribution of picoeukaryotes in the hypoxic northwestern coast of the Gulf of Mexico

PubMed Central

Rocke, Emma; Jing, Hongmei; Liu, Hongbin

2013-01-01

Coastal marine hypoxic, or low-oxygen, episodes are an increasing worldwide phenomenon, but its effect on the microbial community is virtually unknown by far. In this study, the community structure and phylogeny of picoeukaryotes in the Gulf of Mexico, which are exposed to severe hypoxia in these areas was explored through a clone library approach. Both oxic surface waters and suboxic bottom waters were collected in August 2010 from three representative stations on the inner Louisiana shelf near the Atchafalaya and Mississippi River plumes. The bottom waters of the two more western stations were much more hypoxic in comparison to those of the station closest to the Mississippi River plume, which were only moderately hypoxic. A phylogenetic analysis of a total 175 sequences, generated from six 18S rDNA clone libraries, demonstrated a clear dominance of parasitic dinoflagellates from Marine alveolate clades I and II in all hypoxic waters as well as in the surface layer at the more western station closest to the Atchafalaya River plume. Species diversity was significantly higher at the most hypoxic sites, and many novel species were present among the dinoflagellate and stramenopile clades. We concluded that hypoxia in the Gulf of Mexico causes a significant shift in picoeukaryote communities, and that hypoxia may cause a shift in microbial food webs from grazing to parasitism. PMID:23281331

Abandoned mine drainage in the Swatara Creek Basin, southern anthracite coalfield, Pennsylvania, USA: 2. performance of treatment systems

USGS Publications Warehouse

Cravotta, Charles A.

2010-01-01

A variety of passive and semi-passive treatment systems were constructed by state and local agencies to neutralize acidic mine drainage (AMD) and reduce the transport of dissolved metals in the upper Swatara Creek Basin in the Southern Anthracite Coalfield in eastern Pennsylvania. To evaluate the effectiveness of selected treatment systems installed during 1995–2001, the US Geological Survey collected water-quality data at upstream and downstream locations relative to each system eight or more times annually for a minimum of 3 years at each site during 1996–2007. Performance was normalized among treatment types by dividing the acid load removed by the size of the treatment system. For the limestone sand, open limestone channel, oxic limestone drain, anoxic limestone drain (ALD), and limestone diversion well treatment systems, the size was indicated by the total mass of limestone; for the aerobic wetland systems, the size was indicated by the total surface area of ponds and wetlands. Additionally, the approximate cost per tonne of acid treated over an assumed service life of 20 years was computed. On the basis of these performance metrics, the limestone sand, ALD, oxic limestone drain, and limestone diversion wells had similar ranges of acid-removal efficiency and cost efficiency. However, the open limestone channel had lower removal efficiency and higher cost per ton of acid treated. The wetlands effectively attenuated metals transport but were relatively expensive considering metrics that evaluated acid removal and cost efficiency. Although the water-quality data indicated that all treatments reduced the acidity load from AMD, the ALD was most effective at producing near-neutral pH and attenuating acidity and dissolved metals. The diversion wells were effective at removing acidity and increasing pH of downstream water and exhibited unique potential to treat moderate to high flows associated with storm flow conditions.

Microbial Manganese and Sulfate Reduction in Black Sea Shelf Sediments

PubMed Central

Thamdrup, Bo; Rosselló-Mora, Ramón; Amann, Rudolf

2000-01-01

The microbial ecology of anaerobic carbon oxidation processes was investigated in Black Sea shelf sediments from mid-shelf with well-oxygenated bottom water to the oxic-anoxic chemocline at the shelf-break. At all stations, organic carbon (Corg) oxidation rates were rapidly attenuated with depth in anoxically incubated sediment. Dissimilatory Mn reduction was the most important terminal electron-accepting process in the active surface layer to a depth of ∼1 cm, while SO42− reduction accounted for the entire Corg oxidation below. Manganese reduction was supported by moderately high Mn oxide concentrations. A contribution from microbial Fe reduction could not be discerned, and the process was not stimulated by addition of ferrihydrite. Manganese reduction resulted in carbonate precipitation, which complicated the quantification of Corg oxidation rates. The relative contribution of Mn reduction to Corg oxidation in the anaerobic incubations was 25 to 73% at the stations with oxic bottom water. In situ, where Mn reduction must compete with oxygen respiration, the contribution of the process will vary in response to fluctuations in bottom water oxygen concentrations. Total bacterial numbers as well as the detection frequency of bacteria with fluorescent in situ hybridization scaled to the mineralization rates. Most-probable-number enumerations yielded up to 105 cells of acetate-oxidizing Mn-reducing bacteria (MnRB) cm−3, while counts of Fe reducers were <102 cm−3. At two stations, organisms affiliated with Arcobacter were the only types identified from 16S rRNA clone libraries from the highest positive MPN dilutions for MnRB. At the third station, a clone type affiliated with Pelobacter was also observed. Our results delineate a niche for dissimilatory Mn-reducing bacteria in sediments with Mn oxide concentrations greater than ∼10 μmol cm−3 and indicate that bacteria that are specialized in Mn reduction, rather than known Mn and Fe reducers, are important in this niche. PMID:10877783

Roles of Ferrous and Sulfide Ions in the Fromation of Algae—Induced Black Bloom in Hyper Eutrophic Freshwater Lakes in China

NASA Astrophysics Data System (ADS)

Shen, Q.; Gao, Q.; Yu, C.; Zhang, L.; Wang, Z.

2016-12-01

Water column hypoxia is one of the most serious threats from eutrophication to large water bodies. In the past several years, black bloom phenomenon has become a serious ecosystem disaster in some important severe eutrophic lakes in China, which caused not only environment degradation but also drinking water crisis. Black color and offensive odour of the water column are two notorious sensory features. High Fe2+ and ΣH2S (ΣS2-=S2-+HS-+H2S) were typical characteristics of the black bloom water. Analysis of the black substances of the black bloom water using X-ray photoelectron spectroscopy indicated that abundant FeS were included in these particulates. The black color of the black bloom water could be attributed to the formation of FeS in the anoxic/anaerobic water column. Field investigation and laboratory incubation experiment indicated that the formation of black bloom was closely related to the Fe2+ and ΣH2S in surface sediments. The Fe2+ concentration in surface sediment pore water was high and showed a release tendency from the sediment water interface to the overlying water during the formation of black bloom, while the similar trend was found in ΣH2S production at sediment water micro-interface. Both Fe2+ and ΣS2- affected by oxic and redox conditions, respectively, contributed to the formation of black bloom significantly. However, ΣS2- was found to be the limiting factor directly controlling the outbreak of black bloom. Analysis of microbioal community diversity demonstrated that sulfate reducing bacteria (SRB) were abundant in the surface sediment of black bloom, which strongly influenced the production and accumulation of ΣH2S and drove the formation of black bloom.

The comparison of greenhouse gas emissions in sewage treatment plants with different treatment processes.

PubMed

Masuda, Shuhei; Sano, Itsumi; Hojo, Toshimasa; Li, Yu-You; Nishimura, Osamu

2018-02-01

Greenhouse gas emissions from different sewage treatment plants: oxidation ditch process, double-circulated anoxic-oxic process and anoxic-oxic process were evaluated based on the survey. The methane and nitrous oxide characteristics were discussed based on the gaseous and dissolved gas profiles. As a result, it was found that methane was produced in the sewer pipes and the primary sedimentation tank. Additionally, a ventilation system would promote the gasification of dissolved methane in the first treatment units. Nitrous oxide was produced and emitted in oxic tanks with nitrite accumulation inside the sewage treatment plant. A certain amount of nitrous oxide was also discharged as dissolved gas through the effluent water. If the amount of dissolved nitrous oxide discharge is not included, 7-14% of total nitrous oxide emission would be overlooked. Based on the greenhouse gas calculation, electrical consumption and the N 2 O emission from incineration process were major sources in all the plants. For greenhouse gas reduction, oxidation ditch process has an advantage over the other advanced systems due to lower energy consumption, sludge production, and nitrogen removal without gas stripping. Copyright © 2017 Elsevier Ltd. All rights reserved.

Reduction and prediction of N2O emission from an Anoxic/Oxic wastewater treatment plant upon DO control and model simulation.

PubMed

Sun, Shichang; Bao, Zhiyuan; Li, Ruoyu; Sun, Dezhi; Geng, Haihong; Huang, Xiaofei; Lin, Junhao; Zhang, Peixin; Ma, Rui; Fang, Lin; Zhang, Xianghua; Zhao, Xuxin

2017-11-01

In order to make a better understanding of the characteristics of N 2 O emission in A/O wastewater treatment plant, full-scale and pilot-scale experiments were carried out and a back propagation artificial neural network model based on the experimental data was constructed to make a precise prediction of N 2 O emission. Results showed that, N 2 O flux from different units followed a descending order: aerated grit tank>oxic zone≫anoxic zone>final clarifier>primary clarifier, but 99.4% of the total emission of N 2 O (1.60% of N-load) was monitored from the oxic zone due to its big surface area. A proper DO control could reduce N 2 O emission down to 0.21% of N-load in A/O process, and a two-hidden-layers back propagation model with an optimized structure of 4:3:9:1 could achieve a good simulation of N 2 O emission, which provided a new method for the prediction of N 2 O emission during wastewater treatment. Copyright © 2017. Published by Elsevier Ltd.

Rock magnetic and geochemical analyses of surface sediment characteristics in deep ocean environments: A case study across the Ryukyu Trench

NASA Astrophysics Data System (ADS)

Kawamura, N.; Kawamura, K.; Ishikawa, N.

2008-03-01

Magnetic minerals in marine sediments are often dissolved or formed with burial depth, thereby masking the primary natural remanent magnetization and paleoclimate signals. In order to clarify the present sedimentary environment and the progressive changes with burial depth in the magnetic properties, we studied seven cores collected from the Ryukyu Trench, southwest Japan. Magnetic properties, organic geochemistry, and interstitial water chemistry of seven cores are described. Bottom water conditions at the landward slope, trench floor, and seaward slope are relatively suboxic, anoxic, and oxic, respectively. The grain size of the sediments become gradually finer with the distance from Okinawa Island and finer with increasing water depth. The magnetic carriers in the sediments are predominantly magnetite and maghemized magnetite, with minor amounts of hematite. In the topmost sediments from the landward slope, magnetic minerals are diluted by terrigenous materials and microfossils. The downcore variations in magnetic properties and geochemical data provided evidence for the dissolution of fine-grained magnetite with burial depth under an anoxic condition.

SERDP ER-1421 Abiotic and Biotic Mechanisms Controlling In Situ Remediation of NDMA: Final Report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Szecsody, James E.; McKinley, James P.; Crocker, Fiona H.

This laboratory-scale project was initiated to investigate in situ abiotic/biotic mineralization of NDMA. Under iron-reducing conditions, aquifer sediments showed rapid abiotic NDMA degradation to dimethylamine (DMA), nitrate, formate, and finally, CO2. These are the first reported experiments of abiotic NDMA mineralization. The NDMA reactivity of these different iron phases showed that adsorbed ferrous iron was the dominant reactive phase that promoted NDMA reduction, and other ferrous phases present (siderite, iron sulfide, magnetite, structural ferrous iron in 2:1 clays) did not promote NDMA degradation. In contrast, oxic sediments that were biostimulated with propane promoted biomineralization of NDMA by a cometabolic monooxygenasemore » enzyme process. Other monooxygenase enzyme processes were not stimulated with methane or toluene additions, and acetylene addition did not block mineralization. Although NDMA mineralization extent was the highest in oxic, biostimulated sediments (30 to 82%, compared to 10 to 26% for abiotic mineralization in reduced sediments), large 1-D column studies (high sediment/water ratio of aquifers) showed 5.6 times higher NDMA mineralization rates in reduced sediment (half-life 410 ± 147 h) than oxic biomineralization (half life 2293 ± 1866 h). Sequential reduced/oxic biostimulated sediment mineralization (half-life 3180 ± 1094 h) was also inefficient compared to reduced sediment. These promising laboratory-scale results for NDMA mineralization should be investigated at field scale. Future studies of NDMA remediation should focus on the comparison of this in situ abiotic NDMA mineralization (iron-reducing environments) to ex situ biomineralization, which has been shown successful in other studies.« less

Iron traps terrestrially derived dissolved organic matter at redox interfaces

PubMed Central

Riedel, Thomas; Zak, Dominik; Biester, Harald; Dittmar, Thorsten

2013-01-01

Reactive iron and organic carbon are intimately associated in soils and sediments. However, to date, the organic compounds involved are uncharacterized on the molecular level. At redox interfaces in peatlands, where the biogeochemical cycles of iron and dissolved organic matter (DOM) are coupled, this issue can readily be studied. We found that precipitation of iron hydroxides at the oxic surface layer of two rewetted fens removed a large fraction of DOM via coagulation. On aeration of anoxic fen pore waters, >90% of dissolved iron and 27 ± 7% (mean ± SD) of dissolved organic carbon were rapidly (within 24 h) removed. Using ultra-high-resolution MS, we show that vascular plant-derived aromatic and pyrogenic compounds were preferentially retained, whereas the majority of carboxyl-rich aliphatic acids remained in solution. We propose that redox interfaces, which are ubiquitous in marine and terrestrial settings, are selective yet intermediate barriers that limit the flux of land-derived DOM to oceanic waters. PMID:23733946

Perspectives on Proterozoic surface ocean redox from iodine contents in ancient and recent carbonate

NASA Astrophysics Data System (ADS)

Hardisty, Dalton S.; Lu, Zunli; Bekker, Andrey; Diamond, Charles W.; Gill, Benjamin C.; Jiang, Ganqing; Kah, Linda C.; Knoll, Andrew H.; Loyd, Sean J.; Osburn, Magdalena R.; Planavsky, Noah J.; Wang, Chunjiang; Zhou, Xiaoli; Lyons, Timothy W.

2017-04-01

The Proterozoic Eon hosted the emergence and initial recorded diversification of eukaryotes. Oxygen levels in the shallow marine settings critical to these events were lower than today's, although how much lower is debated. Here, we use concentrations of iodate (the oxidized iodine species) in shallow-marine limestones and dolostones to generate the first comprehensive record of Proterozoic near-surface marine redox conditions. The iodine proxy is sensitive to both local oxygen availability and the relative proximity to anoxic waters. To assess the validity of our approach, Neogene-Quaternary carbonates are used to demonstrate that diagenesis most often decreases and is unlikely to increase carbonate-iodine contents. Despite the potential for diagenetic loss, maximum Proterozoic carbonate iodine levels are elevated relative to those of the Archean, particularly during the Lomagundi and Shuram carbon isotope excursions of the Paleo- and Neoproterozoic, respectively. For the Shuram anomaly, comparisons to Neogene-Quaternary carbonates suggest that diagenesis is not responsible for the observed iodine trends. The baseline low iodine levels in Proterozoic carbonates, relative to the Phanerozoic, are linked to a shallow oxic-anoxic interface. Oxygen concentrations in surface waters would have at least intermittently been above the threshold required to support eukaryotes. However, the diagnostically low iodine data from mid-Proterozoic shallow-water carbonates, relative to those of the bracketing time intervals, are consistent with a dynamic chemocline and anoxic waters that would have episodically mixed upward and laterally into the shallow oceans. This redox instability may have challenged early eukaryotic diversification and expansion, creating an evolutionary landscape unfavorable for the emergence of animals.

Community composition of ammonia-oxidizing archaea from surface and anoxic depths of oceanic oxygen minimum zones.

PubMed

Peng, Xuefeng; Jayakumar, Amal; Ward, Bess B

2013-01-01

Ammonia-oxidizing archaea (AOA) have been reported at high abundance in much of the global ocean, even in environments, such as pelagic oxygen minimum zones (OMZs), where conditions seem unlikely to support aerobic ammonium oxidation. Due to the lack of information on any potential alternative metabolism of AOA, the AOA community composition might be expected to differ between oxic and anoxic environments. This hypothesis was tested by evaluating AOA community composition using a functional gene microarray that targets the ammonia monooxygenase gene subunit A (amoA). The relationship between environmental parameters and the biogeography of the Arabian Sea and the Eastern Tropical South Pacific (ETSP) AOA assemblages was investigated using principal component analysis (PCA) and redundancy analysis (RDA). In both the Arabian Sea and the ETSP, AOA communities within the core of the OMZ were not significantly different from those inhabiting the oxygenated surface waters above the OMZ. The AOA communities in the Arabian Sea were significantly different from those in the ETSP. In both oceans, the abundance of archaeal amoA gene in the core of the OMZ was higher than that in the surface waters. Our results indicate that AOA communities are distinguished by their geographic origin. RDA suggested that temperature (higher in the Arabian Sea than in the ETSP) was the main factor that correlated with the differences between the AOA communities. Physicochemical properties that characterized the different environments of the OMZ and surface waters played a less important role, than did geography, in shaping the AOA community composition.

Use of chemical and isotopic tracers to characterize the interactions between ground water and surface water in mantled karst

USGS Publications Warehouse

Katz, B.G.; Coplen, T.B.; Bullen, T.D.; Hal, Davis J.

1997-01-01

In the mantled karst terrane of northern Florida, the water quality of the Upper Floridan aquifer is influenced by the degree of connectivity between the aquifer and the surface. Chemical and isotopic analyses [18O/16O (??18O), 2H/1H (??D), 13C/12C (??13C), tritium(3H), and strontium-87/strontium-86(87Sr/86Sr)]along with geochemical mass-balance modeling were used to identify the dominant hydrochemical processes that control the composition of ground water as it evolves downgradient in two systems. In one system, surface water enters the Upper Floridan aquifer through a sinkhole located in the Northern Highlands physiographic unit. In the other system, surface water enters the aquifer through a sinkhole lake (Lake Bradford) in the Woodville Karst Plain. Differences in the composition of water isotopes (??18O and ??D) in rainfall, ground water, and surface water were used to develop mixing models of surface water (leakage of water to the Upper Floridan aquifer from a sinkhole lake and a sinkhole) and ground water. Using mass-balance calculations, based on differences in ??18O and ??D, the proportion of lake water that mixed with meteoric water ranged from 7 to 86% in water from wells located in close proximity to Lake Bradford. In deeper parts of the Upper Floridan aquifer, water enriched in 18O and D from five of 12 sampled municipal wells indicated that recharge from a sinkhole (1 to 24%) and surface water with an evaporated isotopic signature (2 to 32%) was mixing with ground water. The solute isotopes, ??13C and 87Sr/86Sr, were used to test the sensitivity of binary and ternary mixing models, and to estimate the amount of mass transfer of carbon and other dissolved species in geochemical reactions. In ground water downgradient from Lake Bradford, the dominant processes controlling carbon cycling in ground water were dissolution of carbonate minerals, aerobic degradation of organic matter, and hydrolysis of silicate minerals. In the deeper parts of the Upper Floridan aquifer, the major processes controlling the concentrations of major dissolved species included dissolution of calcite and dolomite, and degradation of organic matter under oxic conditions. The Upper Floridan aquifer is highly susceptible to contamination from activities at the land surface in the Tallahassee area. The presence of post-1950s concentrations of 3H in ground water from depths greater than 100 m below land surface indicates that water throughout much of the Upper Floridan aquifer has been recharged during the last 40 years. Even though mixing is likely between ground water and surface water in many parts of the study area, the Upper Floridan aquifer produces good quality water, which due to dilution effects shows little if any impact from trace elements or nutrients that are present in surface waters.The water quality of the Upper Floridan aquifer is influenced by the degree of connectivity between the aquifer and the surface water. Chemical and isotopic analyses, tritium, and strontium-87/strontium-86 along with geochemical mass-balance modeling were used to identify the dominant hydrochemical processes that control the composition of groundwater. Differences in the composition of water isotopes in rainfall, groundwater and surface water were used to develop mixing models of surface water and groundwater. Even though mixing is likely between groundwater and surface water in many parts of the study area, the Upper Floridan aquifer produces good quality water, showing little impact from trace elements present in surface waters.

Degradation of trifluoroacetate in oxic and anoxic sediments

USGS Publications Warehouse

Visscher, P.T.; Culbertson, C.W.; Oremland, R.S.

1994-01-01

THE deleterious effect of chlorofluorocarbons on stratospheric ozone has led to international cooperation to end their use. The search for acceptable alternatives has focused on hydrofluorocarbons (HFCs) or hydrochlorofluorocarbons (HCFCs) which are attractive because they have relatively short atmospheric residence times. HFCs and HCFCs are attacked by tropospheric hydroxyl radicals, leading to the formation of trifluoroacetate (TFA). Most of the atmospheric TFA is deposited at the Earth's surface, where it is thought to be highly resistant to bacterial attack. Therefore, use of HCFCs and HFCs may lead to accumulation of TFA in soils, where it could prove toxic or inhibitory to plants and soil microbial communities. Although little is known about the toxicity of TFA, monofluoroacetate, which occurs at low levels in some plants and which is susceptible to slow attack by aerobic soil microbes, is known to be acutely toxic. Here we report that TFA can be rapidly degraded microbially under anoxic and oxic conditions. These results imply that significant microbial sinks exist in nature for the elimination of TFA from the environment. We also show that oxic degradation of TFA leads to the formation of fluoroform, a potential ozone-depleting compound with a much longer atmospheric lifetime than the parent compounds.The deleterious effect of chlorofluorcarbons on stratospheric ozone has led to international cooperation to end their use. The search for acceptable alternatives has focused on hydroflnorocarbons (HFCs) or hydrochloroflnorcarbons (HCFs) which are attractive because they have relatively short atmospheric residence times. HFCs and HCFs are attacked by tropospheric hydroxyl radicals, leading to the formation of trifluoroacetate (TFA). Most of the atmospheric TFA is deposited at the Earth's surface, where it is thought to be highly resistant to bacterial attack. Therefore, use of HCFs and HCFs may lead to accummulation of TFA in soils, where it could prove toxic or inhibitory to plants and soil microbial communities. Although little is known about the toxicity of TFA, monofluoracetate, which occurs at low levels in some plants and which is susceptible to slow attack by aerobic soil microbes, is known to be acutely toxic. Here we report that TFA can be rapidly degraded microbially under anoxic and oxic conditions. These results imply that significant microbial sinks exist in nature for the elimination of TFA from the environment. We also show that oxic degradation of TFA leads to the formation of fluoroform, a potential ozone-depleting compound with a much longer atmospheric lifetime than the parent compounds.

Transport and removal of viruses in saturated sand columns under oxic and anoxic conditions--Potential implications for groundwater protection.

PubMed

Frohnert, Anne; Apelt, Susann; Klitzke, Sondra; Chorus, Ingrid; Szewzyk, Regine; Selinka, Hans-Christoph

2014-11-01

To protect groundwater as a drinking water resource from microbiological contamination, protection zones are installed. While travelling through these zones, concentrations of potential pathogens should decline to levels that pose no risks to human health. Removal of viruses during subsurface passage is influenced by physicochemical conditions, such as oxygen concentration, which also affects virus survival. The aim of our study was to evaluate the effect of redox conditions on the removal of viruses during sand filtration. Experiments in glass columns filled with medium-grained sand were conducted to investigate virus removal in the presence and absence of dissolved oxygen. Bacteriophages MS2 and PhiX174, as surrogates for human enteric viruses were spiked in pulsed or in continuous mode and pumped through the columns at a filter velocity of about 1m/d. Virus breakthrough curves were analyzed by calculating total viral elimination and fitted using one-dimensional transport models (CXTFIT and HYDRUS-1D). While short-term experiments with pulsed virus application showed only small differences with regard to virus removal under oxic and anoxic conditions, a long-term experiment with continuous dosing revealed a clearly lower elimination of viruses under anoxic conditions. These findings suggest that less inactivation and less adsorption of viruses in anoxic environments affect their removal. Therefore, in risk assessment studies aimed to secure drinking water resources from viral contamination and optimization of protection zones, the oxic and anoxic conditions in the subsurface should also be considered. Copyright © 2014 Elsevier GmbH. All rights reserved.

Predicting groundwater redox status on a regional scale using linear discriminant analysis.

PubMed

Close, M E; Abraham, P; Humphries, B; Lilburne, L; Cuthill, T; Wilson, S

2016-08-01

Reducing conditions are necessary for denitrification, thus the groundwater redox status can be used to identify subsurface zones where potentially significant nitrate reduction can occur. Groundwater chemistry in two contrasting regions of New Zealand was classified with respect to redox status and related to mappable factors, such as geology, topography and soil characteristics using discriminant analysis. Redox assignment was carried out for water sampled from 568 and 2223 wells in the Waikato and Canterbury regions, respectively. For the Waikato region 64% of wells sampled indicated oxic conditions in the water; 18% indicated reduced conditions and 18% had attributes indicating both reducing and oxic conditions termed "mixed". In Canterbury 84% of wells indicated oxic conditions; 10% were mixed; and only 5% indicated reduced conditions. The analysis was performed over three different well depths, <25m, 25 to 100 and >100m. For both regions, the percentage of oxidised groundwater decreased with increasing well depth. Linear discriminant analysis was used to develop models to differentiate between the three redox states. Models were derived for each depth and region using 67% of the data, and then subsequently validated on the remaining 33%. The average agreement between predicted and measured redox status was 63% and 70% for the Waikato and Canterbury regions, respectively. The models were incorporated into GIS and the prediction of redox status was extended over the whole region, excluding mountainous land. This knowledge improves spatial prediction of reduced groundwater zones, and therefore, when combined with groundwater flow paths, improves estimates of denitrification. Copyright © 2016 Elsevier B.V. All rights reserved.

Effect of dissolved oxygen concentration on iron efficiency: Removal of three chloroacetic acids.

PubMed

Tang, Shun; Wang, Xiao-mao; Mao, Yu-qin; Zhao, Yu; Yang, Hong-wei; Xie, Yuefeng F

2015-04-15

The monochloroacetic, dichloroacetic and trichloroacetic acid (MCAA, DCAA and TCAA) removed by metallic iron under controlled dissolved oxygen conditions (0, 0.75, 1.52, 2.59, 3.47 or 7.09 mg/L DO) was investigated in well-mixed batch systems. The removal of CAAs increased first and then decreased with increasing DO concentration. Compared with anoxic condition, the reduction of MCAA and DCAA was substantially enhanced in the presence of O2, while TCAA reduction was significantly inhibited above 2.59 mg/L. The 1.52 mg/L DO was optimum for the formation of final product, acetic acid. Chlorine mass balances were 69-102%, and carbon mass balances were 92-105%. With sufficient mass transfer from bulk to the particle surface, the degradation of CAAs was limited by their reduction or migration rate within iron particles, which were dependent on the change of reducing agents and corrosion coatings. Under anoxic conditions, the reduction of CAAs was mainly inhibited by the available reducing agents in the conductive layer. Under low oxic conditions, the increasing reducing agents and thin lepidocrocite layer were favorable for CAA dechlorination. Under high oxic conditions, the redundant oxygen competing for reducing agents and significant lepidocrocite growth became the major restricting factors. Various CAA removal mechanisms could be potentially applied to explaining the effect of DO concentration on iron efficiency for contaminant reduction in water and wastewater treatment. Copyright © 2015 Elsevier Ltd. All rights reserved.

Formation of early-middle Miocene red beds in the South China Sea: element geochemistry and mineralogy analysis

NASA Astrophysics Data System (ADS)

Lyu, X.; Liu, Z.

2017-12-01

The formation of oceanic red beds that usually present oxic and oligotrophic conditions with low sedimentation rate has been used to trace depositional paleoenvironment and paleoclimate change. Red beds overlying oceanic basalts were drilled at two adjacent Sites U1433 and U1434 of IODP Expedition 349 in the Southwest Subbasin of the South China Sea. The occurrence of early-middle Miocene red beds may indicate that at that time there was oxic and quiet marine environment in the deep South China Sea. To understand their formation of red-color, local depositional condition, and potential paleoceanographic significance, major elements (XRF), trace and rare earth elements (ICP-MS), Fe chemical speciation (modified sequential iron extraction procedure), and Fe oxic minerals (CBD and DRS) were analyzed. Geochemical and mineralogical data reveal that hematite and goethite are responsible for the reddish color and red beds were deposited under highly oxic, oligotrophic conditions with a little later hydrothermal influence in the South China Sea. Our results indicate that: (1) after treatment using the CBD procedure, the red samples presented a change in color to greenish, showing the iron oxides being responsible for the sediment color; (2) enriched Mn, depleted U, S enrichment factors, and negative Ce anomaly show that the water mass was pre-oxidized before transported to the study location; (3) low primary productivity was inferred from the lower P, Ba enrichment factors in red beds compared to non-red beds; (4) the excess Mo influx at the bottom may come from the later hydrothermal input; (5) the diverse Ca enrichment factors and correlations between Fe and Al suggest different allogenic sources for red beds at our two sites. We conclude that the red beds at Sites U1433 and U1434 despite their diverse sources both developed in externally oxidized water mass and low primary productivity conditions, and partially altered by hydrothermal fluids after their pelagic deposition. In the Miocene, the South China Sea was open to the western Pacific, and our study suggests an oxidized deepwater environment in the Pacific during the Miocene.

Late Quaternary changes in intermediate water oxygenation and oxygen minimum zone, northern Japan: A benthic foraminiferal perspective

NASA Astrophysics Data System (ADS)

Shibahara, Akihiko; Ohkushi, Ken'ichi; Kennett, James P.; Ikehara, Ken

2007-09-01

A strong oxygen minimum zone (OMZ) currently exists at upper intermediate water depths on the northern Japanese margin, NW Pacific. The OMZ results largely from a combination of high surface water productivity and poor ventilation of upper intermediate waters. We investigated late Quaternary history (last 34 kyr) of ocean floor oxygenation and the OMZ using quantitative changes in benthic foraminiferal assemblages in three sediment cores taken from the continental slope off Shimokita Peninsula and Tokachi, northern Japan, at water depths between 975 and 1363 m. These cores are well located within the present-day OMZ, a region of high surface water productivity, and in close proximity to the source region of North Pacific Intermediate Water. Late Quaternary benthic foraminiferal assemblages experienced major changes in response to changes in dissolved oxygen concentration in ocean floor sediments. Foraminiferal assemblages are interpreted to represent three main groups representing oxic, suboxic, and dysoxic conditions. Assemblage changes in all three cores and hence in bottom water oxygenation coincided with late Quaternary climatic episodes, similar to that known for the southern California margin. These episodes, in turn, are correlated with orbital and millennial climate episodes in the Greenland ice core including the last glacial episode, Bølling-Ållerød (B/A), Younger Dryas, Preboreal (earliest Holocene), early Holocene, and late Holocene. The lowest oxygen conditions, marked by dysoxic taxa and laminated sediments in one core, occurred during the B/A and the Preboreal intervals. Suboxic taxa dominated mainly during the last glacial, the Younger Dryas, and most of the Holocene. Dysoxic conditions during the B/A and Preboreal intervals in this region were possibly caused by high surface water productivity at times of reduced intermediate ventilation in the northwestern Pacific. Remarkable similarities are evident in the late Quaternary sequence of benthic foraminiferal assemblage change between the two very distant continental margins of northern Japan and southern California. The oscillations in OMZ strength, reflected by these faunal changes, were widespread and apparently synchronous over wide areas of the North Pacific, reflecting broad changes in intermediate water ventilation and surface ocean productivity closely linked with late Quaternary climate change on millennial and orbital timescales.

Mercury in the Black Sea: New Insights From Measurements and Numerical Modeling

NASA Astrophysics Data System (ADS)

Rosati, G.; Heimbürger, L. E.; Melaku Canu, D.; Lagane, C.; Laffont, L.; Rijkenberg, M. J. A.; Gerringa, L. J. A.; Solidoro, C.; Gencarelli, C. N.; Hedgecock, I. M.; De Baar, H. J. W.; Sonke, J. E.

2018-04-01

Redox conditions and organic matter control marine methylmercury (MeHg) production. The Black Sea is the world's largest and deepest anoxic basin and is thus ideal to study Hg species along the extended redox gradient. Here we present new dissolved Hg and MeHg data from the 2013 GEOTRACES MEDBlack cruise (GN04_leg2) that we integrated into a numerical 1-D model, to track the fate and dynamics of Hg and MeHg. Contrary to a previous study, our new data show highest MeHg concentrations in the permanently anoxic waters. Observed MeHg/Hg percentage (range 9-57%) in the anoxic waters is comparable to other subsurface maxima in oxic open-ocean waters. With the modeling we tested for various Hg methylation and demethylation scenarios along the redox gradient. The results show that Hg methylation must occur in the anoxic waters. The model was then used to simulate the time evolution (1850-2050) of Hg species in the Black Sea. Our findings quantify (1) inputs and outputs of HgT ( 31 and 28 kmol yr-1) and MeHgT ( 5 and 4 kmol yr-1) to the basin, (2) the extent of net demethylation occurring in oxic ( 1 kmol yr-1) and suboxic water ( 6 kmol yr-1), (3) and the net Hg methylation in the anoxic waters of the Black Sea ( 11 kmol yr-1). The model was also used to estimate the amount of anthropogenic Hg (85-93%) in the Black Sea.

Quantifying the sources and sinks of nitrite in the oxygen minimum zone of the Eastern Tropical South Pacific

NASA Astrophysics Data System (ADS)

Ji, Qixing; Widner, Brittany; Jayakumar, Amal; Ward, Bess; Mulholland, Margaret

2017-04-01

In coastal upwelling regions, high surface productivity leads to high export and intense remineralization consuming oxygen. This, in combination with slow ventilation, creates oxygen minimum zones (OMZ) in eastern boundary regions of the ocean, such as the one off the Peruvian coast in the Eastern Tropical South Pacific. The OMZ is characterized by a layer of high nitrite concentration coinciding with water column anoxia. Sharp oxygen gradients are located above and below the anoxic layer (upper and lower oxyclines). Thus, the OMZ harbors diverse microbial metabolisms, several of which involve the production and consumption of nitrite. The sources of nitrite are ammonium oxidation and nitrate reduction. The sinks of nitrite include anaerobic ammonium oxidation (anammox), canonical denitrification and nitrite oxidation to nitrate. To quantify the sources and sinks of nitrite in the Peruvian OMZ, incubation experiments with 15N-labeled substrates (ammonium, nitrite and nitrate) were conducted on a research cruise in January 2015. The direct measurements of instantaneous nitrite production and consumption rates were compared with ambient nitrite concentrations to evaluate the turnover rate of nitrite in the OMZ. The distribution of nitrite in the water column showed a two-peak structure. A primary nitrite maximum (up to 0.5 μM) was located in the upper oxycline. A secondary nitrite maximum (up to 10 μM) was found in the anoxic layer. A nitrite concentration minimum occurred at the oxic-anoxic interface just below the upper oxycline. For the sources of nitrite, highest rates of ammonium oxidation and nitrate reduction were detected in the upper oxycline, where both nitrite and oxygen concentrations were low. Lower rates of nitrite production were detected within the layer of secondary nitrite maximum. For the sinks of nitrite, the rates of anammox, denitrification and nitrite oxidation were the highest just below the oxic-anoxic interface. Low nitrite consumption rates were also detected within the layer of the secondary nitrite maximum. The imbalances between nitrite production and consumption rates help to explain the distribution of nitrite in the water column. The primary nitrite maximum in the upper oxycline is consistent with ammonium oxidation exceeding nitrite oxidation. Nitrite consumption rates exceeding rates of nitrite production result in the low nitrite concentration at the oxic-anoxic interface. Within the secondary nitrite maximum in the anoxic layer, production and consumption of nitrite are equivalent within measurement error. These low turnover rates suggest the stability of the nitrite pool in the secondary nitrite maximum over long time scales (decades to millennial). These data could be implemented into biogeochemical models to decipher the origin and the evolution of nitrite distribution in the OMZs.

Next-Generation Sequencing Assessment of Eukaryotic Diversity in Oil Sands Tailings Ponds Sediments and Surface Water.

PubMed

Aguilar, Maria; Richardson, Elisabeth; Tan, BoonFei; Walker, Giselle; Dunfield, Peter F; Bass, David; Nesbø, Camilla; Foght, Julia; Dacks, Joel B

2016-11-01

Tailings ponds in the Athabasca oil sands (Canada) contain fluid wastes, generated by the extraction of bitumen from oil sands ores. Although the autochthonous prokaryotic communities have been relatively well characterized, almost nothing is known about microbial eukaryotes living in the anoxic soft sediments of tailings ponds or in the thin oxic layer of water that covers them. We carried out the first next-generation sequencing study of microbial eukaryotic diversity in oil sands tailings ponds. In metagenomes prepared from tailings sediment and surface water, we detected very low numbers of sequences encoding eukaryotic small subunit ribosomal RNA representing seven major taxonomic groups of protists. We also produced and analysed three amplicon-based 18S rRNA libraries prepared from sediment samples. These revealed a more diverse set of taxa, 169 different OTUs encompassing up to eleven higher order groups of eukaryotes, according to detailed classification using homology searching and phylogenetic methods. The 10 most abundant OTUs accounted for > 90% of the total of reads, vs. large numbers of rare OTUs (< 1% abundance). Despite the anoxic and hydrocarbon-enriched nature of the environment, the tailings ponds harbour complex communities of microbial eukaryotes indicating that these organisms should be taken into account when studying the microbiology of the oil sands. © 2016 The Author(s) Journal of Eukaryotic Microbiology © 2016 International Society of Protistologists.

Assessing environmental changes in Lake Shihwa, South Korea, based on distributions and stable carbon isotopic compositions of n-alkanes.

PubMed

Kim, Dahae; Kim, Jung-Hyun; Kim, Min-Seob; Ra, Kongtae; Shin, Kyung-Hoon

2018-05-04

We investigate historical environmental changes in an artificial lake, Lake Shihwa in South Korea, based on bulk (TOC, TN, C/N ratio, δ 13 C TOC , and δ 15 N TN ) and molecular (concentrations and δ 13 C of n-alkanes) parameters, by analyzing riverbank sediments (n = 12), lake surface sediments (n = 9), and lake core sediments (n = 108). Although the bulk organic parameters showed similar characteristics for all lake surface sediment samples, the distribution pattern and δ 13 C of n-alkanes revealed distinct differences between 2009 samples and 2012/2016 samples. This change of sedimentary organic matter characteristics can be attributed to operation of the tidal power plant that began in 2011, which improved lake water circulation and thus changed the lake sedimentary environment from anoxic to more oxic conditions. The vertical profiles of bulk and molecular lake sediment core records collected in 2009, especially at the site closest to the dike, showed a drastic shift around 1987, indicating that stronger anoxic sedimentary conditions prevailed after 1987. This is linked to sea dike construction in 1987, which prohibited sea-lake water exchange and thus deteriorated water quality in Lake Shihwa. We conclude that Lake Shihwa has experienced severe environmental changes due to human activities. Copyright © 2018 Elsevier Ltd. All rights reserved.

Isolation of heterotrophic diazotrophic bacteria from estuarine surface waters.

PubMed

Farnelid, Hanna; Harder, Jens; Bentzon-Tilia, Mikkel; Riemann, Lasse

2014-10-01

The wide distribution of diverse nitrogenase (nifH) genes affiliated with those of heterotrophic bacteria in marine and estuarine waters indicates ubiquity and an ecologically relevant role for heterotrophic N2 -fixers (diazotrophs) in aquatic nitrogen (N) cycling. However, the lack of cultivated representatives currently precludes an evaluation of their N2 -fixing capacity. In this study, microoxic or anoxic N-free media were inoculated with estuarine Baltic Sea surface water to select for N2 -fixers. After visible growth and isolation of single colonies on oxic plates or in anoxic agar tubes, nifH gene amplicons were obtained from 64 strains and nitrogenase activity, applying the acetylene reduction assay, was confirmed for 40 strains. Two strains, one Gammaproteobacterium affiliated with Pseudomonas and one Alphaproteobacterium affiliated with Rhodopseudomonas were shown to represent established members of the indigenous diazotrophic community in the Baltic Sea, with abundances of up to 7.9 × 10(4) and 4.7 × 10(4)  nifH copies l(-1) respectively. This study reports media for successful isolation of heterotrophic diazotrophs. The applied methodology and the obtained strains will facilitate future identification of factors controlling heterotrophic diazotrophic activity in aquatic environments, which is a prerequisite for understanding and evaluating their ecology and contribution to N cycling at local and regional scales. © 2013 Society for Applied Microbiology and John Wiley & Sons Ltd.

Buried particulate organic carbon stimulates denitrification and nitrate retention in stream sediments at the groundwater-surface water interface

USGS Publications Warehouse

Stelzer, Robert S.; Scott, J. Thad; Bartsch, Lynn

2015-01-01

The interface between ground water and surface water in streams is a hotspot for N processing. However, the role of buried organic C in N transformation at this interface is not well understood, and inferences have been based largely on descriptive studies. Our main objective was to determine how buried particulate organic C (POC) affected denitrification and NO3− retention in the sediments of an upwelling reach in a sand-plains stream in Wisconsin. We manipulated POC in mesocosms inserted in the sediments. Treatments included low and high quantities of conditioned red maple leaves (buried beneath combusted sand), ambient sediment (sand containing background levels of POC), and a control (combusted sand). We measured denitrification rates in sediments by acetylene-block assays in the laboratory and by changes in N2 concentrations in the field using membrane inlet mass spectrometry. We measured NO3−, NH4+, and dissolved organic N (DON) retention as changes in concentrations and fluxes along groundwater flow paths in the mesocosms. POC addition drove oxic ground water to severe hypoxia, led to large increases in dissolved organic C (DOC), and strongly increased denitrification rates and N (NO3− and total dissolved N) retention relative to the control. In situ denitrification accounted for 30 to 60% of NO3− retention. Our results suggest that buried POC stimulated denitrification and NO3− retention by producing DOC and by creating favorable redox conditions for denitrification.

Anoxygenic photosynthesis modulated Proterozoic oxygen and sustained Earth's middle age

PubMed Central

Johnston, D. T.; Wolfe-Simon, F.; Pearson, A.; Knoll, A. H.

2009-01-01

Molecular oxygen (O2) began to accumulate in the atmosphere and surface ocean ca. 2,400 million years ago (Ma), but the persistent oxygenation of water masses throughout the oceans developed much later, perhaps beginning as recently as 580–550 Ma. For much of the intervening interval, moderately oxic surface waters lay above an oxygen minimum zone (OMZ) that tended toward euxinia (anoxic and sulfidic). Here we illustrate how contributions to primary production by anoxygenic photoautotrophs (including physiologically versatile cyanobacteria) influenced biogeochemical cycling during Earth's middle age, helping to perpetuate our planet's intermediate redox state by tempering O2 production. Specifically, the ability to generate organic matter (OM) using sulfide as an electron donor enabled a positive biogeochemical feedback that sustained euxinia in the OMZ. On a geologic time scale, pyrite precipitation and burial governed a second feedback that moderated sulfide availability and water column oxygenation. Thus, we argue that the proportional contribution of anoxygenic photosynthesis to overall primary production would have influenced oceanic redox and the Proterozoic O2 budget. Later Neoproterozoic collapse of widespread euxinia and a concomitant return to ferruginous (anoxic and Fe2+ rich) subsurface waters set in motion Earth's transition from its prokaryote-dominated middle age, removing a physiological barrier to eukaryotic diversification (sulfide) and establishing, for the first time in Earth's history, complete dominance of oxygenic photosynthesis in the oceans. This paved the way for the further oxygenation of the oceans and atmosphere and, ultimately, the evolution of complex multicellular organisms. PMID:19805080

Anoxygenic photosynthesis modulated Proterozoic oxygen and sustained Earth's middle age.

PubMed

Johnston, D T; Wolfe-Simon, F; Pearson, A; Knoll, A H

2009-10-06

Molecular oxygen (O(2)) began to accumulate in the atmosphere and surface ocean ca. 2,400 million years ago (Ma), but the persistent oxygenation of water masses throughout the oceans developed much later, perhaps beginning as recently as 580-550 Ma. For much of the intervening interval, moderately oxic surface waters lay above an oxygen minimum zone (OMZ) that tended toward euxinia (anoxic and sulfidic). Here we illustrate how contributions to primary production by anoxygenic photoautotrophs (including physiologically versatile cyanobacteria) influenced biogeochemical cycling during Earth's middle age, helping to perpetuate our planet's intermediate redox state by tempering O(2) production. Specifically, the ability to generate organic matter (OM) using sulfide as an electron donor enabled a positive biogeochemical feedback that sustained euxinia in the OMZ. On a geologic time scale, pyrite precipitation and burial governed a second feedback that moderated sulfide availability and water column oxygenation. Thus, we argue that the proportional contribution of anoxygenic photosynthesis to overall primary production would have influenced oceanic redox and the Proterozoic O(2) budget. Later Neoproterozoic collapse of widespread euxinia and a concomitant return to ferruginous (anoxic and Fe(2+) rich) subsurface waters set in motion Earth's transition from its prokaryote-dominated middle age, removing a physiological barrier to eukaryotic diversification (sulfide) and establishing, for the first time in Earth's history, complete dominance of oxygenic photosynthesis in the oceans. This paved the way for the further oxygenation of the oceans and atmosphere and, ultimately, the evolution of complex multicellular organisms.

Rapid Return of Nitrogen but not Phosphorus to Ecosystem Nutrition During Decomposition of Quagga Mussel Tissue in Sand, Mud, or Water During Oxic or Anoxic Incubation: Implications for Phytoplankton Bioenergetics.

NASA Astrophysics Data System (ADS)

Cooney, E. M.; Cuhel, R. L.; Aguilar, C.

2016-02-01

In 2003 Quagga mussels were found to have invaded Lake Michigan. Their presence has changed the structure of the lake both ecologically (benthification) as well as chemically (oligotrophication). They consume large amounts of phytoplankton, which decreases the particulate nitrogen and phosphorous nutrients available to other consumers including zooplankton. As a result, fisheries productivity has decreased nearly 95%. Recently reaching the end of the first life cycle, in death they release a portion of these nutrients back into the freshwater system during decomposition. This work determined amounts of phosphorus and nitrogen nutrient recycling for several relevant sediment-water interface conditions: oxic vs anoxic in water, mud, or sand over a weeklong period. Concentrations of ammonium, soluble reactive phosphorus, and nitrate were used to analyze nutrient release as decomposition took place. In a short time up to 25% of tissue N was released as ammonia, and under oxic conditions in mud or sand, nitrification converted some of the ammonia to nitrate. Unexpectedly, mussels decaying in anoxic conditions released ammonium much more slowly. A slower rate of release in ammonium for the intact body with the shell (burial) was observed when compared to ground mussel tissue (detritivory). Nitrate was removed in anoxic incubations, indicating anaerobic denitrification. Phosphate release was initially higher under anoxic conditions than those decaying aerobically. There was no significant difference in the amount or rate of release of SRP between ground mussel and whole bodied with the shell. The anoxic treatment showed similar patterns of release for both ground mussel and intact body with shell. Most important, phosphate was subsequently removed in all treatments and diffusible nutrient was minimal (<100nM). The results link to nutrient assimilation patterns of deep phytoplankton communities, which can replace nitrate with ammonium as an N source.

Aquifer-scale controls on the distribution of nitrate and ammonium in ground water near La Pine, Oregon, USA

USGS Publications Warehouse

Hinkle, S.R.; Böhlke, J.K.; Duff, J.H.; Morgan, D.S.; Weick, R.J.

2007-01-01

Geochemical and isotopic tools were applied at aquifer, transect, and subtransect scales to provide a framework for understanding sources, transport, and fate of dissolved inorganic N in a sandy aquifer near La Pine, Oregon. NO3 is a common contaminant in shallow ground water in this area, whereas high concentrations of NH4-N (up to 39 mg/L) are present in deep ground water. N concentrations, N/Cl ratios, tracer-based apparent ground-water ages, N isotope data, and hydraulic gradients indicate that septic tank effluent is the primary source of NO3. N isotope data, N/Cl and N/C relations, 3H data, and hydraulic considerations point to a natural, sedimentary organic matter source for the high concentrations of NH4, and are inconsistent with an origin as septic tank N. Low recharge rates and flow velocities have largely restricted anthropogenic NO3 to isolated plumes within several meters of the water table. A variety of geochemical and isotopic data indicate that denitrification also affects NO3 gradients in the aquifer. Ground water in the La Pine aquifer evolves from oxic to increasingly reduced conditions. Suboxic conditions are achieved after about 15-30 y of transport below the water table. NO3 is denitrified near the oxic/suboxic boundary. Denitrification in the La Pine aquifer is characterized well at the aquifer scale with a redox boundary approach that inherently captures spatial variability in the distribution of electron donors. ?? 2006 Elsevier B.V. All rights reserved.

Authigenic Uranium in Eastern Equatorial Pacific Sediments

NASA Astrophysics Data System (ADS)

Marcantonio, F.; Lyle, M. W.; Loveley, M. R.; Ibrahim, R.

2014-12-01

Authigenic U concentrations have been used as an indicator of redox state in marine sediments. Soluble U(VI) in porewaters is reduced to insoluble U(IV) under suboxic conditions setting up a diffusion gradient through which U in bottom waters is supplied to reducing sediments. Researchers have used sedimentary redox enrichment of U as a tool to identify past redox changes, which may be caused by changes in organic carbon rain rates and/or bottom water oxygen levels. Differentiating between these two explanations is important, as the former is tied to the use of authigenic U as a paleoproductivity proxy. We examined sediments from 4 sediment cores retrieved from two different localities in the Panama Basin in the eastern equatorial Pacific. Two cores were retrieved from the northern Panama basin at the Cocos Ridge, (4JC at 5° 44.7'N 85° 45.5' W, 1730 m depth; 8JC at 6° 14.0'N 86° 2.6' W, 1993 m depth), and two were retrieved from the south at the Carnegie Ridge, (11JC at 0° 41.6'S 85° 20.0' W, 2452 m depth; 17JC at 0° 10.8'S 85° 52.0' W, 2846 m depth). Using 230Th systematics and seismic profiling at each of the sites, we've identified significant sediment winnowing (4JC and 11JC) and focusing (8JC and 17JC). At all sites, we believe that changes in age-model-derived sand (i.e., >63µm) mass accumulation rates (MAR) best represent changes in rain rates. Glacial rain rates are higher than those in the Holocene by a factor of 2-3 at both sites. Peak Mn levels (>1%), the brown-to-green color transition (which likely represents the oxic/post-oxic boundary), and peak U concentrations all appear in the same order with increasing depth down core. At the Carnegie sites, where MARs are greater than those at the Cocos sites, increases in authigenic U (up to 4 ppm) occur during the mid- to late Holocene at depths of 10-15 cm. At the Cocos sites, increases in authigenic U (up to 12 ppm) occur lower in the sediment column (25-30 cm) during the late glacial. The decrease in sediment MAR (and, likely, productivity) between the last glacial and the Holocene has most likely driven the syndiagenetic enrichment of U at these sites by diffusion of bottom water U to slightly beyond the oxic/post-oxic boundary. Hence, changing bottom water oxygen levels are not a requirement to explain authigenic U concentrations in eastern equatorial Pacific sediments.

Biodegradation of N-nitrosodimethylamine in soil from a water reclamation facility

USGS Publications Warehouse

Bradley, Paul M.; Carr, Steve A.; Baird, Rodger B.; Chapelle, Francis H.

2005-01-01

The potential introduction of N-nitrosodimethylamine (NDMA) into groundwater during water reclamation activities poses a significant risk to groundwater drinking supplies. Greater than 54% biodegradation of N-[methyl-14C]NDMA to 14CO2 or to 14CO2 and 14CH4 was observed in soil from a water reclamation facility under oxic or anoxic conditions, respectively. Likewise, biodegradation was significant in microcosms containing soil with no history of NDMA contamination. These results indicate that aerobic and anaerobic biodegradation of NDMA may be an effective component of NDMA attenuation in water reclamation facility soils.

Assessing the fate of explosives derived nitrate in mine waste rock dumps using the stable isotopes of oxygen and nitrogen.

PubMed

Hendry, M Jim; Wassenaar, Leonard I; Barbour, S Lee; Schabert, Marcie S; Birkham, Tyler K; Fedec, Tony; Schmeling, Erin E

2018-05-29

Ammonium nitrate (NH 4 NO 3 ) mixed with fuel oil is a common blasting agent used to fragment rock into workable size fractions at mines throughout the world. The decomposition and oxidation of undetonated explosives can result in high NO 3 - concentrations in waters emanating from waste rock dumps. We used the stable isotopic composition of NO 3 - (δ 15 N- and δ 18 O-NO 3 - ) to define and quantify the controls on NO 3 - composition in waste rock dumps by studying water-unsaturated and saturated conditions at nine coal waste rock dumps located in the Elk Valley, British Columbia, Canada. Estimates of the extent of nitrification of NH 4 NO 3 in oxic zones in the dumps, initial NO 3 - concentrations prior to denitrification, and the extent of NO 3 - removal by denitrification in sub-oxic to anoxic zones are provided. δ 15 N data from unsaturated waste rock dumps confirm NO 3 - is derived from blasting. δ 15 N- and δ 18 O-NO 3 - data show extensive denitrification can occur in saturated waste rock and in localized zones of elevated water saturation and low oxygen concentrations in unsaturated waste rock. At the mine dump scale, the extent of denitrification in the unsaturated waste rock was inferred from water samples collected from underlying rock drains. Copyright © 2018. Published by Elsevier B.V.

Factors Affecting Spatial and Temporal Variability in Nutrient and Pesticide Concentrations in the Surficial Aquifer on the Delmarva Peninsula

USGS Publications Warehouse

Debrewer, Linda M.; Ator, Scott W.; Denver, Judith M.

2007-01-01

Water quality in the unconfined, unconsolidated surficial aquifer on the Delmarva Peninsula is influenced by the availability of soluble ions from natural and human sources, and by geochemical factors that affect the mobility and fate of these ions within the aquifer. Ground-water samples were collected from 60 wells completed in the surficial aquifer of the peninsula in 2001 and analyzed for major ions, nutrients, and selected pesticides and degradation products. Analytical results were compared to similar data from a subset of sampled wells in 1988, as well as to land use, soils, geology, depth, and other potential explanatory variables to demonstrate the effects of natural and human factors on water quality in the unconfined surficial aquifer. This study was conducted as part of the National Water-Quality Assessment Program of the U.S. Geological Survey, which is designed (in part) to describe the status and trends in ground-water quality and to provide an understanding of natural and human factors that affect ground-water chemistry in different parts of the United States. Results of this study may be useful for water-resources managers tasked with addressing water-quality issues of local and regional importance because the surficial aquifer on the Delmarva Peninsula is a major source of water for domestic and public supply and provides the majority of flow in local streams. Human impacts are apparent in ground-water quality throughout the surficial aquifer. The surficial aquifer on the Delmarva Peninsula is generally sandy and very permeable with well-oxygenated ground water. Dissolved constituents found throughout various depths of the unconfined aquifer are likely derived from the predominantly agricultural practices on the peninsula, although effects of road salt, mineral dissolution, and other natural and human influences are also apparent in some areas. Nitrate occurred at concentrations exceeding natural levels in many areas, and commonly exceeded 10 milligrams per liter (as nitrogen). In addition to land use in the aquifer recharge area, concentrations of nitrate in ground water are related to regional patterns in soil drainage that affect underlying aquifer redox conditions. Over the peninsula, nitrate concentrations are not related to recharge date of the water, but are positively correlated with depth in shallow wells screened beneath agricultural areas. Nitrate concentrations increased in oxic areas (dissolved oxygen greater than 1 milligram per liter) of the deeper part of the surficial aquifer used for domestic supply by an average of about 2 milligrams per liter between 1988 and 2001, although no changes were apparent in shallower parts of the aquifer over that same period. Water in the surficial aquifer generally flows from land-surface recharge to surface-water discharge areas in less than 30 years. As a result, the entire flow system in the surficial aquifer has likely been affected by human activities on and near the land surface over the past several decades. Pesticide compounds occurred widely at low levels throughout the surficial aquifer. The most commonly used herbicides (metolachlor, alachlor, and atrazine) were the most commonly detected. These pesticides primarily occurred in ground water in the form of degradation products. The widespread occurrence of these and other pesticide compounds reflects their abundant use as well as chemical properties and aquifer characteristics that allow their movement into ground water. Mixtures of pesticides are common. Most samples contained at least 3 different compounds; several samples contained as many as 11. Pesticide concentrations in the surficial aquifer are relatively high beneath recharge areas with well-drained soils in the shallow part of the aquifer and in oxic environments throughout the surficial aquifer. Concentrations are generally below existing drinking-water standards, although standards are not available for all of the pesticide compound

Evolution of oceanic molybdenum and uranium reservoir size around the Ediacaran-Cambrian transition: Evidence from western Zhejiang, South China

NASA Astrophysics Data System (ADS)

Xiang, Lei; Schoepfer, Shane D.; Shen, Shu-zhong; Cao, Chang-qun; Zhang, Hua

2017-04-01

The "Cambrian explosion" is one of the most fascinating episodes of diversification in the history of life; however, its relationship to the oxygenation of the oceans and atmosphere around the Ediacaran-Cambrian transition is not fully understood. Marine inventories of redox-sensitive trace elements reflect the relative balance of oxidative weathering on land and deposition in anoxic water masses, and can be used to explore the evolution of oceanic and atmospheric redox conditions. For this study, we conducted a series of geochemical analyses on the upper Lantian, Piyuancun, and Hetang formations in the Chunye-1 well, part of the lower Yangtze Block in western Zhejiang. Iron speciation results indicate that the entire studied interval was deposited under anoxic conditions, with three intervals of persistent euxinia occurring in the uppermost Lantian Fm., the lower Hetang Formation (Fm.), and the upper Hetang Fm. Molybdenum (Mo) and uranium (U) contents and Mo/TOC and U/TOC ratios from the anoxic/euxinic intervals of the Chunye-1 well, combined with published data from the sections in the middle and upper Yangtze Block, suggest that the oceanic Mo reservoir declined consistently from the Ediacaran to Cambrian Stage 3, while the size of the oceanic U reservoir remained relatively constant. Both metals were depleted in the ocean in lower Cambrian Stage 4, before increasing markedly at the end of Stage 4. The lack of an apparent increase in the size of the marine Mo and U reservoir from the upper Ediacaran to Cambrian Stage 3 suggests that oxic water masses did not expand until Cambrian Stage 4. The increase in marine Mo and U availability in the upper Hetang Fm. may have been due to the expansion of oxic water masses in the oceans, associated with oxygenation of the atmosphere during Cambrian Stage 4. This expansion of oxic waters in the global ocean postdates the main phase of Cambrian diversification, suggesting that pervasive oxygenation of the ocean on a large scale was not the primary control on animal diversity following the Ediacaran-Cambrian transition.

Biogeochemical and hydrologic processes controlling mercury cycling in Great Salt Lake, Utah

NASA Astrophysics Data System (ADS)

Naftz, D.; Kenney, T.; Angeroth, C.; Waddell, B.; Darnall, N.; Perschon, C.; Johnson, W. P.

2006-12-01

Great Salt Lake (GSL), in the Western United States, is a terminal lake with a highly variable surface area that can exceed 5,100 km2. The open water and adjacent wetlands of the GSL ecosystem support millions of migratory waterfowl and shorebirds from throughout the Western Hemisphere, as well as a brine shrimp industry with annual revenues exceeding 70 million dollars. Despite the ecologic and economic significance of GSL, little is known about the biogeochemical cycling of mercury (Hg) and no water-quality standards currently exist for this system. Whole water samples collected since 2000 were determined to contain elevated concentrations of total Hg (100 ng/L) and methyl Hg (33 ng/L). The elevated levels of methyl Hg are likely the result of high rates of SO4 reduction and associated Hg methylation in persistently anoxic areas of the lake at depths greater than 6.5 m below the water surface. Hydroacoustic equipment deployed in this anoxic layer indicates a "conveyor belt" flow system that can distribute methyl Hg in a predominantly southerly direction throughout the southern half of GSL (fig. 1, URL: http://users.o2wire.com/dnaftz/Dave/AGU-abs-figs- AUG06.pdf). Periodic and sustained wind events on GSL may result in transport of the methyl Hg-rich anoxic water and bottom sediments into the oxic and biologically active regions. Sediment traps positioned above the anoxic brine interface have captured up to 6 mm of bottom sediment during cumulative wind-driven resuspension events (fig. 2, URL:http://users.o2wire.com/dnaftz/Dave/AGU-abs-figs-AUG06.pdf). Vertical velocity data collected with hydroacoustic equipment indicates upward flow > 1.5 cm/sec during transient wind events (fig. 3, URL:http://users.o2wire.com/dnaftz/Dave/AGU-abs-figs-AUG06.pdf). Transport of methyl Hg into the oxic regions of GSL is supported by biota samples. The median Hg concentration (wet weight) in brine shrimp increased seasonally from the spring to fall time period and is likely a function of the seasonal aging and resulting Hg bioaccumulation in the adult brine shrimp population. Brine shrimp are the primary food source for eared grebes during the fall molt (August through December); the Hg concentration in eared grebe livers more than doubled during this time period. In 2005, Hg concentration in breast muscle tissue from two duck species was observed to consistently exceed the U.S. Environmental Protection Agency screening level of 0.3 mg/kg (wet weight), resulting in a health advisory issued by the State of Utah to duck hunters regarding consumption of these duck species from the GSL ecosystem.

Arsenic Concentrations and Speciation in Blackwaters of the Great Dismal Swamp, Southeastern Virginia, USA

NASA Astrophysics Data System (ADS)

Batista, F.; Cutter, G. A.; Cutter, L. S.; Johannesson, K. H.

2001-12-01

Arsenic concentrations and speciation were measured in surface water samples collected from the Great Dismal Swamp in southeastern Virginia, USA using, selective hydride generation and atomic adsorption spectroscopy. Phosphate concentrations were also determined in these surface waters using the molybdate blue spectrophotometric method. Great Dismal Swamp waters are characterized as blackwaters, having high dissolved organic carbon (DOC) concentrations that range from 445 iM to 6304 iM, with a mean (n = 12) of 3282+/-2165 iM. pH ranged from 4.30 to 6.42, with a mean (n = 12) of 5.14+/-1.04. The inflow waters (Cypress and Pocosin Swamps) have higher pH's (mean of 6.32+/- 0.10 for n = 5) than waters from Lake Drummond and its immediate inflow and outflow ditches, where the mean pH (n = 7) is 4.30+/-0.04. Total arsenic concentrations in Great Dismal Swamp waters range from 2.18 nM up to 21.42 nM. Phosphate concentrations range from 0.18 iM to 1.42 iM, but are not correlated with arsenate concentrations (r 2 = 0.004). Arsenate typically predominates in oxic, surface waters. However, As(III) was detected at higher concentrations (1 - 17.72 nM, mean value of 8.00+/-5.80 nM for all samples, n = 10) in half of the samples from the lower part of the watershed (i.e., mainly in Lake Drummond and its outflow, the Feeder Ditch; mean of 12.89+/-2.89 nM, n = 5). No methylated species were detected in the selected samples analyzed for organoarsenical forms (monomethyl and dimethyl arsenicals) A strong correlation exists between dissolved As(III) concentrations and dissolved organic carbon concentrations (r2 = 0.88), and this correlation is significant at greater than the 99% confidence level. The high abundance of As(III) in comparison to both thermodynamic predictions, and other surface waters, suggests that either there is a strong anoxic source of this form, or that the high DOC concentrations stabilize it via complexation and slower rate of oxidation.

Functioning of the Ocean Biological Pump in the Oxygen Minimum Zones

NASA Astrophysics Data System (ADS)

Moore, J. K.

2015-12-01

Oxygen minimum zones occur at mid-depths in the water column in regions with weak ventilation and relatively high export of organic matter from surface waters. They are important ocean for ocean biogeochemistry, and potentially for climate, as sites of water column denitrification and nitrous oxide production. Denitrification is the dominant loss process for fixed nitrogen in the oceans, and can thus affect the ocean inventory of this key nutrient. Denitrification is less energetically efficient than oxic remineralization. Larger zooplankton, which feed on sinking particles, are not present in the lowest oxygen waters. Both of these factors suggest that the remineralization of sinking particles may be slower within the OMZs than in more oxygenated waters. There is limited field evidence and from some modeling studies that remineralization is slower (remineralization length scales are longer) within OMZ waters. In this talk, I will present results from the Community Earth System Model (CESM) ocean component attempting to test this hypothesis. Comparing model results with observed ocean biogeochemical tracer distributions (i.e., phosphate, oxygen), I will examine whether slower remineralization within low oxygen waters provides a better match between simulated and observed tracer distributions. Longer remineralization length scales under low oxygen conditions would provide a negative feedback under global warming scenarios. The biological pump would transfer organic materials to depth more efficiently as ocean oxygen concentrations decline and the OMZs expand.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ilgen, A. G.; Kukkadapu, R. K.; Dunphy, D. R.

Heterogeneous redox reactions on clay mineral surfaces control mobility and bioavailability of redox-sensitive nutrients and contaminants. Iron (Fe) residing in clay mineral structures can either catalyze or directly participate in redox reactions; however, chemical controls over its reactivity are not fully understood. In our previous work we demonstrated that converting a minor portion of Fe(III) to Fe(II) (partial reduction) in the octahedral sheet of natural Fe-rich clay mineral nontronite (NAu-1) activates its surface, making it redox-active. In this study we produced and characterized synthetic ferric nontronite (SIP), highlighting structural and chemical similarities and differences between this synthetic nontronite and itsmore » natural counterpart NAu-1, and probed whether mineral surface is redox-active by reacting it with arsenic As(III) under oxic and anoxic conditions. We demonstrate that synthetic nontronite SIP undergoes the same activation as natural nontronite NAu-1 following the partial reduction treatment. Similar to NAu-1, SIP oxidized As(III) to As(V) under both oxic (catalytic pathway) and anoxic (direct oxidation) conditions. The similar reactivity trends observed for synthetic nontronite and its natural counterpart make SIP an appropriate analog for laboratory studies. The development of chemically pure analogs for ubiquitous soil minerals will allow for systematic research of the fundamental properties of these minerals.« less

Synthesis and characterization of redox-active ferric nontronite

DOE PAGES

Ilgen, A. G.; Kukkadapu, R. K.; Dunphy, D. R.; ...

2017-07-12

Heterogeneous redox reactions on clay mineral surfaces control mobility and bioavailability of redox-sensitive nutrients and contaminants. Iron (Fe) residing in clay mineral structures can either catalyze or directly participate in redox reactions; but, chemical controls over its reactivity are not fully understood. In our previous work we demonstrated that converting a minor portion of Fe(III) to Fe(II) (partial reduction) in the octahedral sheet of natural Fe-rich clay mineral nontronite (NAu-1) activates its surface, making it redox-active. In this study we produced and characterized synthetic ferric nontronite (SIP), highlighting structural and chemical similarities and differences between this synthetic nontronite and itsmore » natural counterpart NAu-1, and probed whether mineral surface is redox-active by reacting it with arsenic As(III) under oxic and anoxic conditions. Here, we demonstrate that synthetic nontronite SIP undergoes the same activation as natural nontronite NAu-1 following the partial reduction treatment. Similar to NAu-1, SIP oxidized As(III) to As(V) under both oxic (catalytic pathway) and anoxic (direct oxidation) conditions. The similar reactivity trends observed for synthetic nontronite and its natural counterpart make SIP an appropriate analog for laboratory studies. The development of chemically pure analogs for ubiquitous soil minerals will allow for systematic research of the fundamental properties of these minerals.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ilgen, A. G.; Kukkadapu, R. K.; Dunphy, D. R.

Heterogeneous redox reactions on clay mineral surfaces control mobility and bioavailability of redox-sensitive nutrients and contaminants. Iron (Fe) residing in clay mineral structures can either catalyze or directly participate in redox reactions; but, chemical controls over its reactivity are not fully understood. In our previous work we demonstrated that converting a minor portion of Fe(III) to Fe(II) (partial reduction) in the octahedral sheet of natural Fe-rich clay mineral nontronite (NAu-1) activates its surface, making it redox-active. In this study we produced and characterized synthetic ferric nontronite (SIP), highlighting structural and chemical similarities and differences between this synthetic nontronite and itsmore » natural counterpart NAu-1, and probed whether mineral surface is redox-active by reacting it with arsenic As(III) under oxic and anoxic conditions. Here, we demonstrate that synthetic nontronite SIP undergoes the same activation as natural nontronite NAu-1 following the partial reduction treatment. Similar to NAu-1, SIP oxidized As(III) to As(V) under both oxic (catalytic pathway) and anoxic (direct oxidation) conditions. The similar reactivity trends observed for synthetic nontronite and its natural counterpart make SIP an appropriate analog for laboratory studies. The development of chemically pure analogs for ubiquitous soil minerals will allow for systematic research of the fundamental properties of these minerals.« less

Detoxification of sulphidic African shelf waters by blooming chemolithotrophs

NASA Astrophysics Data System (ADS)

Lavik, Gaute; Stührmann, Torben; Brüchert, Volker; van der Plas, Anja; Mohrholz, Volker; Lam, Phyllis; Mußmann, Marc; Fuchs, Bernhard M.; Amann, Rudolf; Lass, Ulrich; Kuypers, Marcel M. M.

2009-01-01

Coastal waters support ~90 per cent of global fisheries and are therefore an important food reserve for our planet. Eutrophication of these waters, due to human activity, leads to severe oxygen depletion and the episodic occurrence of hydrogen sulphide-toxic to multi-cellular life-with disastrous consequences for coastal ecosytems. Here we show that an area of ~7,000km2 of African shelf, covered by sulphidic water, was detoxified by blooming bacteria that oxidized the biologically harmful sulphide to environmentally harmless colloidal sulphur and sulphate. Combined chemical analyses, stoichiometric modelling, isotopic incubations, comparative 16S ribosomal RNA, functional gene sequence analyses and fluorescence in situ hybridization indicate that the detoxification proceeded by chemolithotrophic oxidation of sulphide with nitrate and was mainly catalysed by two discrete populations of γ- and ɛ-proteobacteria. Chemolithotrophic bacteria, accounting for ~20 per cent of the bacterioplankton in sulphidic waters, created a buffer zone between the toxic sulphidic subsurface waters and the oxic surface waters, where fish and other nekton live. This is the first time that large-scale detoxification of sulphidic waters by chemolithotrophs has been observed in an open-ocean system. The data suggest that sulphide can be completely consumed by bacteria in the subsurface waters and, thus, can be overlooked by remote sensing or monitoring of shallow coastal waters. Consequently, sulphidic bottom waters on continental shelves may be more common than previously believed, and could therefore have an important but as yet neglected effect on benthic communities.

Sediment-water 02 dynamics and feedbacks to sediment oxic, suboxic, and anoxic processes on the Louisiana shelf

EPA Science Inventory

The Mississippi and Atchafalaya Rivers annually discharge 674 km3 of freshwater, 86 x 109 moles nitrogen, 5 x 109 moles phosphorus, and 325 x 109 moles organic carbon to the Louisiana shelf. The seasonal input and transport of these materials causes large temporal and spatial va...

Mercury in the Black Sea: New Insights From Measurements and Numerical Modeling

PubMed Central

Melaku Canu, D.; Lagane, C.; Laffont, L.; Rijkenberg, M. J. A.; Gerringa, L. J. A.; Solidoro, C.; Gencarelli, C. N.; Hedgecock, I. M.; De Baar, H. J. W.; Sonke, J. E.

2018-01-01

Abstract Redox conditions and organic matter control marine methylmercury (MeHg) production. The Black Sea is the world's largest and deepest anoxic basin and is thus ideal to study Hg species along the extended redox gradient. Here we present new dissolved Hg and MeHg data from the 2013 GEOTRACES MEDBlack cruise (GN04_leg2) that we integrated into a numerical 1‐D model, to track the fate and dynamics of Hg and MeHg. Contrary to a previous study, our new data show highest MeHg concentrations in the permanently anoxic waters. Observed MeHg/Hg percentage (range 9–57%) in the anoxic waters is comparable to other subsurface maxima in oxic open‐ocean waters. With the modeling we tested for various Hg methylation and demethylation scenarios along the redox gradient. The results show that Hg methylation must occur in the anoxic waters. The model was then used to simulate the time evolution (1850–2050) of Hg species in the Black Sea. Our findings quantify (1) inputs and outputs of HgT (~31 and ~28 kmol yr−1) and MeHgT (~5 and ~4 kmol yr−1) to the basin, (2) the extent of net demethylation occurring in oxic (~1 kmol yr−1) and suboxic water (~6 kmol yr−1), (3) and the net Hg methylation in the anoxic waters of the Black Sea (~11 kmol yr−1). The model was also used to estimate the amount of anthropogenic Hg (85–93%) in the Black Sea. PMID:29861543

Evaluating host-associated sources of marine methane supersaturation

NASA Astrophysics Data System (ADS)

Blanton, J. M.; Pieper, L. M.; Allen, E. E.

2013-12-01

Methane can be found in surface ocean waters at levels from 5% to 75% greater than expected from exchange with the atmosphere. Because oceanic emissions account for up to 4% of the planet's annual methane inventory, understanding marine sources and sinks is relevant to global greenhouse gas budgets. These methane levels are presumed to result from the activity of microorganisms in the water column, yet this presents a paradox: how can biotic methanogensis, primarily understood as an anaerobic process, take place in oxic waters? One working theory is that methanogens find safe harbor in the gastrointestinal tracts of marine animals. We investigate the possibility that microbial communities within fish, and the fecal material they produce, contribute to in-situ methane production in the open ocean. Using genetic markers, we test the GI tracts of benthic and pelagic marine teleosts for the presence of methanogenic organisms and for components of the methanogenesis pathway. Our results indicate that methanogens may be present in fish, but in low numbers. This work sets the scene for measurement of methane production rates from these gut-associated communities in order to elucidate their contribution to oceanic methane supersaturation.

Sulfate reduction and oxic respiration in marine sediments: implications for organic carbon preservation in euxinic environments

NASA Technical Reports Server (NTRS)

Canfield, D. E.; DeVincenzi, D. L. (Principal Investigator)

1989-01-01

Compilations have been made of sulfate reduction rates and oxic respiration rates over the entire range of marine sedimentation rates, and sedimentary environments, including several euxinic sites. These data show, consistent with the findings of Jorgensen (1982, Nature, 296, 643-645), that sulfate reduction and oxic respiration oxidize equal amounts of organic carbon in nearshore sediments. As sedimentation rates decrease, oxic respiration, becomes progressively more important, and in deep-sea sediments 100-1000 times more organic carbon is oxidized by oxic respiration than by sulfate reduction. By contrast, nearly as much organic carbon is oxidized by sulfate reduction in euxinic sediments as is oxidized by the sum of sulfate reduction and oxic respiration in normal marine sediments of similar deposition rate. This observation appears at odds with the enhanced preservation of organic carbon observed in euxinic sediments. However, only small reductions in (depth-integrated) organic carbon decomposition rates (compared to normal marine) are required to give both high organic carbon concentrations and enhanced carbon preservation in euxinic sediments. Lower rates of organic carbon decomposition (if only by subtle amounts) are explained by the diminished ability of anaerobic bacteria to oxidize the full suite of sedimentary organic compounds.

Contrasting Nitrogen Fate in Watersheds using Agricultural and Water Quality Information

NASA Astrophysics Data System (ADS)

Essaid, H.; Baker, N. T.; McCarthy, K.

2016-12-01

A study combining Surplus Nitrogen (N) estimation with Principal Component (PCA) and End-Member-Mixing Analysis (EMMA) successfully reproduced, explained, and contrasted the general features of N fate and transport in diverse agricultural watersheds in Indiana (IN), Iowa (IA), Maryland (MD), Nebraska (NE), Mississippi (MS) and Washington (WA) that ranged in size from 5 to 1254 km2. Watershed Surplus N was determined by subtracting estimates of crop uptake and volatilization from estimates of N input from atmospheric deposition, plant fixation, fertilizer application and manure. Surplus N was ≤ 20% of total N input in the lower permeability watersheds of MS, IA and IN and most Surplus N in these watersheds was exported downstream. In contrast, Surplus N was > 20% of total N input in the more permeable watersheds of WA, NE and MD and only a fraction of the Surplus N was exported downstream. PCA and EMMA were used to identify end-members contributing to streamflow and NO3 load. Discharge of oxic groundwater (GW) to the stream was the primary source of stream NO3 load in the more permeable watersheds. In the less permeable watersheds GW was predominantly anoxic and tile drainage and runoff were the primary sources of stream NO3 load. These results suggest that a larger fraction of N applied at the land surface was not used by the plants and leached into the subsurface in more permeable watersheds. Although NO3-bearing oxic GW was the main source of stream NO3 in these watersheds, subsurface NO3 removal appeared to be occurring by denitrification along GW flow paths that encountered anoxic conditions and/or reactive streambed sediments. Although plants were able to more efficiently use N applied at the land surface in less permeable watersheds, what wasn't taken up by plants flowed directly to the stream with little opportunity for denitrification. Instream benthic processing was not apparent in small watersheds but became more important as watershed size increased.

Production rates of bacterial tetraether lipids and fatty acids in peatland under varying oxygen concentrations

NASA Astrophysics Data System (ADS)

Huguet, Arnaud; Meador, Travis B.; Laggoun-Défarge, Fatima; Könneke, Martin; Wu, Weichao; Derenne, Sylvie; Hinrichs, Kai-Uwe

2017-04-01

Interpretations of the abundance and distribution of branched glycerol dialkyl glycerol tetraether (brGDGT) lipids have been increasingly applied to infer changes in paleoenvironment and to estimate terrigenous organic matter inputs into estuarine and marine sediments. However, only preliminary information is known regarding the ecology and physiology of the source organisms of these biomarkers. We assessed the production rates of brGDGTs under different redox conditions in peat, where these lipids are found in high concentrations, particularly at greater depths below the fluctuating water table. The incorporation of hydrogen relative to carbon into lipids observed in our dual stable isotope probing assay indicates that brGDGTs were produced by heterotrophic bacteria. Unexpectedly, incubations with stable isotope tracers of the surface horizon (5-20 cm) initiated under oxic conditions before turning suboxic and eventually anoxic exhibited up to one order of magnitude higher rates of brGDGT production (16-87 ng cm-3 y-1) relative to the deeper, anoxic zone (20-35 cm; ca. 7 ng cm-3 y-1), and anoxic incubations of the surface horizon (<3 ng cm-3 y-1). Turnover times of brGDGTs in the surface horizon ranged between 8 and 41 years in the incubations initiated under oxic conditions, in contrast to 123-742 years in anoxic incubations. As brGDGTs were actively produced during both anoxic incubations and those exposed to oxygen, we conclude that their source organisms are likely facultative aerobic heterotrophs that are particularly active in the peat acrotelm. Production rates of bacterial fatty acids (ca. 2 μg cm-3 y-1) were roughly two orders of magnitude higher than those of brGDGTs, suggesting that brGDGT producers are a minor constituent of the microbial community or that brGDGTs are a small component of the microbial cell membrane in comparison to fatty acids, despite the typically high brGDGT concentrations observed in peat. Multivariate analysis identified two branched fatty acids that shared a similar production pattern as brGDGTs among the experimental treatments and may be associated with brGDGT biosynthesis.

Dynamics and stoichiometry of nutrients and phytoplankton in waters influenced by the oxygen minimum zone in the eastern tropical Pacific

NASA Astrophysics Data System (ADS)

Franz, Jasmin; Krahmann, Gerd; Lavik, Gaute; Grasse, Patricia; Dittmar, Thorsten; Riebesell, Ulf

2012-04-01

The tropical South East Pacific is characterized by strong coastal upwelling on the narrow continental shelf and an intense oxygen minimum zone (OMZ) in the intermediate water layer. These hydrographic properties are responsible for a permanent supply of intermediate water masses to the surface rich in nutrients and with a remarkably low inorganic N:P stoichiometry. To investigate the impact of OMZ-influenced upwelling waters on phytoplankton growth, elemental and taxonomical composition we measured hydrographic and biogeochemical parameters along an east-west transect at 10°S in the tropical South East Pacific, stretching from the upwelling region above the narrow continental shelf to the well-stratified oceanic section of the eastern boundary regime. New production in the area of coastal upwelling was driven by large-sized phytoplankton (e.g. diatoms) with generally low N:P ratios (<16:1). While nitrate and phosphate concentrations were at levels not limiting phytoplankton growth along the entire transect, silicate depletion prohibited diatom growth further off-shore. A deep chlorophyll a maximum consisting of pico-/nano- (Synechococcus, flagellates) and microphytoplankton occurred within a pronounced thermocline in subsurface waters above the shelf break and showed intermediate N:P ratios close to Redfield proportions. High PON:POP (>20:1) ratios were observed in the stratified open ocean section of the transect, coinciding with the abundance of two strains of the pico-cyanobacterium Prochlorococcus; a high-light adapted strain in the surface layer and a low-light adapted strain occurring along the oxic-anoxic transition zone below the thermocline. Excess phosphate present along the entire transect did not appear to stimulate growth of nitrogen-fixing phytoplankton, as pigment fingerprinting did not indicate the presence of diazotrophic cyanobacteria at any of our sampling stations. Instead, a large fraction of the excess phosphate generated within the oxygen minimum zone was consumed by non-Redfield production of large phytoplankton in shelf surface waters.

Distribution and flux estimates of soluble, colloidal, and leachable particulate trace metals in dynamic and oxygen depleted Mauritanian shelf waters

NASA Astrophysics Data System (ADS)

Rapp, I.; Schlosser, C.; Gledhill, M.; Achterberg, E. P.

2016-02-01

Fe availability in surface waters determines primary production, N2 fixation and microbial community structure and thus plays an important role in ocean carbon and nitrogen cycles. Eastern boundary upwelling areas with oxygen minimum zones, such as the Mauritanian shelf region, are typically associated with elevated Fe concentrations with shelf sediments as key source of Fe to bottom and surface waters. The magnitude of vertical and horizontal Fe fluxes from shelf sediments to onshore and offshore surface waters are not well constrained and there are still large uncertainties concerning the stabilisation of Fe once released from sediments into suboxic and oxic waters. Supportive data of other trace metals can be used as an indicator of sediment release, scavenging processes and biological utilisation. Here we present soluble (<0.02 µm), dissolved (<0.2 µm) and total dissolvable (unfiltered) trace metal data collected at 10 stations on a 90 nautical mile transect across the Mauritanian shelf region in June 2014 (cruise Meteor 107). The samples were pre-concentrated using an automated off-line pre-concentration device and analysed simultaneously for Cd, Pb, Fe, Ni, Cu, Zn, Mn and Co using a high resolution inductively coupled plasma mass spectrometer (HR-ICP-MS). First results indicate the importance of benthic sources to the overall Fe budget in this region. Both dissolved Fe and Mn showed enhanced concentrations close to the shelf at depths between 40 and 180 m corresponding with low oxygen concentrations (<50 µmol L-1). Elevated soluble, dissolved, and total dissolvable Fe and Mn concentrations at an offshore station coincided with the location of a cyclonic Eddie that was characterised by an oxygen depleted water body. To further assess the accuracy of vertical and horizontal fluxes of Fe and other trace metals, we compare diffusivity estimates determined by a microstructure profiler and the scale length method (de Jong et al. 2012) with observed isotopic Ra data.

The influence of buried nodules on the mobility of metals in deep sea sediments

NASA Astrophysics Data System (ADS)

Heller, Christina; Kuhn, Thomas

2017-04-01

Hydrothermal fluids can extract significant amounts of heat from oceanic lithosphere by lateral fluid flow through permeable basaltic crust of an age of up to 65 Ma. Fluid recharge and discharge occur at basement outcrops in between impermeable pelagic deep sea sediments. Recharge of oxic seawater causes upward oxygen diffusion into sediments overlying the permeable basalt in areas proximal to recharge sites. It is suggested that this oxygen has a strong impact on sediments and Mn-nodules during fluid exposure time. The aim of this study is to investigate if/how fluid flow through oceanic crust influence the distribution and element budget of Mn-nodules. Nodules occur widespread at the seafloor of the Clarion-Clipperton Zone (CCZ) in the equatorial North Pacific and were analyzed in many studies worldwide. Nodules buried in the deep sea sediments could be found only rarely (von Stackelberg, 1997, Geol. Soc. Spec. Publ., 119: 153-176). High resolution side-scan sonar recordings (unpublished Data BGR Hannover) indicate that there exist a coherent layer of nodules buried in the sediments of the working area. During the expedition SO 240/FLUM nodules were found on the sediment surface in 4200 to 4300 m water depth as well as in the sediment down to 985 cm below seafloor. In general, nodules consist of different nm- to µm-thick, dense and porous layers. The geochemical composition of bulk nodules and single nodule layers were determined by XRF, ICP-MS/OES, XRD and by high resolution analyses with electron microprobe and LA-ICP-MS. Dense layers have low Mn/Fe ratios (<4) and high concentrations of Co, Zr and REY, while porous layers are characterized by high Mn/Fe ratios (> 10) and high Ni+Cu and Li concentrations. The different compositions depend on different formation processes of the layers. They were formed by metal precipitation from oxic (hydrogenetic) and suboxic (diagenetic) bottom-near seawater and/or pore water (Wegorzewski and Kuhn, 2014, Mar. Geol. 357, 123-138). Preliminary results show that there are significant differences between the geochemical composition of nodules grown at sediment surface and those found within sediments. Compared to surface nodules, buried nodules are enriched in Co and W, but have lower concentration of Mo, Ba, Zn and Li. The distribution of Rare Earth Elements and Y(REY) is also different. Furthermore, the locations of the buried manganese nodules correlates with increased contents of Mn, Co and other elements in the suboxic pore water. It seems that the hydrogenetic layers of the buried nodules were dissolved and/ or recrystallized due to diagenetic processes in the sediment. As a result, a new Fe-rich layer type was formed, with Mn being released into the pore water and/or being used to form todorokite in the nodules. The mineralogical analyses of surface and buried nodules support this assumption. Until now, it couldńt be proven that the hydrothermal fluid flow in the basalts underneath the sediments has an influence on the nodule geochemistry.

Ediacaran Redox Fluctuations

NASA Astrophysics Data System (ADS)

Sahoo, S. K.; Jiang, G.; Planavsky, N. J.; Kendall, B.; Owens, J. D.; Anbar, A. D.; Lyons, T. W.

2013-12-01

Evidence for pervasive oxic conditions, and likely even deep ocean oxygenation has been documented at three intervals in the lower (ca. 632 Ma), middle (ca. 580 Ma) and upper (ca. 551 Ma) Ediacaran. The Doushantuo Formation in South China hosts large enrichments of redox-sensitive trace element (e.g., molybdenum, vanadium and uranium) in anoxic shales, which are indicative of a globally oxic ocean-atmosphere system. However, ocean redox conditions between these periods continue to be a topic of debate and remain elusive. We have found evidence for widespread anoxic conditions through much of the Ediacaran in the deep-water Wuhe section in South China. During most of the Ediacaran-early Cambrian in basinal sections is characterized by Fe speciation data and pyrite morphologies that indicate deposition under euxinic conditions with near-crustal enrichments of redox-sensitive element and positive pyrite-sulfur isotope values, which suggest low levels of marine sulfate and widespread euxinia. Our work reinforces an emerging view that the early Earth, including the Ediacaran, underwent numerous rises and falls in surface oxidation state, rather than a unidirectional rise as originally imagined. The Ediacaran ocean thus experienced repetitive expansion and contraction of marine chalcophilic trace-metal levels that may have had fundamental impact on the slow evolution of early animals and ecosystems. Further, this framework forces us to re-examine the relationship between Neoproterozoic oxygenation and metazoan diversification. Varying redox conditions through the Cryogenian and Ediacaran may help explain molecular clock and biomarker evidence for an early appearance and initial diversification of metazoans but with a delay in the appearance of most major metazoan crown groups until close to Ediacaran-Cambrian boundary.

Light-Dependent Aerobic Methane Oxidation Reduces Methane Emissions from Seasonally Stratified Lakes

PubMed Central

Oswald, Kirsten; Milucka, Jana; Brand, Andreas; Littmann, Sten; Wehrli, Bernhard; Kuypers, Marcel M. M.; Schubert, Carsten J.

2015-01-01

Lakes are a natural source of methane to the atmosphere and contribute significantly to total emissions compared to the oceans. Controls on methane emissions from lake surfaces, particularly biotic processes within anoxic hypolimnia, are only partially understood. Here we investigated biological methane oxidation in the water column of the seasonally stratified Lake Rotsee. A zone of methane oxidation extending from the oxic/anoxic interface into anoxic waters was identified by chemical profiling of oxygen, methane and δ13C of methane. Incubation experiments with 13C-methane yielded highest oxidation rates within the oxycline, and comparable rates were measured in anoxic waters. Despite predominantly anoxic conditions within the zone of methane oxidation, known groups of anaerobic methanotrophic archaea were conspicuously absent. Instead, aerobic gammaproteobacterial methanotrophs were identified as the active methane oxidizers. In addition, continuous oxidation and maximum rates always occurred under light conditions. These findings, along with the detection of chlorophyll a, suggest that aerobic methane oxidation is tightly coupled to light-dependent photosynthetic oxygen production both at the oxycline and in the anoxic bottom layer. It is likely that this interaction between oxygenic phototrophs and aerobic methanotrophs represents a widespread mechanism by which methane is oxidized in lake water, thus diminishing its release into the atmosphere. PMID:26193458

Experimental burial inhibits methanogenesis and anaerobic decomposition in water-saturated peats.

PubMed

Blodau, Christian; Siems, Melanie; Beer, Julia

2011-12-01

A mechanistic understanding of carbon (C) sequestration and methane (CH(4)) production is of great interest due to the importance of these processes for the global C budget. Here we demonstrate experimentally, by means of column experiments, that burial of water saturated, anoxic bog peat leads to inactivation of anaerobic respiration and methanogenesis. This effect can be related to the slowness of diffusive transport of solutes and evolving energetic constraints on anaerobic respiration. Burial lowered decomposition constants in homogenized peat sand mixtures from about 10(-5) to 10(-7) yr(-1), which is considerably slower than previously assumed, and methanogenesis slowed down in a similar manner. The latter effect could be related to acetoclastic methanogenesis approaching a minimum energy quantum of -25 kJ mol(-1) (CH(4)). Given the robustness of hydraulic properties that locate the oxic-anoxic boundary near the peatland surface and constrain solute transport deeper into the peat, this effect has likely been critical for building the peatland C store and will continue supporting long-term C sequestration in northern peatlands even under moderately changing climatic conditions.

Predictive isotopic biogeochemistry: hydrocarbons from anoxic marine basins

NASA Technical Reports Server (NTRS)

Freeman, K. H.; Wakeham, S. G.; Hayes, J. M.

1994-01-01

Carbon isotopic compositions were determined for individual hydrocarbons in water column and sediment samples from the Cariaco Trench and Black Sea. In order to identify hydrocarbons derived from phytoplankton, the isotopic compositions expected for biomass of autotrophic organisms living in surface waters of both localities were calculated based on the concentrations of CO2(aq) and the isotopic compositions of dissolved inorganic carbon. These calculated values are compared to measured delta values for particulate organic carbon and for individual hydrocarbon compounds. Specifically, we find that lycopane is probably derived from phytoplankton and that diploptene is derived from the lipids of chemoautotrophs living above the oxic/anoxic boundary. Three acyclic isoprenoids that have been considered markers for methanogens, pentamethyleicosane and two hydrogenated squalenes, have different delta values and apparently do not derive from a common source. Based on the concentration profiles and isotopic compositions, the C31 and C33 n-alkanes and n-alkenes have a similar source, and both may have a planktonic origin. If so, previously assigned terrestrial origins of organic matter in some Black Sea sediments may be erroneous.

Magnetic microparticles as a new tool for lake restoration: A microcosm experiment for evaluating the impact on phosphorus fluxes and sedimentary phosphorus pools.

PubMed

Funes, A; de Vicente, J; Cruz-Pizarro, L; Álvarez-Manzaneda, I; de Vicente, I

2016-02-01

In the last decades, magnetic particles (MPs) as adsorbents have gained special attention due to their high adsorption capacity and the possibility of recovering them by applying a magnetic separation gradient. For the first time MPs have been tested as P adsorbents in a microcosm experiment in a context of lake restoration. MPs were added to sediment cores from a hypertrophic lake, at Fe:PMobile molar ratio of 285:1 and 560:1 under both, oxic and anoxic conditions. We have found that, under anoxic conditions (anoxic), MPs are able to reduce P release rate from the sediment to the overlying water and to reduce sedimentary PMobile concentration (a 22-25% reduction within 0-4 cm depth compared to controls). Under oxic conditions, the addition of MPs do not affect P fluxes across the sediment and water interface since the lake sediment is naturally rich in iron oxides. However a measured reduction in sedimentary PMobile concentration (12-16% reduction in 0-10 cm depth) contributes to a potential reduction in long-term P efflux. Copyright © 2015 Elsevier Ltd. All rights reserved.

Relative Abundance and Diversity of Bacterial Methanotrophs at the Oxic-Anoxic Interface of the Congo Deep-Sea Fan.

PubMed

Bessette, Sandrine; Moalic, Yann; Gautey, Sébastien; Lesongeur, Françoise; Godfroy, Anne; Toffin, Laurent

2017-01-01

Sitting at ∼5,000 m water depth on the Congo-Angola margin and ∼760 km offshore of the West African coast, the recent lobe complex of the Congo deep-sea fan receives large amounts of fluvial sediments (3-5% organic carbon). This organic-rich sedimentation area harbors habitats with chemosynthetic communities similar to those of cold seeps. In this study, we investigated relative abundance, diversity and distribution of aerobic methane-oxidizing bacteria (MOB) communities at the oxic-anoxic interface of sedimentary habitats by using fluorescence in situ hybridization and comparative sequence analysis of particulate mono-oxygenase ( pmoA ) genes. Our findings revealed that sedimentary habitats of the recent lobe complex hosted type I and type II MOB cells and comparisons of pmoA community compositions showed variations among the different organic-rich habitats. Furthermore, the pmoA lineages were taxonomically more diverse compared to methane seep environments and were related to those found at cold seeps. Surprisingly, MOB phylogenetic lineages typical of terrestrial environments were observed at such water depth. In contrast, MOB cells or pmoA sequences were not detected at the previous lobe complex that is disconnected from the Congo River inputs.

Synergistic effect of reductive and ligand-promoted dissolution of goethite.

PubMed

Wang, Zimeng; Schenkeveld, Walter D C; Kraemer, Stephan M; Giammar, Daniel E

2015-06-16

Ligand-promoted dissolution and reductive dissolution of iron (hydr)oxide minerals control the bioavailability of iron in many environmental systems and have been recognized as biological iron acquisition strategies. This study investigated the potential synergism between ligands (desferrioxamine B (DFOB) or N,N'-Di(2-hydroxybenzyl)ethylenediamine-N,N'-diacetic acid (HBED)) and a reductant (ascorbate) in goethite dissolution. Batch experiments were performed at pH 6 with ligand or reductant alone and in combination, and under both oxic and anoxic conditions. Goethite dissolution in the presence of reductant or ligand alone followed classic surface-controlled dissolution kinetics. Ascorbate alone does not promote goethite dissolution under oxic conditions due to rapid reoxidation of Fe(II). The rate coefficients for goethite dissolution by ligands are closely correlated with the stability constants of the aqueous Fe(III)-ligand complexes. A synergistic effect of DFOB and ascorbate on the rate of goethite dissolution was observed (total rates greater than the sum of the individual rates), and this effect was most pronounced under oxic conditions. For HBED, macroscopically the synergistic effect was hidden due to the inhibitory effect of ascorbate on HBED adsorption. After accounting for the concentrations of adsorbed ascorbate and HBED, a synergistic effect could still be identified. The potential synergism between ligand and reductant for iron (hydr)oxide dissolution may have important implications for iron bioavailability in soil environments.

Dynamics of archaea at fine spatial scales in Shark Bay mat microbiomes

NASA Astrophysics Data System (ADS)

Wong, Hon Lun; Visscher, Pieter T.; White, Richard Allen, III; Smith, Daniela-Lee; Patterson, Molly M.; Burns, Brendan P.

2017-04-01

The role of archaea in microbial mats is poorly understood. Delineating the spatial distribution of archaea with mat depth will enable resolution of putative niches in these systems. In the present study, high throughput amplicon sequencing was undertaken in conjunction with analysis of key biogeochemical properties of two mats (smooth and pustular) from Shark Bay, Australia. One-way analysis of similarity tests indicated the archaeal community structures of smooth and pustular mats were significantly different (global R = 1, p = 0.1%). Smooth mats possessed higher archaeal diversity, dominated by Parvarchaeota. The methanogenic community in smooth mats was dominated by hydrogenotrophic Methanomicrobiales, as well as methylotrophic Methanosarcinales, Methanococcales, Methanobacteriales and Methanomassiliicoccaceae. Pustular mats were enriched with Halobacteria and Parvarchaeota. Key metabolisms (bacterial and archaeal) were measured, and the rates of oxygen production/consumption and sulfate reduction were up to four times higher in smooth than in pustular mats. Methane production peaked in the oxic layers and was up to seven-fold higher in smooth than pustular mats. The finding of an abundance of anaerobic methanogens enriched at the surface where oxygen levels were highest, coupled with peak methane production in the oxic zone, suggests putative surface anoxic niches in these microbial mats.

Transport of oxaliplatin species in water-saturated natural soil.

PubMed

Goykhman, Natalia; Dror, Ishai; Berkowitz, Brian

2018-06-05

This study reports the transport characteristics of the organometallic anticancer compound oxaliplatin and its derivatives in natural soil-water environments. Although pharmaceuticals and their derivatives have for many years been detected in water resources, and linked to toxicological impacts on ecological systems, their transport in soil and groundwater is not fully understood. Specifically, studies that describe transport of organometallic pharmaceuticals in porous media are rare, and the transport characteristics of platinum complexes have received little attention. Oxaliplatin transport was studied in sand, as a function of two added natural chelators (citrate and humic acid), and in soil, under four continuously monitored, environmentally-relevant redox conditions: oxic, nitrate reducing, iron reducing and methanogenic. In sand, oxaliplatin species retention was about 7%, and affected only mildly by added citrate, and by humic acid under buffered pH. Transport with unbuffered humic acid was affected significantly by pH variations, and exhibited strong retention at pH < 8. In soil, unexpectedly similar breakthrough patterns of oxaliplatin species were found for all redox conditions, exhibiting linear, reversible retention of 79-87%. The strongest retention was observed under iron reducing conditions, whereas the weakest retention was under oxic conditions. Increased cation activity appears to promote weaker sorption. The results indicate that soil composition is the leading factor affecting oxaliplatin species mobility and fate in the soil-water environment, followed by the weaker factors of redox conditions and cation activities. Copyright © 2018 Elsevier Ltd. All rights reserved.

Influence of different anoxic time exposures on active biomass, protozoa and filamentous bacteria in activated sludge.

PubMed

Rodriguez-Perez, S; Fermoso, F G; Arnaiz, C

Medium-sized wastewater treatment plants are considered too small to implement anaerobic digestion technologies and too large for extensive treatments. A promising option as a sewage sludge reduction method is the inclusion of anoxic time exposures. In the present study, three different anoxic time exposures of 12, 6 and 4 hours have been studied to reduce sewage sludge production. The best anoxic time exposure was observed under anoxic/oxic cycles of 6 hours, which reduced 29.63% of the biomass production compared with the oxic control conditions. The sludge under different anoxic time exposures, even with a lower active biomass concentration than the oxic control conditions, showed a much higher metabolic activity than the oxic control conditions. Microbiological results suggested that both protozoa density and abundance of filamentous bacteria decrease under anoxic time exposures compared to oxic control conditions. The anoxic time exposures 6/6 showed the highest reduction in both protozoa density, 37.5%, and abundance of filamentous bacteria, 41.1%, in comparison to the oxic control conditions. The groups of crawling ciliates, carnivorous ciliates and filamentous bacteria were highly influenced by the anoxic time exposures. Protozoa density and abundance of filamentous bacteria have been shown as promising bioindicators of biomass production reduction.

Carbon monoxide as a metabolic energy source for extremely halophilic microbes: implications for microbial activity in Mars regolith.

PubMed

King, Gary M

2015-04-07

Carbon monoxide occurs at relatively high concentrations (≥800 parts per million) in Mars' atmosphere, where it represents a potentially significant energy source that could fuel metabolism by a localized putative surface or near-surface microbiota. However, the plausibility of CO oxidation under conditions relevant for Mars in its past or at present has not been evaluated. Results from diverse terrestrial brines and saline soils provide the first documentation, to our knowledge, of active CO uptake at water potentials (-41 MPa to -117 MPa) that might occur in putative brines at recurrent slope lineae (RSL) on Mars. Results from two extremely halophilic isolates complement the field observations. Halorubrum str. BV1, isolated from the Bonneville Salt Flats, Utah (to our knowledge, the first documented extremely halophilic CO-oxidizing member of the Euryarchaeota), consumed CO in a salt-saturated medium with a water potential of -39.6 MPa; activity was reduced by only 28% relative to activity at its optimum water potential of -11 MPa. A proteobacterial isolate from hypersaline Mono Lake, California, Alkalilimnicola ehrlichii MLHE-1, also oxidized CO at low water potentials (-19 MPa), at temperatures within ranges reported for RSL, and under oxic, suboxic (0.2% oxygen), and anoxic conditions (oxygen-free with nitrate). MLHE-1 was unaffected by magnesium perchlorate or low atmospheric pressure (10 mbar). These results collectively establish the potential for microbial CO oxidation under conditions that might obtain at local scales (e.g., RSL) on contemporary Mars and at larger spatial scales earlier in Mars' history.

Carbon monoxide as a metabolic energy source for extremely halophilic microbes: Implications for microbial activity in Mars regolith

PubMed Central

King, Gary M.

2015-01-01

Carbon monoxide occurs at relatively high concentrations (≥800 parts per million) in Mars’ atmosphere, where it represents a potentially significant energy source that could fuel metabolism by a localized putative surface or near-surface microbiota. However, the plausibility of CO oxidation under conditions relevant for Mars in its past or at present has not been evaluated. Results from diverse terrestrial brines and saline soils provide the first documentation, to our knowledge, of active CO uptake at water potentials (−41 MPa to −117 MPa) that might occur in putative brines at recurrent slope lineae (RSL) on Mars. Results from two extremely halophilic isolates complement the field observations. Halorubrum str. BV1, isolated from the Bonneville Salt Flats, Utah (to our knowledge, the first documented extremely halophilic CO-oxidizing member of the Euryarchaeota), consumed CO in a salt-saturated medium with a water potential of −39.6 MPa; activity was reduced by only 28% relative to activity at its optimum water potential of −11 MPa. A proteobacterial isolate from hypersaline Mono Lake, California, Alkalilimnicola ehrlichii MLHE-1, also oxidized CO at low water potentials (−19 MPa), at temperatures within ranges reported for RSL, and under oxic, suboxic (0.2% oxygen), and anoxic conditions (oxygen-free with nitrate). MLHE-1 was unaffected by magnesium perchlorate or low atmospheric pressure (10 mbar). These results collectively establish the potential for microbial CO oxidation under conditions that might obtain at local scales (e.g., RSL) on contemporary Mars and at larger spatial scales earlier in Mars’ history. PMID:25831529

Bacterial, Archaeal, and Eukaryotic Diversity across Distinct Microhabitats in an Acid Mine Drainage

PubMed Central

Mesa, Victoria; Gallego, Jose L. R.; González-Gil, Ricardo; Lauga, Béatrice; Sánchez, Jesús; Méndez-García, Celia; Peláez, Ana I.

2017-01-01

Acid mine drainages are characterized by their low pH and the presence of dissolved toxic metallic species. Microorganisms survive in different microhabitats within the ecosystem, namely water, sediments, and biofilms. In this report, we surveyed the microbial diversity within all domains of life in the different microhabitats at Los Rueldos abandoned mercury underground mine (NW Spain), and predicted bacterial function based on community composition. Sediment samples contained higher proportions of soil bacteria (AD3, Acidobacteria), as well as Crenarchaeota and Methanomassiliicoccaceae archaea. Oxic and hypoxic biofilm samples were enriched in bacterial iron oxidizers from the genus Leptospirillum, order Acidithiobacillales, class Betaproteobacteria, and archaea from the class Thermoplasmata. Water samples were enriched in Cyanobacteria and Thermoplasmata archaea at a 3–98% of the sunlight influence, whilst Betaproteobacteria, Thermoplasmata archaea, and Micrarchaea dominated in acid water collected in total darkness. Stalactites hanging from the Fe-rich mine ceiling were dominated by the neutrophilic iron oxidizer Gallionella and other lineages that were absent in the rest of the microhabitats (e.g., Chlorobi, Chloroflexi). Eukaryotes were detected in biofilms and open-air water samples, and belonged mainly to clades SAR (Alveolata and Stramenopiles), and Opisthokonta (Fungi). Oxic and hypoxic biofilms displayed higher proportions of ciliates (Gonostomum, Oxytricha), whereas water samples were enriched in fungi (Paramicrosporidium and unknown microbial Helotiales). Predicted function through bacterial community composition suggested adaptive evolutive convergence of function in heterogeneous communities. Our study showcases a broad description of the microbial diversity across different microhabitats in the same environment and expands the knowledge on the diversity of microbial eukaryotes in AMD habitats. PMID:28955322

Carbon dioxide and methane fluxes from the transitional zone of a Virginia ephemeral wetland

NASA Astrophysics Data System (ADS)

Atkins, J. W.; Epstein, H. E.; Welsch, D. L.

2014-12-01

The spatial and temporal controls mediating the switch between anaerobic and aerobic respiration within soils located in transitional zones adjacent to ephemeral wetlands remains unclear. As ephemeral wetlands dry down, a soil moisture gradient develops in adjacent transitional zones resulting in changes to the soil environment—moving from anoxic to oxic conditions. Under oxic conditions, aerobic decomposition and CO2 fluxes should dominate, while under anoxic conditions, anaerobic decomposition and CH4 emissions should be more prominent. To investigate the spatial controls and temporal dynamics of anaerobic and aerobic respiration we ran three 20 m transects starting from the late spring peak wetland edge (June 1, 2014 max. lake extent) of Lake Arnold, an ephemeral wetland located at Blandy Experimental Farm in Boyce, Virginia. At 10 m intervals along each transect, high-resolution soil moisture and temperature sensors were installed at three depth levels in the soil (5 cm, 20 cm, and 50 cm). Soil surface CO2 efflux was measured weekly at 5 m intervals using a portable, infra-red gas analyzer and surface chamber (EGM-4 and SRC-1; PP Systems; Amherst, MA). CH4 emissions were sampled weekly using a non-steady state chamber at 10 m intervals along each transect and analyzed in the lab using gas chromatography. Redox potential was measured weekly at two soil depths (5 cm and 20 cm) at 5 m intervals using platinum electrodes and a Ag/Cl reference electrode. Lake Arnold water levels decreased at a rate of 18.16 mm day-1 during the month of July. Preliminary results show a distinct drop in soil moisture at 5 and 20 cm depths at the 0 and 10 m distances along each transect. At 50 cm, soil moisture shows no distinct trend. Late July measurements of redox potential ranged from -196 mV to 865 mV and was correlated with soil moisture (R2 = 0.52). Rates of soil CO2 efflux were diminished at volumetric water contents (VWC) above 45% (ranging from 2.45 - 7.3 µmol CO2 m-2 sec-1). Below 45% VWC, soil CO2 efflux rates ranged from 4.5 - 9.6 µmol CO2 m-2 sec-1.

Ocean N2O Emissions : Recent Global Estimates and Anthropogenically Influenced Changes

NASA Astrophysics Data System (ADS)

Suntharalingam, P.; Buithenuis, E.; Andrews, O.; Le Quere, C.

2016-12-01

Oceanic N2O is produced by microbial activity during organic matter cycling in the subsurface ocean; its production mechanisms display sensitivity to ambient oxygen level. In the oxic ocean, N2O is produced as a byproduct during the oxidation of ammonia to nitrate, mediated by ammonia oxidizing bacteria and archea. N2O is also produced and consumed in sub-oxic and anoxic waters through the action of marine denitrifiers during the multi-step reduction of nitrate to gaseous nitrogen. The oceanic N2O distribution therefore displays significant heterogeneity with background levels of 10-20 nmol/l in the well-oxygenated ocean basins, high concentrations (> 40 nmol/l) in hypoxic waters, and N2O depletion in the core of ocean oxygen minimum zones (OMZs). Oceanic N2O emissions are estimated to account for up to a third of the pre-industrial N2O fluxes to the atmosphere, however the natural cycle of ocean N2O has been perturbed in recent decades by inputs of anthropogenically derived nutrient, and by the impacts of climate change. Anthropogenic nitrogen inputs (e.g., NOx and NHy from fossil fuel combustion and agricultural fertilizer) enter the ocean via atmospheric deposition and riverine fluxes, influencing oceanic N2O production via their impact on the marine organic matter cycle. In addition, climate variations associated with surface ocean warming affect oceanic circulation and nutrient transport pathways, influencing marine productivity and the ventilation of oxygen minimum zones. Recent studies have suggested that possible expansion of oceanic OMZs in a warming climate could lead to significant changes in N2O production and fluxes from these regions. We will summarise the current state of knowledge on the ocean N2O budget and net flux to the atmosphere. Recently reported estimates have been based on (i) empirical relationships derived from ocean tracer data (e.g., involving excess N2O and Apparent Oxygen Utilization (AOU) correlations), (ii) ocean biogeochemical models, and (iii) air-sea flux calculations which combine surface ocean N2O measurements with gas-exchange relationships. We will also present results from ongoing ocean biogeochemistry model analyses evaluating the separate influences of climate variation and anthropogenic nutrient inputs on ocean N2O emissions for recent decades.

Paleo-environmental conditions of the Early Cambrian Niutitang Formation in the Fenggang area, the southwestern margin of the Yangtze Platform, southern China: Evidence from major elements, trace elements and other proxies

NASA Astrophysics Data System (ADS)

Li, Jin; Tang, Shuheng; Zhang, Songhang; Xi, Zhaodong; Yang, Ning; Yang, Guoqiao; Li, Lei; Li, Yanpeng

2018-06-01

The Precambrian/Cambrian transition was a key time in Earth history, especially for marine biological evolution and oceanic chemistry. The redox-stratification with oxic shallow water and anoxic (even euxinic) deeper water in the Early Cambrian Yangtze Sea, which gradually became completely oxygenated, has been suggested as a possible trigger for the "Cambrian explosion" of biological diversity. However, for some areas in northern Guizhou where the exploration and research are lacking, identifying this pattern of redox-stratification by paleo-environmental analysis from borehole data is still in need. Here, we report a remarkable variation range in trace elements (Mo, V, U, Ni, Th, Co, Sc, Zn and Cu), molar Corg:P ratios and pyrite morphology from 27 core samples from one new drill hole (XY1, located in the Fenggang area, northern Guizhou) on the Yangtze Platform, South China. High levels of Ba (from 3242 ppm to 33,800 ppm) and total organic carbon (TOC; from 4% to 9.36%) in 15 core samples in the Lower Member (LM) of the Niutitang Formation indicated elevated primary productivity in the study area. Redox change was recorded based on enrichment factors (EFs) for RSTEs (Mo, U, and V), redox proxies (V/(V + Ni), Ni/Co, V/Sc and Th/U), Corg:P ratios and particle size of framboidal pyrite. These signatures demonstrate that the LM was deposited under anoxic conditions with sulfidic episodes, whereas the Upper Member (UM) of the Niutitang Formation was deposited under suboxic/oxic conditions with intermittently anoxic episodes. Mo/TOC ratios (from 3.72 to 39.86, mean 18.76) suggest weak-moderate water mass restriction. Mo-U covariation patterns (strong but variable enrichment of Mo and U; MoEF ranging from 31.45 to 257.97; UEF ranging from 4.68 to 39.07) in the LM show alternation of particulate shuttling and redox conditions occurred in the Early Cambrian Yangtze Sea, whereas Mo-U covariation patterns (moderate Mo enrichment but depletion or non-enrichment of U; mean MoEF: 7.29; mean UEF: 0.95) in the UM may indicate the combined influence of particulate shuttling and diagenetic diffusion of U via bioactivities, which result in low U values and an anoxic signature from frambiodal pyrite particle size (mean: 4.556 μm; median: 4.41 μm). Additionally, excess Ba (Baxs) concentration (33,800 ppm and 32,500 ppm) and association patterns of trace-metal enrichment in the LM indicate the existence of submarine hydrothermal events. In addition, during deposition of the UM, bioactivities indicated by Mo-U systematics and oxic conditions indicated by redox sensitive trace elements (RSTEs) and multiple-proxies, may be a cause of biological diversification recorded in the Early Cambrian. Finally, data in this record a progressive transition from anoxic bottom waters with euxinic episodes to overwhelming oxic conditions during Early Cambrian.

Metal dynamics in Lake Vanda (Wright Valley, Antarctica)

NASA Technical Reports Server (NTRS)

Green, W. J.; Ferdelman, T. G.; Canfield, D. E.; DeVincenzi, D. L. (Principal Investigator)

1989-01-01

Data are reported for Mn, Fe, Co, Ni, Cu and Cd in the Onyx River, and for Mn, Co, Ni, Cu and Cd in Lake Vanda, a closed-basin Antarctic lake. Oxic water concentrations for Co, Ni, Cu and Cd were quite low and approximate pelagic ocean values. Scavenging of these metals by sinking particles is strongly indicated. Deep-lake profiles reveal a sharp peak in the concentrations of Mn, Fe and Co at the oxic-anoxic boundary at 60 m. Maxima for Ni, Cu and Cd occur higher in the water column, in the vicinity of a Mn submaximum, suggesting early release of these metals from sinking manganese oxide-coated particles. A rough steady-state model leads to the conclusion that there is a large downward flux of Mn into the deep lake and that this flux is sufficient to explain the annual loss of Co, Ni, Cu and Cd. A pronounced geochemical separation between Fe and Mn apparently occurs in this system--Fe being best lost in near-shore environments and Mn being lost in deeper waters. Comparison of metal residence times in Lake Vanda with those in the oceans shows that in both systems Mn, Fe and Co are much more reactive than Ni, Cu and Cd. Energetically favorable inclusion of the more highly charged metals, Mn(IV), Fe(III) and Co(III), into oxide-based lattices is a plausible explanation.

Protist communities in a marine oxygen minimum zone off Costa Rica by 454 pyrosequencing

NASA Astrophysics Data System (ADS)

Jing, H.; Rocke, E.; Kong, L.; Xia, X.; Liu, H.; Landry, M. R.

2015-08-01

Marine planktonic protists, including microalgae and protistan grazers, are an important contributor to global primary production and carbon and mineral cycles, however, little is known about their population shifts along the oxic-anoxic gradient in the water column. We used 454 pyrosequencing of the 18S rRNA gene and gene transcripts to study the community composition of whole and active protists throughout a water column in the Costa Rica Dome, where a stable oxygen minimum zone (OMZ) exists at a depth of 400~700 m. A clear shift of protist composition from photosynthetic Dinoflagellates in the surface to potential parasitic Dinoflagellates and Ciliates in the deeper water was revealed along the vertical profile at both rRNA and rDNA levels. Those protist groups recovered only at the rDNA level represent either lysed aggregates sinking from the upper waters or potential hosts for parasitic groups. UPGMA clustering demonstrated that total and active protists in the anoxic core of OMZ (550 m) were distinct from those in other water depths. The reduced community diversity and presence of a parasitic/symbiotic trophic lifestyle in the OMZ, especially the anoxic core, suggests that OMZs can exert a selective pressure on protist communities. Such changes in community structure and a shift in trophic lifestyle could result in a modulation of the microbial loop and associated biogeochemical cycling.

Bacterial diversity in the oxygen minimum zone of the eastern tropical South Pacific.

PubMed

Stevens, Heike; Ulloa, Osvaldo

2008-05-01

The structure and diversity of bacterial communities associated with the oxygen minimum zone (OMZ) of the eastern tropical South Pacific was studied through phylogenetic analysis. Clone libraries of 16S rRNA gene fragments were constructed using environmental DNA collected from the OMZ (60 m and 200 m), the sea surface (10 m), and the deep oxycline (450 m). At the class level, the majority of sequences affiliated to the gamma- (53.7%) and alpha-Proteobacteria (19.7%), and to the Bacteroidetes (11.2%). A vertical partitioning of the bacterial communities was observed, with main differences between the suboxic OMZ and the more oxygenated surface and deep oxycline waters. At the surface, the microbial community was predominantly characterized by SAR86, Loktanella and unclassified Flavobacteriaceae, whereas the deeper layer was dominated by Sulfitobacter and unclassified Alteromonadaceae. In the OMZ, major constituents affiliated to the marine SAR11 clade and to thiotrophic gamma-symbionts (25% of all sequences), a group not commonly found in pelagic waters. Sequences affiliating to the phylum Chloroflexi, to the AGG47 and SAR202 clades, to the delta-Proteobacteria, to the Acidobacteria, and to the 'anammox group' of the Planctomycetes were found exclusively in the OMZ. The bacterial richness in the OMZ was higher than in the oxic surface and deeper oxycline, as revealed by rarefaction analysis and the Chao1 richness estimator (surface: 45 +/- 8, deeper oxycline: 76 +/- 26; OMZ (60 m): 97 +/- 33, OMZ (200 m): 109 +/- 31). OMZ bacterial diversity indices (Fisher's: approximately 30 +/- 5, Shannon's: approximately 3.31, inverse Simpson's: approximately 20) were similar to those found in other pelagic marine environments. Thus, our results indicate a distinct and diverse bacterial community within the OMZ, with presumably novel and yet uncultivated bacterial lineages.

The effects of redox fluctuation on iron-organic matter interactions in wet tropical soils

NASA Astrophysics Data System (ADS)

Bhattacharyya, A.; Campbell, A.; Lin, Y.; Nico, P. S.; Silver, W. L.; Pett-Ridge, J.

2016-12-01

Two-thirds of the C in the terrestrial biosphere is stored as soil organic C, and much of this is stabilized via iron (Fe) mineral-organic matter (OM) associations that are susceptible to redox effects. The rapid C cycling typical of wet tropical ecosystems- driven by ample moisture and temperature- may also be fueled by a characteristically dynamic redox environment. Yet the net result of altered tropical soil climate and fluctuating soil redox regimes on Fe-organic matter associations is poorly understood. In this study, we hypothesized that the timing of redox transitions (frequency of O2 introduction and ferrous iron (Fe2+) generation) will lead to differences in Fe (oxyhydr)oxide mineral crystallinity and C degradation rates and alter the proportion of organic C associated with iron minerals. Surface soils from a humid tropical forest in Puerto Rico were incubated for 44 days under four redox regimes: (1) static anoxic, (2) static oxic, (3) 4 days anoxic, 4 days oxic, and (4) 4 days anoxic, 8 days oxic. Replicate microcosms were harvested at multiple time points, including before and after a redox switch (oxic to anoxic or vice versa). Selective chemical extractions, bulk Fe K-edge EXAFS and STXM/NEXAFS spectromicroscopy were used to comprehensively probe treatment effects on Fe and C speciation. Static redox conditions had a significant effect on Fe2+ and dissolved organic carbon (DOC) concentrations, and prolonged anoxia promoted reductive dissolution of Fe-oxides and an increase in amorphous or short-range ordered (SRO) Fe oxides. Preferential dissolution of this less-crystalline Fe pool was more prominent during rapid redox switches from oxic to anoxic conditions, and coincided with increased DOC. Bulk Fe K-edge EXAFS spectroscopy identified Fe3+ as the dominant Fe species in all treatments and indicated O/N atoms in the first Fe co-ordination sphere and features similar to SRO Fe-oxide phases (e.g. ferrihydrite or nano-goethite) in the second co-ordination sphere. STXM/NEXAFS analyses indicated an increase in lignin-like biomolecules under static anoxic conditions, and a potential role of Fe-lignin interactions under strong reducing conditions. Our current findings highlight the necessity to explore natural redox-dynamic systems in greater detail in order to develop a better model for climate change.

Microbial life associated with low-temperature alteration of ultramafic rocks in the Leka ophiolite complex.

PubMed

Daae, F L; Økland, I; Dahle, H; Jørgensen, S L; Thorseth, I H; Pedersen, R B

2013-07-01

Water-rock interactions in ultramafic lithosphere generate reduced chemical species such as hydrogen that can fuel subsurface microbial communities. Sampling of this environment is expensive and technically demanding. However, highly accessible, uplifted oceanic lithospheres emplaced onto continental margins (ophiolites) are potential model systems for studies of the subsurface biosphere in ultramafic rocks. Here, we describe a microbiological investigation of partially serpentinized dunite from the Leka ophiolite (Norway). We analysed samples of mineral coatings on subsurface fracture surfaces from different depths (10-160 cm) and groundwater from a 50-m-deep borehole that penetrates several major fracture zones in the rock. The samples are suggested to represent subsurface habitats ranging from highly anaerobic to aerobic conditions. Water from a surface pond was analysed for comparison. To explore the microbial diversity and to make assessments about potential metabolisms, the samples were analysed by microscopy, construction of small subunit ribosomal RNA gene clone libraries, culturing and quantitative-PCR. Different microbial communities were observed in the groundwater, the fracture-coating material and the surface water, indicating that distinct microbial ecosystems exist in the rock. Close relatives of hydrogen-oxidizing Hydrogenophaga dominated (30% of the bacterial clones) in the oxic groundwater, indicating that microbial communities in ultramafic rocks at Leka could partially be driven by H2 produced by low-temperature water-rock reactions. Heterotrophic organisms, including close relatives of hydrocarbon degraders possibly feeding on products from Fischer-Tropsch-type reactions, dominated in the fracture-coating material. Putative hydrogen-, ammonia-, manganese- and iron-oxidizers were also detected in fracture coatings and the groundwater. The microbial communities reflect the existence of different subsurface redox conditions generated by differences in fracture size and distribution, and mixing of fluids. The particularly dense microbial communities in the shallow fracture coatings seem to be fuelled by both photosynthesis and oxidation of reduced chemical species produced by water-rock reactions. © 2013 John Wiley & Sons Ltd.

Giant Hydrogen Sulfide Plume in the Oxygen Minimum Zone off Peru Supports Chemolithoautotrophy

PubMed Central

Großkopf, Tobias; Kalvelage, Tim; Löscher, Carolin R.; Paulmier, Aurélien; Contreras, Sergio; Siegel, Herbert; Holtappels, Moritz; Rosenstiel, Philip; Schilhabel, Markus B.; Graco, Michelle; Schmitz, Ruth A.; Kuypers, Marcel M. M.; LaRoche, Julie

2013-01-01

In Eastern Boundary Upwelling Systems nutrient-rich waters are transported to the ocean surface, fuelling high photoautotrophic primary production. Subsequent heterotrophic decomposition of the produced biomass increases the oxygen-depletion at intermediate water depths, which can result in the formation of oxygen minimum zones (OMZ). OMZs can sporadically accumulate hydrogen sulfide (H2S), which is toxic to most multicellular organisms and has been implicated in massive fish kills. During a cruise to the OMZ off Peru in January 2009 we found a sulfidic plume in continental shelf waters, covering an area >5500 km2, which contained ∼2.2×104 tons of H2S. This was the first time that H2S was measured in the Peruvian OMZ and with ∼440 km3 the largest plume ever reported for oceanic waters. We assessed the phylogenetic and functional diversity of the inhabiting microbial community by high-throughput sequencing of DNA and RNA, while its metabolic activity was determined with rate measurements of carbon fixation and nitrogen transformation processes. The waters were dominated by several distinct γ-, δ- and ε-proteobacterial taxa associated with either sulfur oxidation or sulfate reduction. Our results suggest that these chemolithoautotrophic bacteria utilized several oxidants (oxygen, nitrate, nitrite, nitric oxide and nitrous oxide) to detoxify the sulfidic waters well below the oxic surface. The chemolithoautotrophic activity at our sampling site led to high rates of dark carbon fixation. Assuming that these chemolithoautotrophic rates were maintained throughout the sulfidic waters, they could be representing as much as ∼30% of the photoautotrophic carbon fixation. Postulated changes such as eutrophication and global warming, which lead to an expansion and intensification of OMZs, might also increase the frequency of sulfidic waters. We suggest that the chemolithoautotrophically fixed carbon may be involved in a negative feedback loop that could fuel further sulfate reduction and potentially stabilize the sulfidic OMZ waters. PMID:23990875

Giant hydrogen sulfide plume in the oxygen minimum zone off Peru supports chemolithoautotrophy.

PubMed

Schunck, Harald; Lavik, Gaute; Desai, Dhwani K; Großkopf, Tobias; Kalvelage, Tim; Löscher, Carolin R; Paulmier, Aurélien; Contreras, Sergio; Siegel, Herbert; Holtappels, Moritz; Rosenstiel, Philip; Schilhabel, Markus B; Graco, Michelle; Schmitz, Ruth A; Kuypers, Marcel M M; Laroche, Julie

2013-01-01

In Eastern Boundary Upwelling Systems nutrient-rich waters are transported to the ocean surface, fuelling high photoautotrophic primary production. Subsequent heterotrophic decomposition of the produced biomass increases the oxygen-depletion at intermediate water depths, which can result in the formation of oxygen minimum zones (OMZ). OMZs can sporadically accumulate hydrogen sulfide (H2S), which is toxic to most multicellular organisms and has been implicated in massive fish kills. During a cruise to the OMZ off Peru in January 2009 we found a sulfidic plume in continental shelf waters, covering an area >5500 km(2), which contained ∼2.2×10(4) tons of H2S. This was the first time that H2S was measured in the Peruvian OMZ and with ∼440 km(3) the largest plume ever reported for oceanic waters. We assessed the phylogenetic and functional diversity of the inhabiting microbial community by high-throughput sequencing of DNA and RNA, while its metabolic activity was determined with rate measurements of carbon fixation and nitrogen transformation processes. The waters were dominated by several distinct γ-, δ- and ε-proteobacterial taxa associated with either sulfur oxidation or sulfate reduction. Our results suggest that these chemolithoautotrophic bacteria utilized several oxidants (oxygen, nitrate, nitrite, nitric oxide and nitrous oxide) to detoxify the sulfidic waters well below the oxic surface. The chemolithoautotrophic activity at our sampling site led to high rates of dark carbon fixation. Assuming that these chemolithoautotrophic rates were maintained throughout the sulfidic waters, they could be representing as much as ∼30% of the photoautotrophic carbon fixation. Postulated changes such as eutrophication and global warming, which lead to an expansion and intensification of OMZs, might also increase the frequency of sulfidic waters. We suggest that the chemolithoautotrophically fixed carbon may be involved in a negative feedback loop that could fuel further sulfate reduction and potentially stabilize the sulfidic OMZ waters.

Flow and geochemistry along shallow ground-water flowpaths in an agricultural area in southeastern Wisconsin

USGS Publications Warehouse

Saad, D.A.; Thorstenson, D.C.

1998-01-01

Ground water recharging at mid- and downgradient wells is oxic and contains dissolved nitrate, whereas the ground water discharging to the stream is anoxic and contains dissolved ammonium. Redox environments were defined at each well on the basis of relative concentrations of various dissolved redox-active species. Chemically permissible flowpaths inferred from the observed sequence of redox environments at well sites are consistent with flowpaths in the ground-water flow model. The transition from nitrate in recharging ground water to ammonium in ground water discharging to the stream suggests the possibility of nitrate reduction along the flowpath. None of the techniques employed in this study, however, were able to prove the occurrence of this reaction.

Anoxic and Oxic Oxidation of Rocks Containing Fe(II)Mg-Silicates and Fe(II)-Monosulfides as Source of Fe(III)-Minerals and Hydrogen. Geobiotropy.

PubMed

Bassez, Marie-Paule

2017-12-01

In this article, anoxic and oxic hydrolyses of rocks containing Fe (II) Mg-silicates and Fe (II)-monosulfides are analyzed at 25 °C and 250-350 °C. A table of the products is drawn. It is shown that magnetite and hydrogen can be produced during low-temperature (25 °C) anoxic hydrolysis/oxidation of ferrous silicates and during high-temperature (250 °C) anoxic hydrolysis/oxidation of ferrous monosulfides. The high-T (350 °C) anoxic hydrolysis of ferrous silicates leads mainly to ferric oxides/hydroxides such as the hydroxide ferric trihydroxide, the oxide hydroxide goethite/lepidocrocite and the oxide hematite, and to Fe(III)-phyllosilicates. Magnetite is not a primary product. While the low-T (25 °C) anoxic hydrolysis of ferrous monosulfides leads to pyrite. Thermodynamic functions are calculated for elementary reactions of hydrolysis and carbonation of olivine and pyroxene and E-pH diagrams are analyzed. It is shown that the hydrolysis of the iron endmember is endothermic and can proceed within the exothermic hydrolysis of the magnesium endmember and also within the exothermic reactions of carbonations. The distinction between three products of the iron hydrolysis, magnetite, goethite and hematite is determined with E-pH diagrams. The hydrolysis/oxidation of the sulfides mackinawite/troilite/pyrrhotite is highly endothermic but can proceed within the heat produced by the exothermic hydrolyses and carbonations of ferromagnesian silicates and also by other sources such as magma, hydrothermal sources, impacts. These theoretical results are confirmed by the products observed in several related laboratory experiments. The case of radiolyzed water is studied. It is shown that magnetite and ferric oxides/hydroxides such as ferric trihydroxide, goethite/lepidocrocite and hematite are formed in oxic hydrolysis of ferromagnesian silicates at 25 °C and 350 °C. Oxic oxidation of ferrous monosulfides at 25 °C leads mainly to pyrite and ferric oxides/hydroxides such as ferric trihydroxide, goethite/lepidocrocite and hematite and also to sulfates, and at 250 °C mainly to magnetite instead of pyrite, associated to the same ferric oxides/hydroxides and sulfates. Some examples of geological terrains, such as Mawrth Vallis on Mars, the Tagish Lake meteorite and hydrothermal venting fields, where hydrolysis/oxidation of ferromagnesian silicates and iron(II)-monosulfides may occur, are discussed. Considering the evolution of rocks during their interaction with water, in the absence of oxygen and in radiolyzed water, with hydrothermal release of H 2 and the plausible associated formation of components of life, geobiotropic signatures are proposed. They are mainly Fe(III)-phyllosilicates, magnetite, ferric trihydroxide, goethite/lepidocrocite, hematite, but not pyrite.

Anoxic and Oxic Oxidation of Rocks Containing Fe(II)Mg-Silicates and Fe(II)-Monosulfides as Source of Fe(III)-Minerals and Hydrogen. Geobiotropy.

NASA Astrophysics Data System (ADS)

Bassez, Marie-Paule

2017-12-01

In this article, anoxic and oxic hydrolyses of rocks containing Fe (II) Mg-silicates and Fe (II)-monosulfides are analyzed at 25 °C and 250-350 °C. A table of the products is drawn. It is shown that magnetite and hydrogen can be produced during low-temperature (25 °C) anoxic hydrolysis/oxidation of ferrous silicates and during high-temperature (250 °C) anoxic hydrolysis/oxidation of ferrous monosulfides. The high-T (350 °C) anoxic hydrolysis of ferrous silicates leads mainly to ferric oxides/hydroxides such as the hydroxide ferric trihydroxide, the oxide hydroxide goethite/lepidocrocite and the oxide hematite, and to Fe(III)-phyllosilicates. Magnetite is not a primary product. While the low-T (25 °C) anoxic hydrolysis of ferrous monosulfides leads to pyrite. Thermodynamic functions are calculated for elementary reactions of hydrolysis and carbonation of olivine and pyroxene and E-pH diagrams are analyzed. It is shown that the hydrolysis of the iron endmember is endothermic and can proceed within the exothermic hydrolysis of the magnesium endmember and also within the exothermic reactions of carbonations. The distinction between three products of the iron hydrolysis, magnetite, goethite and hematite is determined with E-pH diagrams. The hydrolysis/oxidation of the sulfides mackinawite/troilite/pyrrhotite is highly endothermic but can proceed within the heat produced by the exothermic hydrolyses and carbonations of ferromagnesian silicates and also by other sources such as magma, hydrothermal sources, impacts. These theoretical results are confirmed by the products observed in several related laboratory experiments. The case of radiolyzed water is studied. It is shown that magnetite and ferric oxides/hydroxides such as ferric trihydroxide, goethite/lepidocrocite and hematite are formed in oxic hydrolysis of ferromagnesian silicates at 25 °C and 350 °C. Oxic oxidation of ferrous monosulfides at 25 °C leads mainly to pyrite and ferric oxides/hydroxides such as ferric trihydroxide, goethite/lepidocrocite and hematite and also to sulfates, and at 250 °C mainly to magnetite instead of pyrite, associated to the same ferric oxides/hydroxides and sulfates. Some examples of geological terrains, such as Mawrth Vallis on Mars, the Tagish Lake meteorite and hydrothermal venting fields, where hydrolysis/oxidation of ferromagnesian silicates and iron(II)-monosulfides may occur, are discussed. Considering the evolution of rocks during their interaction with water, in the absence of oxygen and in radiolyzed water, with hydrothermal release of H2 and the plausible associated formation of components of life, geobiotropic signatures are proposed. They are mainly Fe(III)-phyllosilicates, magnetite, ferric trihydroxide, goethite/lepidocrocite, hematite, but not pyrite.

Fate of Uranium During Transport Across the Groundwater-Surface Water Interface

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jaffe, Peter R.; Kaplan, Daniel I.

Discharge of contaminated groundwater to surface waters is of concern at many DOE facilities. For example, at F-Area and TNX-Area on the Savannah River Site, contaminated groundwater, including uranium, is already discharging into natural wetlands. It is at this interface where contaminants come into contact with the biosphere. These this research addressed a critical knowledge gap focusing on the geochemistry of uranium (or for that matter, any redox-active contaminant) in wetland systems. Understanding the interactions between hydrological, microbial, and chemical processes will make it possible to provide a more accurate conceptual and quantitative understanding of radionuclide fate and transport undermore » these unique conditions. Understanding these processes will permit better long-term management and the necessary technical justification for invoking Monitored Natural Attenuation of contaminated wetland areas. Specifically, this research did provide new insights on how plant-induced alterations to the sediment biogeochemical processes affect the key uranium reducing microorganisms, the uranium reduction, its spatial distribution, the speciation of the immobilized uranium, and its long-term stability. This was achieved by conducting laboratory mesocosm wetland experiments as well as field measurements at the SRNL. Results have shown that uranium can be immobilized in wetland systems. To a degree some of the soluble U(VI) was reduced to insoluble U(IV), but the majority of the immobilized U was incorporated into iron oxyhydroxides that precipitated onto the root surfaces of wetland plants. This U was immobilized mostly as U(VI). Because it was immobilized in its oxidized form, results showed that dry spells, resulting in the lowering of the water table and the exposure of the U to oxic conditions, did not result in U remobilization.« less

Ether Lipids of Planktonic Archaea in the Marine Water Column

PubMed Central

Hoefs, M.; Schouten, S.; De Leeuw, J. W.; King, L. L.; Wakeham, S. G.; Damste, J.

1997-01-01

Acyclic and cyclic biphytanes derived from the membrane ether lipids of archaea were found in water column particulate and sedimentary organic matter from several oxic and anoxic marine environments. Compound-specific isotope analyses of the carbon skeletons suggest that planktonic archaea utilize an isotopically heavy carbon source such as algal carbohydrates and proteins or dissolved bicarbonate. Due to their high preservation potential, these lipids provide a fossil record of planktonic archaea and suggest that they have thrived in marine environments for more than 50 million years. PMID:16535669

Manganese Driven Carbon Oxidation along Oxic-Anoxic Interfaces in Forest Soils

NASA Astrophysics Data System (ADS)

Jones, M. E.; Keiluweit, M.

2017-12-01

Soils are the largest and most dynamic terrestrial carbon pool, storing a total of 3000 Pg of C - more than the atmosphere and biosphere combined. Because microbial oxidation determines the proportion of carbon that is either stored in the soil or emitted as climate active CO2, its rate directly impacts the global carbon cycle. Recently, a strong correlation between oxidation rates and manganese (Mn) content has been observed in forest soils globally, leading researchers conclude that Mn "is the single main factor governing" the oxidation of plant-derived particulate organic carbon (POC). Many soils are characterized by steep oxygen gradients, forming oxic-anoxic transitions that enable rapid redox cycling of Mn. Oxic-anoxic interfaces have been shown to promote fungal Mn oxidation and the formation of ligand-stabilized Mn(III), which ranks second only to superoxide as the most powerful oxidizing agent in the environment. Here we examined fungal Mn(III) formation along redox gradients in forest soils and their impact on POC oxidation rates. In both field and laboratory settings, oxic-anoxic transition zones showed the greatest Mn(III) concentrations, along with enhanced fungal growth, oxidative potential, production of soluble oxidation products, and CO2 production. Additional electrochemical and X-ray (micro)spectroscopic analyses indicated that oxic-anoxic interfaces represent ideal niches for fungal Mn(III) formation, owing to the ready supply of Mn(II), ligands and O2. Combined, our results suggest that POC oxidation relies on fungal Mn cycling across oxic-anoxic interfaces to produce Mn(III) based oxidants. Because predicted changes in the frequency and timing of precipitation dramatically alter soil moisture regimes in forest soils, understanding the mechanistic link between Mn cycling and carbon oxidation along oxic-anoxic interfaces is becoming increasingly important.

Title: Biogenic Magnetite Prevails in Oxic Pelagic Red Clay Core in the South Pacific Gyre

NASA Astrophysics Data System (ADS)

Shimono, T.; Yamazaki, T.

2012-12-01

Magnetotactic bacteria have been observed in wide variety of environments, including soils, freshwater lakes, and marine sediments, since Blakemore (1975) first described in 1975. Magnetotactic bacteria, which most commonly live within the oxic-anoxic transition zone (OATZ) of aquatic environments, produce intracellular crystals of magnetic minerals, specifically magnetite or greigite. It is considered that the magnetite/greigite crystals facilitate the bacteria's search for optimal conditions within the sharp chemical gradients of the OATZ. Petermann and Bleil (1993) reported living magnetotactic bacteria in pelagic and hemipelagic sediments near OATZ in the eastern South Atlantic at water depths to about 3,000 m, but they couldn't find actively swimming magnetotactic bacteria in sediments of deeper water depths. The South Pacific Gyre (SPG) is far from continents and the lowest productivity region on Earth. IODP site U1365 (water depth ~5,700 m) cored pelagic red clay of 75.5 m thick above ~100 Ma basement (except for the chart layer from ~42 to 63.5 m) in the western edge of the SPG. The core mainly consists of iron rich clay. The color is dark reddish and/or dark brown throughout the core. We conducted a paleomagnetic and environmental rock magnetic study of the pelagic clay core. The magnetostratigraphy revealed the top 5 m sediments cover the last 5 My, and sedimentation rate decreases downward from 1.7 to 0.6 m/m.y. Geochemical measurements of pore water indicate that dissolved oxygen was present throughout the core (>50 μM). Thus oxygen penetrates through the entire sediment column to the sediment/basalt interface, and there is no OATZ. Magnetic mineral assemblage of this core is dominated by biogenic magnetite despite no OATZ. First-order reversal curve (FORC) diagrams of all specimens have a narrow central ridge along the Hc axis with very small vertical spread. This indicates very weak magnetostatic interaction (Roberts et al., 2000), and is the characteristic of biogenic magnetite (Egli et al., 2010; Roberts et al., 2011). Presence of biogenic magnetite was confirmed by TEM observation. Occurrence of biogenic magnetite was reported also in pelagic red clay of the North Pacific with TEM observations (Yamazaki and Ioka, 1997), and these samples also display the characteristic FORC diagrams. These observations suggest that biogenic magnetites commonly occur in oxic pelagic red clay without OATZ.

Methane production as key to the greenhouse gas budget of thawing permafrost

NASA Astrophysics Data System (ADS)

Knoblauch, Christian; Beer, Christian; Liebner, Susanne; Grigoriev, Mikhail N.; Pfeiffer, Eva-Maria

2018-04-01

Permafrost thaw liberates frozen organic carbon, which is decomposed into carbon dioxide (CO2) and methane (CH4). The release of these greenhouse gases (GHGs) forms a positive feedback to atmospheric CO2 and CH4 concentrations and accelerates climate change1,2. Current studies report a minor importance of CH4 production in water-saturated (anoxic) permafrost soils3-6 and a stronger permafrost carbon-climate feedback from drained (oxic) soils1,7. Here we show through seven-year laboratory incubations that equal amounts of CO2 and CH4 are formed in thawing permafrost under anoxic conditions after stable CH4-producing microbial communities have established. Less permafrost carbon was mineralized under anoxic conditions but more CO2-carbon equivalents (CO2-Ce) were formed than under oxic conditions when the higher global warming potential (GWP) of CH4 is taken into account8. A model of organic carbon decomposition, calibrated with the observed decomposition data, predicts a higher loss of permafrost carbon under oxic conditions (113 ± 58 g CO2-C kgC-1 (kgC, kilograms of carbon)) by 2100, but a twice as high production of CO2-Ce (241 ± 138 g CO2-Ce kgC-1) under anoxic conditions. These findings challenge the view of a stronger permafrost carbon-climate feedback from drained soils1,7 and emphasize the importance of CH4 production in thawing permafrost on climate-relevant timescales.

Simulated Patterns of Unforced Centennial-Scale Climate Variability in the Tropical Pacific

NASA Astrophysics Data System (ADS)

Sahoo, S. K.; Jiang, G.; Planavsky, N. J.; Kendall, B.; Owens, J. D.; Anbar, A. D.; Lyons, T. W.

2011-12-01

Evidence for pervasive oxic conditions, and likely even deep ocean oxygenation has been documented at three intervals in the lower (ca. 632 Ma), middle (ca. 580 Ma) and upper (ca. 551 Ma) Ediacaran. The Doushantuo Formation in South China hosts large enrichments of redox-sensitive trace element (e.g., molybdenum, vanadium and uranium) in anoxic shales, which are indicative of a globally oxic ocean-atmosphere system. However, ocean redox conditions between these periods continue to be a topic of debate and remain elusive. We have found evidence for widespread anoxic conditions through much of the Ediacaran in the deep-water Wuhe section in South China. During most of the Ediacaran-early Cambrian in basinal sections is characterized by Fe speciation data and pyrite morphologies that indicate deposition under euxinic conditions with near-crustal enrichments of redox-sensitive element and positive pyrite-sulfur isotope values, which suggest low levels of marine sulfate and widespread euxinia. Our work reinforces an emerging view that the early Earth, including the Ediacaran, underwent numerous rises and falls in surface oxidation state, rather than a unidirectional rise as originally imagined. The Ediacaran ocean thus experienced repetitive expansion and contraction of marine chalcophilic trace-metal levels that may have had fundamental impact on the slow evolution of early animals and ecosystems. Further, this framework forces us to re-examine the relationship between Neoproterozoic oxygenation and metazoan diversification. Varying redox conditions through the Cryogenian and Ediacaran may help explain molecular clock and biomarker evidence for an early appearance and initial diversification of metazoans but with a delay in the appearance of most major metazoan crown groups until close to Ediacaran-Cambrian boundary.

Migration of 75Se(IV) in crushed Beishan granite: Effects of the iron content.

PubMed

He, Jiangang; Ma, Bin; Kang, Mingliang; Wang, Chunli; Nie, Zhe; Liu, Chunli

2017-02-15

The diffusion of selenite (labeled with 75 Se) in compacted Beishan granite (BsG) was investigated using the in-diffusion capillary method at pH values from ∼2.0 to ∼11.0 under oxic and anoxic conditions. The results indicate that the apparent diffusion coefficient (D a ) values of selenite in BsG always reached the minimum at approximately pH 5. Unexpectedly, the D a values under oxic conditions are nearly one order of magnitude lower than those under the anoxic conditions. Further characterization reveals the existence of redox-sensitive Fe(II)-containing components, which can be responsible for the great difference in D a values. Fe(2p) X-ray photoelectron spectroscopy (XPS) results show that more Fe(III)-oxyhydroxide coating is formed on the granite's surface under aerobic conditions than is formed under anaerobic conditions. Correspondingly, Se(3d) spectra indicate that more selenium is sorbed under oxic conditions, and the sorbed amount always reached the maximum at pH values from ∼4 to ∼5. A linear combination fit of X-ray absorption near edge structure (XANES) spectroscopy data revealed that Se(0) was formed under anoxic condition and that selenite preferred to form inner-sphere complexes with Fe(III)-oxyhydroxide. Overall, this study indicates that natural Fe-bearing minerals can greatly attenuate selenite diffusion and the retardation would be enhanced under aerobic conditions. Copyright © 2016 Elsevier B.V. All rights reserved.

An initial examination of tungsten geochemistry along groundwater flow paths

NASA Astrophysics Data System (ADS)

Dave, H. B.; Johannesson, K. H.

2008-12-01

Groundwater samples were collected along groundwater flow paths from the Upper Floridan (Florida), Carrizo Sand (Texas), and the Aquia (Maryland) aquifers and analyzed for tungsten (W) concentrations by high- resolution inductively couple plasma mass spectrometry. At each well head, groundwater samples were also analyzed for pH, specific conductance, temperature, alkalinity, dissolved oxygen (DO), oxidation-reduction potential (Eh), dissolved iron speciation, and dissolved sulfide [S(-II)] concentrations. Sediment samples from the Carrizo Sand and Aquia aquifers were also collected and subjected to sequential extractions to provide additional insights into the solid-phase speciation of W in these aquifers. Tungsten concentrations varied along the groundwater flow paths chiefly in response to changing pH, and to a lesser extent, variations in the redox conditions. For groundwater from the Carrizo Sand aquifer, W ranges between 3.64 and 1297 pmol/kg, exhibiting the lowest values proximal to the recharge zone. Tungsten concentrations progressively increase along the flow path, reaching 1297 pmol/kg in the sulfidic groundwaters located approximately 60 km downgradient from the recharge area. Tungsten is strongly correlated with S(-II) concentrations and pH in Carrizo groundwaters (r = 0.95 and 0.78, respectively). Within the Aquia aquifer, however, W generally occurs at lower concentrations than the Carrizo (14 to 184 pmol/kg; mean = 80 pmol/kg), and shows no systematic trends along the flow path (e.g., r = 0.08 and 0.4 for W vs. S(-II) and pH, respectively). Our data are consistent with the increase in W concentrations in Carrizo groundwaters reflecting, in part, pH-related desorption, which has been shown to be substantial for pH greater than 8. Moreover, because of the broad similarities in the chemistry of W and Mo, which forms thiomolybdates in sulfidic waters, we suggest that thiotungstate complexes may form in sulfidic groundwaters, thus partially explaining the elevated W in sulfidic waters of the Carrizo aquifer. We propose that the substantially lower W concentrations in Aquia groundwaters reflect the fact that these waters are suboxic and have not undergone sulfate reduction. Hence, the evolution of W concentrations in the Aquia aquifer is consistent with conservative behavior in these generally oxic to suboxic groundwaters. In summary, our data indicate that pH related adsorption/desorption reactions are the key factors controlling W concentrations in oxic and sub-oxic waters, whereas formation of thiotungstate complexes may be important in sulfidic/anoxic waters.

Ordovician Jeleniów Claystone Formation of the Holy Cross Mountains, Poland - Reconstruction of Redox Conditions Using Pyrite Framboid Study

NASA Astrophysics Data System (ADS)

Smolarek, Justyna; Marynowski, Leszek; Trela, Wiesław

2014-09-01

The aim of this research is to reconstruct palaeoredox conditions during sedimentation of the Jeleniów Claystone Formation deposits, using framboid pyrite diameter measurements. Analysis of pyrite framboids diameter distribution is an effective method in the palaeoenvironmental interpretation which allow for a more detailed insight into the redox conditions, and thus the distinction between euxinic, dysoxic and anoxic conditions. Most of the samples is characterized by framboid indicators typical for anoxic/euxinic conditions in the water column, with average (mean) values ranging from 5.29 to 6.02 urn and quite low standard deviation (SD) values ranging from 1.49 to 3.0. The remaining samples have shown slightly higher values of framboid diameter typical for upper dysoxic conditions, with average values (6.37 to 7.20 um) and low standard deviation (SD) values (1.88 to 2.88). From the depth of 75.5 m till the shallowest part of the Jeleniów Claystone Formation, two samples have been examined and no framboids has been detected. Because secondary weathering should be excluded, the lack of framboids possibly indicates oxic conditions in the water column. Oxic conditions continue within the Wólka Formation based on the lack of framboids in the ZB 51.6 sample.

Ordovician Jeleniów Claystone Formation of the Holy Cross Mountains, Poland - Reconstruction of redox conditions using pyrite framboid study

NASA Astrophysics Data System (ADS)

Smolarek, Justyna; Marynowski, Leszek; Trela, Wiesław

2014-09-01

The aim of this research is to reconstruct palaeoredox conditions during sedimentation of the Jeleniów Claystone Formation deposits, using framboid pyrite diameter measurements. Analysis of pyrite framboids diameter distribution is an effective method in the palaeoenvironmental interpretation which allow for a more detailed insight into the redox conditions, and thus the distinction between euxinic, dysoxic and anoxic conditions. Most of the samples is characterized by framboid indicators typical for anoxic/euxinic conditions in the water column, with average (mean) values ranging from 5.29 to 6.02 μm and quite low standard deviation (SD) values ranging from 1.49 to 3.0. The remaining samples have shown slightly higher values of framboid diameter typical for upper dysoxic conditions, with average values (6.37 to 7.20 μm) and low standard deviation (SD) values (1.88 to 2.88). From the depth of 75.5 m till the shallowest part of the Jeleniów Claystone Formation, two samples have been examined and no framboids has been detected. Because secondary weathering should be excluded, the lack of framboids possibly indicates oxic conditions in the water column. Oxic conditions continue within the Wólka Formation based on the lack of framboids in the ZB 51.6 sample

Sulfur during the Transition from Anoxic to Oxic Atmospheres

NASA Technical Reports Server (NTRS)

Zahnle, Kevin; Catling, David; Claire, Mark

2006-01-01

The invention of oxygenic photosynthesis was likely accompanied by the introduction of large amounts of O2 and complementary reduced gases (chiefly CH4) into the atmosphere. To first approximation the venting of O2 and CH4 are stochiometrically linked. We therefore present a suite of numerical photochemical models that address the anoxic-oxic transition in an atmosphere driven by large linked inputs of biogenic 02 and CH4. We find in general that, in steady state, there are two solutions, one oxic and the other anoxic. The anoxic solution appears to be linearly stable. If volcanic SO2 fluxes are large, S disproportionates into oxidized (H2S04) and reduced (S8) exit channels. As elemental sulfur is insoluble it provides a means of preserving photochemical mass-independent fractionation (MIF). On the other hand, if the source of volcanic SO2 is smaller than today, all S can leave the atmosphere as S8. Under these conditions there would be no MIF signal. The oxic solution appears to be linearly unstable. In the oxic solutions S is invariably oxidized to sulfate, and the MIF signal would be absent. The transitional atmosphere is relatively unstable and is also the most photochemically active. Consequently it is the transitional atmosphere, not the oxic or anoxic atmospheres, that has the lowest CH4 levels and weakest greenhouse warming. As a practical matter we expect the transitional atmospheres to vary strongly in response to diurnal and seasonal biological forcing.

Distribution patterns of particulate trace metals in the water column and nepheloid layer of the Gulf of Riga.

PubMed

Poikāne, Rita; Carstensen, Jacob; Dahllöf, Ingela; Aigars, Juris

2005-07-01

The dynamics (fate) of trace metals in suspended particulate matter within the Gulf of Riga has not yet been adequately addressed in the scientific literature. Therefore, during a two year period (2001-2002) samples of suspended particulate matter and surface sediments for trace metal analysis were collected in the Gulf of Riga and the Daugava river, and these data were combined with background information from the national marine monitoring program in Latvia. This paper presents a descriptive study of solid phase trace metals (aluminium, iron, cadmium, chromium, copper, manganese, nickel, lead and zinc) dynamics and their spatial distribution within the Gulf of Riga based on Principal Component Analysis and Cluster analysis. Fluvial particulate matter and particulate Al, Fe, Cr and Ni were brought into the Gulf of Riga mainly during spring flood and thereafter quickly diluted by the water masses of the Gulf of Riga. Fine-grained suspended material and particulate Al and Fe were well mixed and evenly distributed through all deepwater basins of the Gulf of Riga. The increase of particulate Mn below the thermocline in August and a strong negative correlation with dissolved oxygen concentrations suggested that particulate Mn in the water column and the sediments were regulated mainly by changing oxic-anoxic conditions in the sediments of the Gulf of Riga. The observed correlation between Al and Fe in the water column is in contrast to that observed in the nepheloid layer where Fe correlated with Mn, obviously due to fast diagenetic processes on sediment surface. The observed negative correlation of Cd and Zn with total carbon and total nitrogen in the nepheloid layer might indicate different sedimentation mechanisms of these elements, however, this assumption is still inconclusive.

Nitrogen fixation in denitrified marine waters.

PubMed

Fernandez, Camila; Farías, Laura; Ulloa, Osvaldo

2011-01-01

Nitrogen fixation is an essential process that biologically transforms atmospheric dinitrogen gas to ammonia, therefore compensating for nitrogen losses occurring via denitrification and anammox. Currently, inputs and losses of nitrogen to the ocean resulting from these processes are thought to be spatially separated: nitrogen fixation takes place primarily in open ocean environments (mainly through diazotrophic cyanobacteria), whereas nitrogen losses occur in oxygen-depleted intermediate waters and sediments (mostly via denitrifying and anammox bacteria). Here we report on rates of nitrogen fixation obtained during two oceanographic cruises in 2005 and 2007 in the eastern tropical South Pacific (ETSP), a region characterized by the presence of coastal upwelling and a major permanent oxygen minimum zone (OMZ). Our results show significant rates of nitrogen fixation in the water column; however, integrated rates from the surface down to 120 m varied by ∼30 fold between cruises (7.5±4.6 versus 190±82.3 µmol m(-2) d(-1)). Moreover, rates were measured down to 400 m depth in 2007, indicating that the contribution to the integrated rates of the subsurface oxygen-deficient layer was ∼5 times higher (574±294 µmol m(-2) d(-1)) than the oxic euphotic layer (48±68 µmol m(-2) d(-1)). Concurrent molecular measurements detected the dinitrogenase reductase gene nifH in surface and subsurface waters. Phylogenetic analysis of the nifH sequences showed the presence of a diverse diazotrophic community at the time of the highest measured nitrogen fixation rates. Our results thus demonstrate the occurrence of nitrogen fixation in nutrient-rich coastal upwelling systems and, importantly, within the underlying OMZ. They also suggest that nitrogen fixation is a widespread process that can sporadically provide a supplementary source of fixed nitrogen in these regions.

Fate and transport of linear alkylbenzenesulfonate in a sewage- contaminated aquifer: A comparison of natural-gradient pulsed tracer tests

USGS Publications Warehouse

Krueger, C.J.; Barber, L.B.; Metge, D.W.; Field, J.A.

1998-01-01

Two natural-gradient tracer tests were conducted to determine the transport and biodegradation behavior of linear alkylbenzenesulfonate (LAS) surfactant under in situ conditions in a sewage-contaminated aquifer. The tests were conducted in two biogeochemically distinct zones of the aquifer: (1) an aerobic uncontaminated zone (oxic zone) and (2) a moderately aerobic, sewage-contaminated zone (transition zone). Chromatographic separation of the surfactant mixture was observed in both zones and attributed to the retardation of the longer alkyl chain homologues during transport. No significant loss of IAS mass was observed for the oxic zone while 20% of the LAS mass injected into the transition zone was removed due to biodegradation. Biodegradation preferentially removed the longer alkyl chain homologues and the external isomers (i.e., 2- and 3-phenyl). The removal of LAS mass coincided with a decrease in dissolved oxygen concentrations, the appearance of LAS metabolites, and an increase in the number of free-living bacteria with a concomitant change in bacteria morphology. The formation of LAS metabolites accounted for 86% of the LAS mass removed in the transition zone. Over the duration of the test, sorption and biodegradation enriched the LAS mixture in the more water-soluble and biologically resistant components.Two natural-gradient tracer tests were conducted to determine the transport and biodegradation behavior of linear alkylbenzenesulfonate (LAS) surfactant under in situ conditions in a sewage-contaminated aquifer. The tests were conducted in two biogeochemically distinct zones of the aquifer: (1) an aerobic uncontaminated zone (oxic zone) and (2) a moderately aerobic, sewage-contaminated zone (transition zone). Chromatographic separation of the surfactant mixture was observed in both zones and attributed to the retardation of the longer alkyl chain homologues during transport. No significant loss of LAS mass was observed for the oxic zone while 20% of the LAS mass injected into the transition zone was removed due to biodegradation. Biodegradation preferentially removed the longer alkyl chain homologues and the external isomers (i.e., 2- and 3-phenyl). The removal of LAS mass coincided with a decrease in dissolved oxygen concentrations, the appearance of LAS metabolites, and an increase in the number of free-living bacteria with a concomitant change in bacteria morphology. The formation of LAS metabolites accounted for 86% of the LAS mass removed in the transition zone. Over the duration of the test, sorption and biodegradation enriched the LAS mixture in the more water-soluble and biologically resistant components.

Chemical Characteristics, Water Sources and Pathways, and Age Distribution of Ground Water in the Contributing Recharge Area of a Public-Supply Well near Tampa, Florida, 2002-05

USGS Publications Warehouse

Katz, Brian G.; Crandall, Christy A.; Metz, Patricia A.; McBride, W. Scott; Berndt, Marian P.

2007-01-01

In 2001, the National Water-Quality Assessment (NAWQA) Program of the U.S. Geological Survey began a series of studies on the transport of anthropogenic and natural contaminants (TANC) to public-supply wells. The main goal of the TANC program was to better understand the source, transport, and receptor factors that control contaminant movement to public-supply wells in representative aquifers of the United States. Studies were first conducted at regional scales at four of the eight TANC study areas during 2002-03 and at small (local) scales during 2003-05 in California, Nebraska, Connecticut, and Florida. In the Temple Terrace study area near Tampa, Florida, multiple chemical indicators and geochemical and ground-water flow modeling techniques were used to assess the vulnerability of a public-supply well in the karstic Upper Floridan aquifer to contamination from anthropogenic and naturally occurring contaminants. During 2003-05, water samples were collected from the public-supply well and 13 surrounding monitoring wells that all tap the Upper Floridan aquifer, and from 15 monitoring wells in the overlying surficial aquifer system and the intermediate confining unit that are located within the modeled ground-water contributing recharge area of the public-supply well. Six volatile organic compounds and four pesticides were detected in trace concentrations (well below drinking-water standards) in water from the public-supply well, which had an open interval from 36 to 53 meters below land surface. These contaminants were detected more frequently in water samples from monitoring wells in the overlying clastic surficial aquifer system than in water from monitoring wells in the Upper Floridan aquifer in the study area. Likewise, nitrate-N concentrations in the public-supply well (0.72-1.4 milligrams per liter) were more similar to median concentrations in the oxic surficial aquifer system (2.1 milligrams per liter) than to median nitrate-N concentrations in the anoxic Upper Floridan aquifer (0.06 milligram per liter) under sulfate-reducing conditions. High concentrations of radon-222 and uranium in the public-supply well compared to those in monitoring wells in the Upper Floridan aquifer appear to originate from water moving downward through sands and discontinuous clay lenses that overlie the aquifer. Water samples also were collected from three overlapping depth intervals (38-53, 43-53, and 49-53 meters below land surface) in the public-supply well. The 49- to 53-meter interval was identified as a high-flow zone during geophysical logging of the wellbore. Water samples were collected from these depth intervals at a low pumping rate by placing a low-capacity submersible pump (less than 0.02 cubic meter per minute) at the top of each interval. To represent higher pumping conditions, a large-capacity portable submersible pump (1.6 cubic meters per minute) was placed near the top of the open interval; water-chemistry samples were collected using the low-capacity submersible pump. The 49- to 53-meter depth interval had distinctly different chemistry than the other two sampled intervals. Higher concentrations of nitrate-N, atrazine, radon, trichloromethane (chloroform), and arsenic (and high arsenic (V)/arsenic (III) ratios); lower concentrations of dissolved solids, strontium, iron, manganese, and lower nitrogen and sulfur isotope ratios were found in this highly transmissive zone in the limestone than in water from the two other depth intervals. Movement of water likely occurs from the overlying sands and clays of the oxic surficial aquifer system and intermediate confining unit (that contains high radon-222 and nitrate-N concentrations) into the anoxic Upper Floridan aquifer (that contains low radon-222 and nitrate-N concentrations). Differences in arsenic concentrations in water from the various depth intervals in the public-supply well (3.2-19.0 micrograms per liter) were related to pumping conditions. The high arsenic

Benthic flux of dissolved organic matter from lake sediment at different redox conditions and the possible effects of biogeochemical processes.

PubMed

Yang, Liyang; Choi, Jung Hyun; Hur, Jin

2014-09-15

The benthic fluxes of dissolved organic carbon (DOC), chromophoric and fluorescent dissolved organic matter (CDOM and FDOM) were studied for the sediment from an artificial lake, based on laboratory benthic chamber experiments. Conservative estimates for the benthic flux of DOC were 71 ± 142 and 51 ± 101 mg m(-2) day(-1) at hypoxic and oxic conditions, respectively. Two humic-like (C1 and C2), one tryptophan-like (C3), and one microbial humic-like (C4) components were identified from the samples using fluorescence excitation emission matrices and parallel factor analysis (EEM-PARAFAC). During the incubation period, C3 was removed while C4 was accumulated in the overlying water with no significant difference in the trends between the redox conditions. The humification index (HIX) increased with time. The combined results for C3, C4 and HIX suggested that microbial transformation may be an important process affecting the flux behaviors of DOM. In contrast, the overall accumulations of CDOM, C1, and C2 in the overlying water occurred only for the hypoxic condition, which was possibly explained by their enhanced photo-degradation and sorption to redox-sensitive minerals under the oxic condition. Our study demonstrated significant benthic flux of DOM in lake sediment and also the possible involvement of biogeochemical transformation in the processes, providing insight into carbon cycling in inland waters. Copyright © 2014 Elsevier Ltd. All rights reserved.

N2O production and consumption from stable isotopic and concentration data in the Peruvian coastal upwelling system

NASA Astrophysics Data System (ADS)

Bourbonnais, Annie; Letscher, Robert T.; Bange, Hermann W.; Échevin, Vincent; Larkum, Jennifer; Mohn, Joachim; Yoshida, Naohiro; Altabet, Mark A.

2017-04-01

The ocean is an important source of nitrous oxide (N2O) to the atmosphere, yet the factors controlling N2O production and consumption in oceanic environments are still not understood nor constrained. We measured N2O concentrations and isotopomer ratios, as well as O2, nutrient and biogenic N2 concentrations, and the isotopic compositions of nitrate and nitrite at several coastal stations during two cruises off the Peru coast ( 5-16°S, 75-81°W) in December 2012 and January 2013. N2O concentrations varied from below equilibrium values in the oxygen deficient zone (ODZ) to up to 190 nmol L-1 in surface waters. We used a 3-D-reaction-advection-diffusion model to evaluate the rates and modes of N2O production in oxic waters and rates of N2O consumption versus production by denitrification in the ODZ. Intramolecular site preference in N2O isotopomer was relatively low in surface waters (generally -3 to 14‰) and together with modeling results, confirmed the dominance of nitrifier-denitrification or incomplete denitrifier-denitrification, corresponding to an efflux of up to 0.6 Tg N yr-1 off the Peru coast. Other evidence, e.g., the absence of a relationship between ΔN2O and apparent O2 utilization and significant relationships between nitrate, a substrate during denitrification, and N2O isotopes, suggest that N2O production by incomplete denitrification or nitrifier-denitrification decoupled from aerobic organic matter remineralization are likely pathways for extreme N2O accumulation in newly upwelled surface waters. We observed imbalances between N2O production and consumption in the ODZ, with the modeled proportion of N2O consumption relative to production generally increasing with biogenic N2. However, N2O production appeared to occur even where there was high N loss at the shallowest stations.

Speciation and isotopic composition of sulfur in sediments from Jellyfish Lake, Palau

USGS Publications Warehouse

Bates, A.L.; Spiker, E. C.; Orem, W.H.; Burnett, W.C.

1993-01-01

Jellyfish Lake, Palau, is a meromictic marine lake with high organic productivity, low reactive Fe content, and anoxic bottom waters. Sediment samples from Jellyfish Lake were examined for the distribution of sulfur species and their isotopic signatures in order to gain a better understanding of sedimentary sulfur incorporation in Fe-poor environments. Surface samples were taken along a transect from a near-shore site to the center of the lake, and include a sample below oxic water, a sample below the chemocline layer, and samples below anoxic waters. Three additional samples were taken from a core, 2 m long, collected near the lake center. Sulfur to organic carbon weight ratios in all samples were lower than the expected value of 0.36 for normal marine sediment, probably because the lake water is deficient in reactive Fe to form iron sulfides. Total sulfur contents in the surface sediments indicated no changes with distance from shore; however, the sulfur content of the surface sample at the chemocline layer may be slightly higher. Total sulfur content increased with depth in the core and is inversely related to organic carbon content. Organic sulfur is the major sulfur species in the samples, followed in descending order by sulfate, disulfides and monosulfides. Sulfate sulfur isotope ??34S-values are positive (from +20.56 to +12.04???), reflecting the marine source of sulfate in Jellyfish Lake. Disulfide and monosulfide ??34S-values are negative (from -25.07 to -7.60???), because of fractionation during bacterial reduction of sulfate. Monosulfide ??34S-values are somewhat higher than those of disulfides, and they are close to the ??34S-values of organic sulfur. These results indicate that most of the organic sulfur is formed by reaction of bacteriogenic monosulfides, or possibly monosulfide-derived polysulfides, with organic matter in the sediment. ?? 1993.

Radiocarbon chronology of Black Sea sediments

NASA Astrophysics Data System (ADS)

Jones, Glenn A.; Gagnon, Alan R.

1994-03-01

Accelerator Mass Spectrometer (AMS) radiocarbon analyses have been made on 102 samples from 12 sediment cores and 23 samples from two water column profiles. These materials, collected during the first leg of the 1988 joint U.S.-Turkish Black Sea Expedition, provide the most comprehensive radiocarbon chronology of Black Sea sediments yet attempted. Radiocarbon analyses from carefully collected box cores and a mollusc shell collected live in 1931 suggest the prebomb surface waters had a Δ 14C value of -55% (460 years) and that the maximum detrital correction for radiocarbon ages of Unit I sediments is 580 years for the organic carbon and 260 years for the carbonate fractions. Evidence does not support the 1430-2000 years pre-bomb surface water and/or detrital corrections argued for in past studies. The best estimates for the age of the beginning of the final invasion of the coccolithophore Emiliania huxleyi (Unit 1/2 boundary of Ross and DEGENS, 1974, The Black Sea—geology, chemistry and biology, pp. 183-199) and the age of the first invasion of E. huxeleyi (Unit I/II boundary of HAYet al., 1991, Deep-Sea Research, 38, S1211-S1235) are 1635 ± 60 and 2720 ± 160 years BP, respectively. Sapropel formation began at approximately 7540 ± 130 years BP at all depths in the basin, a pattern in disagreement with those predicted by existing time-evolution models of sapropel formation for this basin. Our data suggest that the oxic-anoxic interface has remained relatively stable throughout the Holocene, is controlled largely by the physical oceanography of the basin, and has not evolved as assumed by previous workers.

Freshwater discharges drive high levels of methylmercury in Arctic marine biota.

PubMed

Schartup, Amina T; Balcom, Prentiss H; Soerensen, Anne L; Gosnell, Kathleen J; Calder, Ryan S D; Mason, Robert P; Sunderland, Elsie M

2015-09-22

Elevated levels of neurotoxic methylmercury in Arctic food-webs pose health risks for indigenous populations that consume large quantities of marine mammals and fish. Estuaries provide critical hunting and fishing territory for these populations, and, until recently, benthic sediment was thought to be the main methylmercury source for coastal fish. New hydroelectric developments are being proposed in many northern ecosystems, and the ecological impacts of this industry relative to accelerating climate changes are poorly characterized. Here we evaluate the competing impacts of climate-driven changes in northern ecosystems and reservoir flooding on methylmercury production and bioaccumulation through a case study of a stratified sub-Arctic estuarine fjord in Labrador, Canada. Methylmercury bioaccumulation in zooplankton is higher than in midlatitude ecosystems. Direct measurements and modeling show that currently the largest methylmercury source is production in oxic surface seawater. Water-column methylation is highest in stratified surface waters near the river mouth because of the stimulating effects of terrestrial organic matter on methylating microbes. We attribute enhanced biomagnification in plankton to a thin layer of marine snow widely observed in stratified systems that concentrates microbial methylation and multiple trophic levels of zooplankton in a vertically restricted zone. Large freshwater inputs and the extensive Arctic Ocean continental shelf mean these processes are likely widespread and will be enhanced by future increases in water-column stratification, exacerbating high biological methylmercury concentrations. Soil flooding experiments indicate that near-term changes expected from reservoir creation will increase methylmercury inputs to the estuary by 25-200%, overwhelming climate-driven changes over the next decade.

Nitrous oxide from aerated dairy manure slurries: Effects of aeration rates and oxic/anoxic phasing.

PubMed

Molodovskaya, Marina; Singurindy, Olga; Richards, Brian K; Steenhuis, Tammo S

2008-12-01

Small-scale laboratory research was conducted to compare the effects of different aeration rates and oxic/anoxic phasing on nitrous oxide (N(2)O) formation from dairy manure slurries. Manure slurry samples were incubated in triplicate for three-weeks under a range of continuous sweep gas flows (0.01-0.23L min(-1)kg(-1) slurry) with and without oxygen (air and dinitrogen gas). The net release of N(2)O-N was affected by both aeration rates and oxic/anoxic conditions, whereas ammonia volatilization depended mainly on gas flow rates. Maximum N(2)O-N losses after three-weeks incubation were 4.2% of total slurry N. Major N losses (up to 50% of total slurry N) were caused by ammonia volatilization that increased with increasing gas flow rates. The lowest nitrous oxide and ammonia production was observed from low flow phased oxic/anoxic treatment.

Reaction paths and host phases of uranium isotopes (235U; 238U), Saanich Inlet

NASA Astrophysics Data System (ADS)

Amini, M.; Holmden, C. E.; Francois, R. H.

2009-12-01

In recent times, Uranium has become increasingly the focus of stable isotope fractionation studies. Variations in 238U/235U have been reported as a result of redox reactions [1,2] from the nuclear field shift effect [3], and a mass-dependent, microbially-mediated, kinetic isotope effect [4]. The 238U/235U variability caused by changes in environmental redox conditions leads to an increase in the 238U/235U ratios of the reduced U species sequestered into marine sediments. This points to U isotope variability as a new tool to study ancient ocean redox changes. However, the process by which reduced sediments become enriched in the heavy isotopes of U is not yet known, and hence the utility of 238U/235U as a redox tracer remains to be demonstrated. In order to further constrain sedimentary U enrichment and related isotope effect, we are investigating U isotopic compositions of water samples and fresh surface sediment grab samples over a range of redox conditions in the seasonally anoxic Saanich Inlet, on the east coast of Vancouver Island. U was sequentially extracted from sediments in order to characterize specific fractions for their isotopic composition. The measurements were carried out by MC-ICPMS using 233U/236U-double spike technique. The data are reported as δ238U relative to NBL 112a with a 238U/235U ratio of 137.88 (2sd). External precision is better than 0.10‰ (2sd). Fifteeen analyses of seawater yielded δ238U of -0.42±0.08‰ (2sd). The results for the water samples indicate a homogenous δ238U value throughout the Saanich Inlet water column that matches the global seawater signature. All of the water samples from above and below average -0.42±0.05‰ (2sd). In contrast, a plankton net sample yielded a distinctly different, (about 0.5‰ lighter) isotope value. Bacterial reduction experiments [4] have also shown isotope enrichment factors of about -0.3‰. In addition, metal isotope fractionation occurs during adsorption with the light isotope being preferentially adsorbed [5]. Whether plankton mediated chemical reduction or scavenging causes this fractionation will be further investigated by leaching experiments on sediment trap samples. By contrast, weak acidic leachates (at pH 6) of suboxic bottom sediments, tend towards higher δ238U values. For oxic sediments, U contents of this fraction were below detection limit. Stronger leaching at pH 3 removed most of the uranium from suboxic and oxic sediments. For oxic sediments, this fraction yields the seawater δ238U signature, while the U released from the suboxic sample is about 0.2‰ heavier. This matches the value for previously reported bulk analyses of suboxic sediments [1] implying that the reduced sedimentary U is released by this treatment,. Major and trace element analyses and XRD patterns will help relating this fraction to a specific mineral or reactive phase. [1] Weyer et al. (2007) GCA 72, 345-399. [2] Stirling et al. (2007) EPSL 264, 208-225. [3] Schauble (2007) GCA 71, 2170-2189. [4] Rademacher et al. (2006) Environ. Sci. Technol. 40,6943-6948. [5] Wasylenki (2009) GCA A1419.

Antimony isotopic composition in river waters affected by ancient mining activity.

PubMed

Resongles, Eléonore; Freydier, Rémi; Casiot, Corinne; Viers, Jérôme; Chmeleff, Jérôme; Elbaz-Poulichet, Françoise

2015-11-01

In this study, antimony (Sb) isotopic composition was determined in natural water samples collected along two hydrosystems impacted by historical mining activities: the upper Orb River and the Gardon River watershed (SE, France). Antimony isotope ratio was measured by HG-MC-ICP-MS (Hydride Generation Multi-Collector Inductively Coupled Plasma Mass Spectrometer) after a preconcentration and purification step using a new thiol-cellulose powder (TCP) procedure. The external reproducibility obtained for δ(123)Sb measurements of our in-house Sb isotopic standard solution and a certified reference freshwater was 0.06‰ (2σ). Significant isotopic variations were evident in surface waters from the upper Orb River (-0.06‰≤δ(123)Sb≤+0.11‰) and from the Gardon River watershed (+0.27‰≤δ(123)Sb≤+0.83‰). In particular, streams that drained different former mining sites exploited for Sb or Pb-Zn exhibited contrasted Sb isotopic signature, that may be related to various biogeochemical processes occurring during Sb transfer from rocks, mine wastes and sediments to the water compartment. Nevertheless, Sb isotopic composition appeared to be stable along the Gardon River, which might be attributed to the conservative transport of Sb at distance from mine-impacted streams, due to the relative mobile behavior of Sb(V) in natural oxic waters. This study suggests that Sb isotopic composition could be a useful tool to track pollution sources and/or biogeochemical processes in hydrologic systems. Copyright © 2015 Elsevier B.V. All rights reserved.

Effects of changing redox conditions on the dynamics of dissolved organic matter and CO2 in paddy soils

NASA Astrophysics Data System (ADS)

Hanke, Alexander; Cao, Zhi Hong; Liu, Qin; Muhr, Jan; Kalbitz, Karsten

2010-05-01

The current knowledge about dissolved organic matter (DOM) dynamics in soils and its dependence on different C pools based mainly on observations and experiments in aerobic environments. We have only a limited understanding about the effects of changing redox conditions on production and composition of DOM although this fraction of soil organic matter is important for greenhouse gas emission and carbon storage in soils. In many ecosystems temporal and spatial changes of oxic and anoxic conditions are evident and might even increase in future. It is assumed that changing redox conditions are the key drivers of DOM dynamics in such ecosystems. More detailed we tested the following hypotheses: Anoxic conditions result in relative DOM accumulation due to less mineralization of already produced DOM Close relationship between DOM production and CO2 emission 14C signature of CO2 enables the identification of different C pools degraded at oxic and anoxic conditions We chose paddy soils as a model ecosystem because these soils are anoxic during the rice growing period and oxic during harvest and growth of other crops. Furthermore, paddy soils have oxic and anoxic horizons. Soils of a unique chronosequence of paddy soil evolution (50 to 2000 years, China) were studied in direct comparison to non-paddy soils of the same age. In these soils, exposed to different redox conditions over defined periods of times, the dynamics of DOM, CO2, 14C of the CO2 and other redox sensitive elements were followed in laboratory experiments. In the latter redox conditions were changed every 3 weeks from oxic to anoxic and vice versa. Besides analysis of the composition of the soil solution and the gas phase we determined differences in C pools being respired at oxic and anoxic conditions by 14C AMS of the CO2. The measured redox potentials of -50 mV to 250mV at anoxic conditions and 350 mV to 550 mV at oxic conditions were in the expected range and proofed the appropriate setting of the chosen incubation method. PH values varied between 5.5 and 7.5, where anoxic samples had higher values than oxic ones. We further observed only small DOC contents of less than 1mg per g C. Under anoxic conditions as well as among the non-paddy soils DOC production was slightly higher than their respective counterparts. However, we could not find large effects of the time of rice cultivation. Nevertheless, the 2000 year old paddy soil showed highest DOC and CO2 production. The increase of DOC and CO2 production was strongest when the oxic period disrupted the anoxic conditions. 14C data revealed that CO2 respired from the 700 year old paddy soil was much older than from the 2000 year old paddy soil independently from redox condition. Furthermore, C mineralized at anoxic conditions was older than at oxic ones. During the incubation experiment the C consumption shifted from older pools to younger ones. We conclude that DOM accumulated at anoxic conditions will be quickly mineralized at oxic conditions. The influence of soil development on the C dynamics was less important than expected, thus fresh organic matter seems to play a more decisive role. The unexpected large decomposition of old organic matter at anoxic conditions hints to changes in the microbial community involved.

Using multiple chemical indicators to assess sources of nitrate and age of groundwater in a karstic spring basin

USGS Publications Warehouse

Katz, B.; Copeland, R.; Greenhalgh, T.; Ceryak, R.; Zwanka, W.

2005-01-01

Human health and ecological concerns have arisen due to a steady increase in nitrate-N concentrations during the past 40 years in Fannin Springs (0.3-4.7 mg/L), a regional discharge point with an average flow of >2.8 m3/second (>100 ft3/second) for water from the karstic Upper Floridan aquifer (UFA). Multiple chemical indicators (major dissolved species, 15N and 18O of nitrate, dissolved gases, 78 pesticides and degradates, and 67 organic compounds typically found in domestic and industrial wastewater) and transient tracers (3H/3He, chlorofluorocarbons [CFCs], sulfur hexafluoride [SF6]) were analyzed in water samples from nine wells along three transects and in spring water to assess groundwater age and potential contaminant sources. Land use is predominantly agricultural (52 percent) and forest (31 percent) in the 320 km2 (124 mi2) spring basin, which was delineated from a potentiometric-surface map of the UFA using high-resolution water-level data. Nitrate-N concentrations were highly variable in the oxic UFA and ranged from <0.02 to 4.7 mg/L. ?? 15N-NO3 values (3.4-9.9 per mil) indicated that nitrate contamination originated from inorganic sources (synthetic fertilizer) and organic sources (manure spreading or waste disposal). Higher nitrate concentrations and the younger age of spring water relative to water from upgradient wells indicate better communication with N sources at the surface. Apparent ages of groundwater correlated positively with well depth (P < 0.05) and were younger in water from wells nearer to the spring (<8 years) compared with other wells (10-50 years). Most transient tracer concentrations were consistent with binary mixing curves representing mixtures of water recharged during the past 10 years and older water (recharged before 1940). Young water mixing fractions ranged from 0.07 to 0.90. Trace levels of herbicides found in groundwater and spring water were indicative of applications for vegetative control in agricultural and other land-use types.

Intense molybdenum accumulation in sediments underneath a nitrogenous water column and implications for the reconstruction of paleo-redox conditions based on molybdenum isotopes

NASA Astrophysics Data System (ADS)

Scholz, Florian; Siebert, Christopher; Dale, Andrew W.; Frank, Martin

2017-09-01

The concentration and isotope composition of molybdenum (Mo) in sediments and sedimentary rocks are widely used proxies for anoxic conditions in the water column of paleo-marine systems. While the mechanisms leading to Mo fixation in modern restricted basins with anoxic and sulfidic (euxinic) conditions are reasonably well constrained, few studies have focused on Mo cycling in the context of open-marine anoxia. Here we present Mo data for water column particulate matter, modern surface sediments and a paleo-record covering the last 140,000 years from the Peruvian continental margin. Mo concentrations in late Holocene and Eemian (penultimate interglacial) shelf sediments off Peru range from ∼70 to 100 μg g-1, an extent of Mo enrichment that is thought to be indicative of (and limited to) euxinic systems. To investigate if this putative anomaly could be related to the occasional occurrence of sulfidic conditions in the water column overlying the Peruvian shelf, we compared trace metal (Mo, vanadium, uranium) enrichments in particulate matter from oxic, nitrate-reducing (nitrogenous) and sulfidic water masses. Coincident enrichments of iron (Fe) (oxyhydr)oxides and Mo in the nitrogenous water column as well as co-variation of dissolved Fe and Mo in the sediment pore water suggest that Mo is delivered to the sediment surface by Fe (oxyhydr)oxides. Most of these precipitate in the anoxic-nitrogenous water column due to oxidation of sediment-derived dissolved Fe with nitrate as a terminal electron acceptor. Upon reductive dissolution in the surface sediment, a fraction of the Fe and Mo is re-precipitated through interaction with pore water sulfide. The Fe- and nitrate-dependent mechanism of Mo accumulation proposed here is supported by the sedimentary Mo isotope composition, which is consistent with Mo adsorption onto Fe (oxyhydr)oxides. Trace metal co-variation patterns as well as Mo and nitrogen isotope systematics suggest that the same mechanism of Mo delivery caused the 'anomalously' high interglacial Mo accumulation rates in the paleo-record. Our findings suggest that Fe- and nitrate-dependent Mo shuttling under nitrogenous conditions needs to be considered a possible reason for sedimentary Mo enrichments during past periods of widespread anoxia in the open ocean.

Relative vulnerability of public supply wells to VOC contamination in hydrologically distinct regional aquifers

USGS Publications Warehouse

Kauffman, L.J.; Chapelle, F.H.

2010-01-01

A process-based methodology was used to compare the vulnerability of public supply wells tapping seven study areas in four hydrologically distinct regional aquifers to volatile organic compound (VOC) contamination. This method considers (1) contributing areas and travel times of groundwater flowpaths converging at individual supply wells, (2) the oxic and/or anoxic conditions encountered along each flowpath, and (3) the combined effects of hydrodynamic dispersion and contaminant- and oxic/anoxic-specific biodegradation. Contributing areas and travel times were assessed using particle tracks generated from calibrated regional groundwater flow models. These results were then used to estimate VOC concentrations relative to an unspecified initial concentration (C/C0) at individual public supply wells. The results show that the vulnerability of public supply wells to VOC contamination varies widely between different regional aquifers. Low-recharge rates, long travel times, and the predominantly oxic conditions characteristic of Basin and Range aquifers in the western United States leads to lower vulnerability to VOCs, particularly to petroleum hydrocarbons such as benzene and toluene. On the other hand, high recharge rates and short residence times characteristic of the glacial aquifers of the eastern United States leads to greater vulnerability to VOCs. These differences lead to distinct patterns of C/C0 values estimated for public supply wells characteristic of each aquifer, information that can be used by resource managers to develop monitoring plans based on relative vulnerability, to locate new public supply wells, or to make land-use management decisions. Journal compilation ?? 2010 National Ground Water Association. No claim to original US government works.

Coupled Mo-U abundances and isotopes in a small marine euxinic basin: Constraints on processes in euxinic basins

NASA Astrophysics Data System (ADS)

Bura-Nakić, Elvira; Andersen, Morten B.; Archer, Corey; de Souza, Gregory F.; Marguš, Marija; Vance, Derek

2018-02-01

Sedimentary molybdenum (Mo) and uranium (U) abundances, as well as their isotope systematics, are used to reconstruct the evolution of the oxygenation state of the surface Earth from the geological record. Their utility in this endeavour must be underpinned by a thorough understanding of their behaviour in modern settings. In this study, Mo-U concentrations and their isotope compositions were measured in the water column, sinking particles, sediments and pore waters of the marine euxinic Lake Rogoznica (Adriatic Sea, Croatia) over a two year period, with the aim of shedding light on the specific processes that control Mo-U accumulation and isotope fractionations in anoxic sediment. Lake Rogoznica is a 15 m deep stratified sea-lake that is anoxic and euxinic at depth. The deep euxinic part of the lake generally shows Mo depletions consistent with near-quantitative Mo removal and uptake into sediments, with Mo isotope compositions close to the oceanic composition. The data also, however, show evidence for periodic additions of isotopically light Mo to the lake waters, possibly released from authigenic precipitates formed in the upper oxic layer and subsequently processed through the euxinic layer. The data also show evidence for a small isotopic offset (∼0.3‰ on 98Mo/95Mo) between particulate and dissolved Mo, even at highest sulfide concentrations, suggesting minor Mo isotope fractionation during uptake into euxinic sediments. Uranium concentrations decrease towards the bottom of the lake, where it also becomes isotopically lighter. The U systematics in the lake show clear evidence for a dominant U removal mechanism via diffusion into, and precipitation in, euxinic sediments, though the diffusion profile is mixed away under conditions of increased density stratification between an upper oxic and lower anoxic layer. The U diffusion-driven precipitation is best described with an effective 238U/235U fractionation of +0.6‰, in line with other studied euxinic basins. Combining the Mo and U systematics in Lake Rogoznica and other euxinic basins, it is apparent that the two different uptake mechanisms of U and Mo can lead to spatially and temporally variable Mo/U and Mo-U isotope systematics that depend on the rate of water renewal versus removal to sediment, the sulfide concentration, and the geometry of the basin. This study further emphasises the potential of combining multiple observations, from Mo-U enrichment and isotope systematics, for disentangling the various processes via which redox conditions control the chemistry of modern and ancient sediments.

Uptake of elements from seawater by ferromanganese crusts: Solid-phase associations and seawater speciation

USGS Publications Warehouse

Koschinsky, A.; Hein, J.R.

2003-01-01

Marine Fe-Mn oxyhydroxide crusts form by precipitation of dissolved components from seawater. Three hydrogenetic crust samples (one phosphatized) and two hydrothermal Mn-oxide samples were subjected to a sequential-leaching procedure in order to determine the host phases of 40 elements. Those host-phase associations are discussed with respect to element speciation in seawater. The partitioning of elements between the two major phases, Mn oxide and Fe oxyhydroxide, can in a first-order approximation be explained by a simple sorption model related to the inorganic speciation of the elements in seawater, as has been proposed in earlier models. Free and weakly complexed cations, such as alkali and alkaline earth metals, Mn, Co, Ni, Zn, T1(I), and partly Y, are sorbed preferentially on the negatively charged surface of the MnO2 in hydrogenetic crusts. The driving force is a strong coulombic interaction. All neutral or negatively charged chloro (Cd, Hg, T1), carbonate (Cu, Y, Pb, and U), and hydroxide (Be, Sc, Ti, Fe, Zr, Nb, In, Sn, Sb, Te, Hf, Ta, Bi, Th, and T1(III)) complexes and oxyanions (V, Cr, As, Se, Mo, and W) bind to the slightly positively charged surface of the amorphous FeOOH phase. While coulombic interaction can explain the sorption of the negatively charged species, the binding of neutral species is based on specific chemical interaction. Organic complexation of elements in deep-ocean water seems to be at most of minor importance. Surface oxidation can explain some strong metal associations, e.g. of Co and T1 with the MnO2 and Te with the FeOOH. Sorption reactions initially driven by coulombic forces are often followed by the formation of specific bonds between the adsorbate and the atoms of the oxide surface. Differences in the associations of some metals between the non-phosphatized and phosphatized hydrogenetic crusts and between the hydrogenetic and the hydrothermal samples reflect the different physico-chemical environments of formation and speciations in oxic seawater vs. less-oxic fluids, especially for the redox-sensitive metals such as Mo and V. These environmental-related differences indicate that the methodology of chemical speciation used here in combination with spectroscopic methods may allow for the detection of changes in paleoceanographic conditions recorded during the several tens of millions of years of crust growth. ?? 2003 Elsevier Science B.V. All rights reserved.

Cr(VI) Occurrence and Geochemistry in Water From Public-Supply Wells in California

DOE PAGES

Izbicki, John A.; Wright, Michael T.; Seymour, Whitney A.; ...

2015-08-18

Hexavalent chromium, Cr(VI), in 918 wells sampled throughout California between 2004 and 2012 by the Groundwater Ambient Monitoring and Assessment Program—Priority Basin Project (GAMA—PBP) ranged from less than the study reporting limit (SRL) of 1 microgram per liter (μg/L) to 32 μg/L. Statewide, Cr(VI) was reported in 31 percent of sampled wells and equaled or exceeded the recently established (2014) California Maximum Contaminant Level (MCL) for Cr(VI) of 10 μg/L in 4 percent of sampled wells. Cr(VI) data collected for regulatory purposes overestimate Cr(VI) occurrence. Ninety percent of chromium was present as Cr(VI), which was detected more frequently and atmore » higher concentrations in alkaline (pH > 8), oxic water, and more frequently in agricultural and urban land uses compared to native land uses. Chemical, isotopic (tritium and carbon-14), and noble-gas data show high Cr(VI) in water from wells in alluvial aquifers in the southern California deserts result from long groundwater-residence times and geochemical reactions such as silicate weathering that increase pH, while oxic conditions persist. High Cr(VI) in water from wells in alluvial aquifers along the west-side of the Central Valley results from high-chromium abundance in source rock eroded to form those aquifers, and areal recharge processes (including irrigation return) that mobilize chromium from the unsaturated zone. Cr(VI) co-occurred with oxyanions having similar chemistry, including vanadium, selenium, and uranium. Cr(VI) was positively correlated with nitrate, consistent with increased concentrations in areas of agricultural land use and mobilization of chromium from the unsaturated zone by irrigation return.« less

Tidal and Seasonal River Stage Fluctuations Impact the Formation of Permeable Natural Reactive Barriers in Riverbank Sediments

NASA Astrophysics Data System (ADS)

Shuai, P.; Myers, K.; Knappett, P.; Cardenas, M. B.

2017-12-01

River stage fluctuations, induced by ocean tides and rainfall, enhance the exchange between oxic river water and reducing groundwater. When mixing occurs within riverbank aquifers high in dissolved iron (Fe) and arsenic (As), the timing and extent of mixing likely control the accumulation and mobility of arsenic (As) within the hyporheic zone. Here we analyzed the impact of tidal and seasonal water level fluctuations on the formation of a Permeable Natural Reactive Barrier (PNRB) within an aquifer adjacent to the Meghna River, Bangladesh and its impact on As mobility. We found that the periodicity and amplitude of river stage fluctuations strongly control the spatial and temporal distribution of the PNRB, comprised of rapidly precipitated iron oxides, in this riverbank along a relatively straight reach of the Meghna River. The PNRB forms much faster and with higher concentration of Fe-oxide under semi-diurnal (12 hr) tidal fluctuations compared to simulations run assuming only neap-spring tides (14 day). As tidal amplitude increases, a larger contact area between oxic river water and reducing groundwater results which in turn leads to the horizontal expansion of the PNRB into the riverbank. Seasonal fluctuations expand the PNRB up to 60 m horizontally and 5 m vertically. In contrast neap-spring tidal fluctuations result in a smaller PNRB that is 10 and 3 m in the horizontal and vertical dimensions. The predicted changes in the spatial distribution of iron oxides within the riverbank would trap and release As at different times of the year. The PNRB could act as a secondary source of As to drinking water aquifers under sustained groundwater pumping scenarios near the river.

Cr(VI) occurrence and geochemistry in water from public-supply wells in California

USGS Publications Warehouse

Izbicki, John; Wright, Michael; Seymour, Whitney A.; McCleskey, R. Blaine; Fram, Miranda S.; Belitz, Kenneth; Esser, Bradley K.

2015-01-01

Hexavalent chromium, Cr(VI), in 918 wells sampled throughout California between 2004 and 2012 by the Groundwater Ambient Monitoring and Assessment-Priority Basin Project (GAMA-PBP) ranged from less than the study reporting limit of 1 microgram per liter (μg/L) to 32 μg/L. Statewide, Cr(VI) was reported in 31 percent of wells and equaled or exceeded the recently established (2014) California Maximum Contaminant Level (MCL) for Cr(VI) of 10 μg/L in 4 percent of wells. Cr(VI) data collected for regulatory purposes overestimated Cr(VI) occurrence compared to spatially-distributed GAMA-PBP data. Ninety percent of chromium was present as Cr(VI), which was detected more frequently and at higher concentrations in alkaline (pH ≥ 8), oxic water; and more frequently in agricultural and urban land uses compared to native land uses. Chemical, isotopic (tritium and carbon-14), and noble-gas data show high Cr(VI) in water from wells in alluvial aquifers in the southern California deserts result from long groundwater-residence times and geochemical reactions such as silicate weathering that increase pH, while oxic conditions persist. High Cr(VI) in water from wells in alluvial aquifers along the west-side of the Central Valley results from high-chromium in source rock eroded to form those aquifers, and areal recharge processes (including irrigation return) that can mobilize chromium from the unsaturated zone. Cr(VI) co-occurred with oxyanions having similar chemistry, including vanadium, selenium, and uranium. Cr(VI) was positively correlated with nitrate, consistent with increased concentrations in areas of agricultural land use and mobilization of chromium from the unsaturated zone by irrigation return.

Zero-valent iron treatment of dark brown colored coffee effluent: Contributions of a core-shell structure to pollutant removals.

PubMed

Tomizawa, Mayuka; Kurosu, Shunji; Kobayashi, Maki; Kawase, Yoshinori

2016-12-01

The decolorization and total organic carbon (TOC) removal of dark brown colored coffee effluent by zero-valent iron (ZVI) have been systematically examined with solution pH of 3.0, 4.0, 6.0 and 8.0 under oxic and anoxic conditions. The optimal decolorization and TOC removal were obtained at pH 8.0 with oxic condition. The maximum efficiencies of decolorization and TOC removal were 92.6 and 60.2%, respectively. ZVI presented potential properties for pollutant removal at nearly neutral pH because of its core-shell structure in which shell or iron oxide/hydroxide layer on ZVI surface dominated the decolorization and TOC removal of coffee effluent. To elucidate the contribution of the core-shell structure to removals of color and TOC at the optimal condition, the characterization of ZVI surface by scanning electron microscopy (SEM) with an energy dispersive X-ray spectroscope (EDS), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) was conducted. It was confirmed that the core-shell structure was formed and the shell on ZVI particulate surface and the precipitates formed during the course of ZVI treatment consisted of iron oxides and hydroxides. They were significantly responsible for decolorization and TOC removal of coffee effluent via adsorption to shell on ZVI surface and inclusion into the precipitates rather than the oxidative degradation by OH radicals and the reduction by emitted electrons. The presence of dissolved oxygen (DO) enhanced the formation of the core-shell structure and as a result improved the efficiency of ZVI treatment for the removal of colored components in coffee effluents. ZVI was found to be an efficient material toward the treatment of coffee effluents. Copyright © 2016 Elsevier Ltd. All rights reserved.

Marine sulfur cycle constrained from isotope analysis of different forms of sulfur in the 3.2 Ga black shale (DXCL-DP) from Pilbara, Australia

NASA Astrophysics Data System (ADS)

Kobayashi, Y.; Yamaguchi, K. E.; Sakamoto, R.; Naraoka, H.; Kiyokawa, S.; Ikehara, M.; Ito, T.

2012-12-01

Co-evolution of early life and surface environment has been one of the most important events on Earth. Rise of atmospheric oxygen, or as known as GOE (Great Oxidation Event: e.g., Holland, 1994), has been widely believed to have occurred at around 2.4 billion years ago. But geological and geochemical evidence suggest possibility of much earlier (by hundreds of millions of years) existence of oxic atmosphere and oceans. In order to further investigate the mystery of biological and environmental evolution, we conducted continental drilling in northwestern Pilbara, Western. Australia, to obtain 3.2 billion-years-old least-metamorphosed drillcore black shale samples (DXCL-DP:Dixon Island - Cleaverville Drilling Project; Yamaguchi et al., 2009). Preliminary stable isotope analyses using these samples suggested that photosynthetic organisms produced organic matter (Hosoi et al., 2011), nitrogen fixing bacteria were intermittently active (Yamada et al., 2011), and sulfate-reducing bacteria were active in environment with a limited supply of sulfate (Sakamoto et al., 2011) in the 3.2 Ga ocean. Bulk S isotope compositions could only provide limited information on the biogeochemical cycling of sedimentary S, because it is normally present as different facies (acid-volatile sulfur: AVS, pyrite: FeS2, sulfate, organic sulfur: Sorg, and elemental sulfur: S0) that depend on physicochemical and biological conditions. Therefore, abundance and isotope ratios of these species possess very useful information on oceanic and diagenetic conditions such as redox state and microbiological activity. In order to constrain biogeochemical cycling of S in the 3.2 Ga ocean, we conducted sequential extraction analysis using the DXCL-DP black shales to obtain different S-bearing species and S isotopic analysis. Average S contents for each form of S-bearing species were: ΣS = 2.56 wt.%, AVS = 0.02 wt.%, pyrite = 1.61 wt.%, and sulfate = 0.57 wt%. Relationship between amounts of pyrite-S and organic C suggest presence of syngenetic pyrite (formed in water column) as well as diagenetic pyrite. Average S isotope compositions are: pyrite = 12.3±6.3 ‰, sulfate = 17.3 ± 7.1 ‰, and difference between them are up to as high as 16.8 ‰. These results show that depositional environment was probably close to the modern Black Sea, where sulfate-reducing bacteria are active in anaerobic water mass in semi-closed deep basin, with a limited supply of sulfate from the oxic surface ocean.

Nitrate-dependent iron oxidation limits iron transport in anoxic ocean regions

NASA Astrophysics Data System (ADS)

Scholz, Florian; Löscher, Carolin R.; Fiskal, Annika; Sommer, Stefan; Hensen, Christian; Lomnitz, Ulrike; Wuttig, Kathrin; Göttlicher, Jörg; Kossel, Elke; Steininger, Ralph; Canfield, Donald E.

2016-11-01

Iron is an essential element for life on Earth and limits primary production in large parts of the ocean. Oxygen-free continental margin sediments represent an important source of bioavailable iron to the ocean, yet little of the iron released from the seabed reaches the productive sea surface. Even in the anoxic water of oxygen minimum zones, where iron solubility should be enhanced, most of the iron is rapidly re-precipitated. To constrain the mechanism(s) of iron removal in anoxic ocean regions we explored the sediment and water in the oxygen minimum zone off Peru. During our sampling campaign the water column featured two distinct redox boundaries separating oxic from nitrate-reducing (i.e., nitrogenous) water and nitrogenous from weakly sulfidic water. The sulfidic water mass in contact with the shelf sediment contained elevated iron concentrations >300 nM. At the boundary between sulfidic and nitrogenous conditions, iron concentrations dropped sharply to <20 nM coincident with a maximum in particulate iron concentration. Within the iron gradient, we found an increased expression of the key functional marker gene for nitrate reduction (narG). Part of this upregulation was related to the activity of known iron-oxidizing bacteria. Collectively, our data suggest that iron oxidation and removal is induced by nitrate-reducing microbes, either enzymatically through anaerobic iron oxidation or by providing nitrite for an abiotic reaction. Given the important role that iron plays in nitrogen fixation, photosynthesis and respiration, nitrate-dependent iron oxidation likely represents a key-link between the marine biogeochemical cycles of nitrogen, oxygen and carbon.

Methyl tert-butyl ether biodegradation by indigenous aquifer microorganisms under natural and artificial oxic conditions

USGS Publications Warehouse

Landmeyer, J.E.; Chapelle, F.H.; Herlong, H.H.; Bradley, P.M.

2001-01-01

Microbial communities indigenous to a shallow groundwater system near Beaufort, SC, degraded milligram per liter concentrations of methyl tert-butyl ether (MTBE) under natural and artificial oxic conditions. Significant MTBE biodegradation was observed where anoxic, MTBE-contaminated groundwater discharged to a concrete-lined ditch. In the anoxic groundwater adjacent to the ditch, concentrations of MTBE were > 1 mg/L. Where groundwater discharge occurs, dissolved oxygen (DO) concentrations beneath the ditch exceeded 1.0 mg/L to a depth of 1.5 m, and MTBE concentrations decreased to <1 ??g/L prior to discharge. MTBE mass flux calculations indicate that 96% of MTBE mass loss occurs in the relatively small oxic zone prior to discharge. Samples of a natural microbial biofilm present in the oxic zone beneath the ditch completely degraded [U-14C]MTBE to [14C]CO2 in laboratory liquid culture studies, with no accumulation of intermediate compounds. Upgradient of the ditch in the anoxic, MTBE and BTEX-contaminated aquifer, addition of a soluble oxygen release compound resulted in oxic conditions and rapid MTBE biodegradation by indigenous microorganisms. In an observation well located closest to the oxygen addition area, DO concentrations increased from 0.4 to 12 mg/L in <60 days and MTBE concentrations decreased from 20 to 3 mg/L. In the same time period at a downgradient observation well, DO increased from <0.2 to 2 mg/L and MTBE concentrations decreased from 30 to <5 mg/L. These results indicate that microorganisms indigenous to the groundwater system at this site can degrade milligram per liter concentrations of MTBE under natural and artificial oxic conditions.

Variation in aluminum, iron, and particle concentrations in oxic groundwater samples collected by use of tangential-flow ultrafiltration with low-flow sampling

NASA Astrophysics Data System (ADS)

Szabo, Zoltan; Oden, Jeannette H.; Gibs, Jacob; Rice, Donald E.; Ding, Yuan

2002-02-01

Particulates that move with ground water and those that are artificially mobilized during well purging could be incorporated into water samples during collection and could cause trace-element concentrations to vary in unfiltered samples, and possibly in filtered samples (typically 0.45-um (micron) pore size) as well, depending on the particle-size fractions present. Therefore, measured concentrations may not be representative of those in the aquifer. Ground water may contain particles of various sizes and shapes that are broadly classified as colloids, which do not settle from water, and particulates, which do. In order to investigate variations in trace-element concentrations in ground-water samples as a function of particle concentrations and particle-size fractions, the U.S. Geological Survey, in cooperation with the U.S. Air Force, collected samples from five wells completed in the unconfined, oxic Kirkwood-Cohansey aquifer system of the New Jersey Coastal Plain. Samples were collected by purging with a portable pump at low flow (0.2-0.5 liters per minute and minimal drawdown, ideally less than 0.5 foot). Unfiltered samples were collected in the following sequence: (1) within the first few minutes of pumping, (2) after initial turbidity declined and about one to two casing volumes of water had been purged, and (3) after turbidity values had stabilized at less than 1 to 5 Nephelometric Turbidity Units. Filtered samples were split concurrently through (1) a 0.45-um pore size capsule filter, (2) a 0.45-um pore size capsule filter and a 0.0029-um pore size tangential-flow filter in sequence, and (3), in selected cases, a 0.45-um and a 0.05-um pore size capsule filter in sequence. Filtered samples were collected concurrently with the unfiltered sample that was collected when turbidity values stabilized. Quality-assurance samples consisted of sequential duplicates (about 25 percent) and equipment blanks. Concentrations of particles were determined by light scattering.

Stimulated anoxic biodegradation of aromatic hydrocarbons using Fe(III) ligands

USGS Publications Warehouse

Lovley, D.R.; Woodward, J.C.; Chapelle, F.H.

1994-01-01

Contamination of ground waters with water-soluble aromatic hydrocarbons, common components of petroleum pollution, often produces anoxic conditions under which microbial degradation of the aromatics is slow. Oxygen is often added to contaminated ground water to stimulate biodegradation, but this can be technically difficult and expensive. Insoluble Fe(III) oxides, which are generally abundant in shallow aquifers, are alternative potential oxidants, but are difficult for microorganisms to access. Here we report that adding organic ligands that bind to Fe(III) dramatically increases its bioavailability, and that in the presence of these ligands, rates of degradation of aromatic hydrocarbons in anoxic aquifer sediments are comparable to those in oxic sediments. We find that even benzene, which is notoriously refractory in the absence of oxygen, can be rapidly degraded. Our results suggest that increasing the bioavailability of Fe(III) by adding suitable ligands provides a potential alternative to oxygen addition for the bioremediation of petroleum-contaminated aquifers.Contamination of ground waters with water-soluble aromatic hydrocarbons, common components of petroleum pollution, often produces anoxic conditions under which microbial degradation of the aromatics is slow. Oxygen is often added to contaminated ground water to stimulate biodegradation, but this can be technically difficult and expensive. Insoluble Fe(III) oxides, which are generally abundant in shallow aquifers, are alternative potential oxidants, but are difficult for microorganisms to access. Here we report that adding organic ligands that bind to Fe(III) dramatically increases its bioavailability, and that in the presence of these ligands, rates of degradation of aromatic hydrocarbons in anoxic aquifer sediments are comparable to those in oxic sediments. We find that even benzene, which is notoriously refractory in the absence of oxygen, can be rapidly degraded. Our results suggest that increasing the bioavailability of Fe(III) by adding suitable ligands provides a potential alternative to oxygen addition for the bioremediation of petroleum-contamined aquifers.

MOLECULAR OXYGEN AND THE ADSORPTION OF PHENOLS - EFFECT OF FUNCTIONAL GROUPS

EPA Science Inventory

This study reveals that the presence of molecular oxygen (oxic conditions) has a significant impact on the exhibited adsorptive capacity of granular activated carbon (GAC) for several phenolic compounds. The increase in the GAC adsorptive capacity under oxic conditions results f...

Microbial diversity and stratification of South Pacific abyssal marine sediments.

PubMed

Durbin, Alan M; Teske, Andreas

2011-12-01

Abyssal marine sediments cover a large proportion of the ocean floor, but linkages between their microbial community structure and redox stratification have remained poorly constrained. This study compares the downcore gradients in microbial community composition to porewater oxygen and nitrate concentration profiles in an abyssal marine sediment column in the South Pacific Ocean. Archaeal 16S rRNA clone libraries showed a stratified archaeal community that changed from Marine Group I Archaea in the aerobic and nitrate-reducing upper sediment column towards deeply branching, uncultured crenarchaeotal and euryarchaeotal lineages in nitrate-depleted, anaerobic sediment horizons. Bacterial 16S rRNA clone libraries revealed a similar shift on the phylum and subphylum level within the bacteria, from a complex community of Alpha-, Gamma- and Deltaproteobacteria, Actinobacteria and Gemmatimonadetes in oxic surface sediments towards uncultured Chloroflexi and Planctomycetes in the anaerobic sediment column. The distinct stratification of largely uncultured bacterial and archaeal groups within the oxic and nitrate-reducing marine sediment column provides initial constraints for their microbial habitat preferences. © 2011 Society for Applied Microbiology and Blackwell Publishing Ltd.

Biodegradation of MTBE by indigenous aquifer microorganisms under artificial oxic conditions

USGS Publications Warehouse

Landmeyer, J.E.; Bradley, P.M.

2001-01-01

The hypothesis that artificial oxic conditions will lead to MTBE biodegradation by indigenous microorganisms in anoxic, gasoline-contaminated aquifers was examined by adding oxygen in the form of a metal peroxide slurry to an anoxic part of gasoline-contaminated aquifer in South Carolina. Field observations of relatively rapid aerobic MTBE biodegradation following oxygen addition suggest that the indigenous bacteria have become acclimated not only to mg/L concentrations of MTBE in the gasoline plume, but also to periodic delivery of oxygen by recharge events. Significant natural attenuation of MTBE could occur if the oxygen limitations naturally associated with gasoline releases can be removed, either under natural conditions where discharging anoxic groundwater comes into contact with oxygen, or artificial conditions where oxygen can be added to aquifers containing mg/L concentrations of MTBE. This final solution might be an effective strategy for intercepting characteristically long MTBE plumes, particularly at sites not characterized by groundwater discharge to land surface. This is an abstract of a paper presented at the 222nd ACS National Meting (Chicago, IL 8/26-30/2001).

Ground-Water Geochemistry of Kwajalein Island, Republic of the Marshall Islands, 1991

USGS Publications Warehouse

Tribble, Gordon W.

1997-01-01

Ground water on Kwajalein Island is an important source of drinking water, particularly during periods of low rainfall. Fresh ground water is found as a thin lens underlain by saltwater. The concentration of dissolved ions increases with depth below the water table and proximity to the shoreline as high-salinity seawater mixes with fresh ground water. The maximum depth of the freshwater lens is 37 ft. Chloride is assumed to be non-reactive under the range of geochemical conditions on the atoll. The concentration of chloride thus is used as a conservative constituent to evaluate freshwater-saltwater mixing within the aquifer. Concentrations of sodium and for the most part, potassium and sulfate, also appear to be determined by conservative mixing between saltwater and rain. Concentrations of calcium, magnesium, and strontium are higher than expected from conservative mixing; these higher concentrations are a result of the dissolution of carbonate minerals. An excess in dissolved inorganic carbon results from carbonate-mineral dissolution and from the oxidation of organic matter in the aquifer; the stoichiometric difference between excess dissolved inorganic carbon and excess bivalent cations is used as a measure of the amount of organic-matter oxidation. Organic-matter oxidation also is indicated by the low concentration of dissolved oxygen, high concentrations of nutrients, and the presence of hydrogen sulfide in many of the water samples. Low levels of dissolved oxygen indicate oxic respiration, and sulfate reduction is indicated by hydrogen sulfide. The amount of dissolved inorganic carbon released during organic-matter oxidation is nearly equivalent to the amount of carbonate-mineral dissolution. Organic-matter oxidation and carbonate-mineral dissolution seem to be most active either in the unsaturated zone or near the top of the water table. The most plausible explanation is that high amounts of oxic respiration in the unsaturated zone generate carbon dioxide, which causes carbonate minerals to dissolve. Ground water contaminated by petroleum hydrocarbons had the highest levels of mineral dissolution and organic respiration (including sulfate reduction), indicating that bacteria are oxidizing the contaminants.

A micropalaeontological perspective on export productivity, oxygenation and temperature in NE Atlantic deep-waters across Terminations I and II

NASA Astrophysics Data System (ADS)

Grunert, Patrick; Skinner, Luke; Hodell, David A.; Piller, Werner E.

2015-08-01

Census counts of benthic foraminifera were studied from the SW Iberian Margin to reconstruct past changes in deep-water hydrography across Terminations I and II. Detailed benthic faunal data (> 125 μm size-fraction) allow us to evaluate the limitations imposed by taphonomic processes and restricted size-fractions. The comparison of recent (mudline) and fossil assemblages at IODP Site U1385 indicates the quick post-mortem disintegration of shells of astrorhizoid taxa (~ 80% of the present-day fauna), resulting in impoverished fossil assemblages. While the application of quantitative proxy methods is problematic under these circumstances, the fossil assemblages can still provide a qualitative palaeoenvironmental signal that, while most fully expressed in the 125-212 μm size-fraction, is nonetheless also expressed to some degree in the > 212 μm size-fraction. Variations in the benthic foraminiferal assemblages reveal information about changing organic matter supply, deep-water oxygenation and temperature. MIS 2 is generally characterized by an elevated trophic state and variable oxic conditions, with oxygenation minima culminating in the Younger Dryas (YD) and Heinrich Stadials (HS) 1, 2 and 3. Low oxic conditions coincide with decreased water-temperature and lower benthic δ13C, pointing to the strong influence of a southern sourced water-mass during these periods. HS 1 is the most extreme of these intervals, providing further evidence for a severe temporary reduction or even shutdown of AMOC. With the inception of MIS 1, organic matter supply reduced and a better ventilated deep-water environment bathed by NEADW is established. For Termination II, clear indications of southern-sourced water are limited to the early phase of HS 11. During the latter part of HS 11, the deep-water environment seems to be determined by strongly increased supply of organic matter, potentially explaining the decoupling of benthic δ13C and Mg/Ca records of earlier studies as a phytodetritus effect on the carbon isotope signal. However, the presence of a warm, nutrient-rich and poorly oxygenated water-mass cannot be ruled out. With the inception of interglacial MIS 5e trophic conditions are reduced and ventilation by NEADW increases.

A comprehensive sulfur and oxygen isotope study of sulfur cycling in a shallow, hyper-euxinic meromictic lake

NASA Astrophysics Data System (ADS)

Gilhooly, William P.; Reinhard, Christopher T.; Lyons, Timothy W.

2016-09-01

Mahoney Lake is a permanently anoxic and sulfidic (euxinic) lake that has a dense plate of purple sulfur bacteria positioned at mid-water depth (∼7 m) where free sulfide intercepts the photic zone. We analyzed the isotopic composition of sulfate (δ34SSO4 and δ18OSO4), sulfide (δ34SH2S), and the water (δ18OH2O) to track the potentially coupled processes of dissimilatory sulfate reduction and phototrophic sulfide oxidation within an aquatic environment with extremely high sulfide concentrations (>30 mM). Large isotopic offsets observed between sulfate and sulfide within the monimolimnion (δ34SSO4-H2S = 51‰) and within pore waters along the oxic margin (δ34SSO4-H2S > 50‰) are consistent with sulfate reduction in both the sediments and the anoxic water column. Given the high sulfide concentrations of the lake, sulfur disproportionation is likely inoperable or limited to a very narrow zone in the chemocline, and therefore the large instantaneous fractionations are best explained by the microbial process of sulfate reduction. Pyrite extracted from the sediments reflects the isotopic composition of water column sulfide, suggesting that pyrite buried in the euxinic depocenter of the lake formed in the water column. The offset between sulfate and dissolved sulfide decreases at the chemocline (δ34SSO4-H2S = 37‰), a trend possibly explained by elevated sulfate reduction rates and inconsistent with appreciable disproportionation within this interval. Water column sulfate exhibits a linear response in δ18OSO4-δ34SSO4 and the slope of this relationship suggests relatively high sulfate reduction rates that appear to respond to seasonal changes in the productivity of purple sulfur bacteria. Although photosynthetic activity within the microbial plate influences the δ18OSO4-δ34SSO4 relationship, the biosignature for photosynthetic sulfur bacteria is restricted to the oxic/anoxic transition zone and is apparently minor relative to the more prevalent process of sulfate reduction operative throughout the light-deprived deeper anoxic water column and sediment pore waters.

Microbial community compositions in different functional zones of Carrousel oxidation ditch system for domestic wastewater treatment.

PubMed

Xu, Dong; Liu, Sitong; Chen, Qian; Ni, Jinren

2017-12-01

The microbial community diversity in anaerobic-, anoxic- and oxic-biological zones of a conventional Carrousel oxidation ditch system for domestic wastewater treatment was systematically investigated. The monitored results of the activated sludge sampled from six full-scale WWTPs indicated that Proteobacteria, Chloroflexi, Bacteroidetes, Actinobacteria, Verrucomicrobia, Acidobacteria and Nitrospirae were dominant phyla, and Nitrospira was the most abundant and ubiquitous genus across the three biological zones. The anaerobic-, anoxic- and oxic-zones shared approximately similar percentages across the 50 most abundant genera, and three genera (i.e. uncultured bacterium PeM15, Methanosaeta and Bellilinea) presented statistically significantly differential abundance in the anoxic-zone. Illumina high-throughput sequences related to ammonium oxidizer organisms and denitrifiers with top50 abundance in all samples were Nitrospira, uncultured Nitrosomonadaceae, Dechloromonas, Thauera, Denitratisoma, Rhodocyclaceae (norank) and Comamonadaceae (norank). Moreover, environmental variables such as water temperature, water volume, influent ammonium nitrogen, influent chemical oxygen demand (COD) and effluent COD exhibited significant correlation to the microbial community according to the Monte Carlo permutation test analysis (p < 0.05). The abundance of Nitrospira, uncultured Nitrosomonadaceae and Denitratisoma presented strong positive correlations with the influent/effluent concentration of COD and ammonium nitrogen, while Dechloromonas, Thauera, Rhodocyclaceae (norank) and Comamonadaceae (norank) showed positive correlations with water volume and temperature. The established relationship between microbial community and environmental variables in different biologically functional zones of the six representative WWTPs at different geographical locations made the present work of potential use for evaluation of practical wastewater treatment processes.

Treatability of nonylphenol ethoxylate surfactants in on-site wastewater disposal systems.

PubMed

Huntsman, Brent E; Staples, Charles A; Naylor, Carter G; Williams, Jim-Bob

2006-11-01

The fate of nine-mole nonylphenol ethoxylate (NPE9) discharged to an on-site wastewater disposal (septic) system was the focus of a 2-year investigation. Known amounts of NPE9-based detergent were metered daily into the plumbing at a single-family household. The ethoxylate-containing wastewater was discharged to the highly anoxic environment of a 4500-L septic tank before distribution to the oxic subsurface via 100 m of leach line. After 180 days of injecting detergent to the septic system, periodic soil pore water and/or groundwater samples were collected and analyzed for nonylphenol ethoxylates (NPEs), nonylphenol ether carboxylates, and nonylphenol. The NPE9 and degradation intermediates that were measured were reduced by 99.99% on a molar basis. An 18% reduction in molar concentration within the septic tank was observed. This was followed by a further 96.7% reduction of molar concentration within the leach lines. As the pore water migrated through the vadose zone, an additional 99.69% reduction in molar concentration was measured between the bottom of the leach lines (leach line effluent) and the lowest vadose zone monitoring location. The results obtained from these analyses indicate that degradation of the surfactant occurs within the anoxic portion of the disposal system with continued rapid biodegradation in the oxic unsaturated zone. Only trace amounts of degradation residuals were detected in soil pore water. The concentration and distribution of various degradation intermediates with respect to location, time, and ambient physical conditions were evaluated. Rapid and systematic degradation of NPE in on-site wastewater disposal systems was documented.

Factors controlling the regional distribution of vanadium in ground water

USGS Publications Warehouse

Wright, Michael T.; Belitz, Kenneth

2010-01-01

Although the ingestion of vanadium (V) in drinking water may have possible adverse health effects, there have been relatively few studies of V in groundwater. Given the importance of groundwater as a source of drinking water in many areas of the world, this study examines the potential sources and geochemical processes that control the distribution of V in groundwater on a regional scale. Potential sources of V to groundwater include dissolution of V rich rocks, and waste streams from industrial processes. Geochemical processes such as adsorption/desorption, precipitation/dissolution, and chemical transformations control V concentrations in groundwater. Based on thermodynamic data and laboratory studies, V concentrations are expected to be highest in samples collected from oxic and alkaline groundwater. However, the extent to which thermodynamic data and laboratory results apply to the actual distribution of V in groundwater is not well understood. More than 8400 groundwater samples collected in California were used in this study. Of these samples, high (> or = 50 μg/L) and moderate (25 to 49 μg/L) V concentrations were most frequently detected in regions where both source rock and favorable geochemical conditions occurred. The distribution of V concentrations in groundwater samples suggests that significant sources of V are mafic and andesitic rock. Anthropogenic activities do not appear to be a significant contributor of V to groundwater in this study. High V concentrations in groundwater samples analyzed in this study were almost always associated with oxic and alkaline groundwater conditions, which is consistent with predictions based on thermodynamic data.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Izbicki, John A.; Wright, Michael T.; Seymour, Whitney A.

Hexavalent chromium, Cr(VI), in 918 wells sampled throughout California between 2004 and 2012 by the Groundwater Ambient Monitoring and Assessment Program—Priority Basin Project (GAMA—PBP) ranged from less than the study reporting limit (SRL) of 1 microgram per liter (μg/L) to 32 μg/L. Statewide, Cr(VI) was reported in 31 percent of sampled wells and equaled or exceeded the recently established (2014) California Maximum Contaminant Level (MCL) for Cr(VI) of 10 μg/L in 4 percent of sampled wells. Cr(VI) data collected for regulatory purposes overestimate Cr(VI) occurrence. Ninety percent of chromium was present as Cr(VI), which was detected more frequently and atmore » higher concentrations in alkaline (pH > 8), oxic water, and more frequently in agricultural and urban land uses compared to native land uses. Chemical, isotopic (tritium and carbon-14), and noble-gas data show high Cr(VI) in water from wells in alluvial aquifers in the southern California deserts result from long groundwater-residence times and geochemical reactions such as silicate weathering that increase pH, while oxic conditions persist. High Cr(VI) in water from wells in alluvial aquifers along the west-side of the Central Valley results from high-chromium abundance in source rock eroded to form those aquifers, and areal recharge processes (including irrigation return) that mobilize chromium from the unsaturated zone. Cr(VI) co-occurred with oxyanions having similar chemistry, including vanadium, selenium, and uranium. Cr(VI) was positively correlated with nitrate, consistent with increased concentrations in areas of agricultural land use and mobilization of chromium from the unsaturated zone by irrigation return.« less

Top-down Controls on Bacterial Transport in Oxic and Suboxic Subsurface Environments

NASA Astrophysics Data System (ADS)

Choi, K.; Dobbs, F. C.

2001-12-01

The purpose of this investigation was to assess the impact of top-down processes (protistan grazing and viral infection) on bacterial transport through a shallow, unconfined, sandy aquifer at the Department of Energy study site in Oyster, Virginia. A cultured, adhesion-deficient, viably stained, indigenous bacterial strain (DA001) was injected during a field experiment performed at an oxic site in October 1999, while DA001 and an iron-reducing bacterial strain (OY107) were co-injected at a nearby suboxic site in July 2001. Groundwater samples were collected before and after injection and abundance of protists and virus-like particles (the latter at the oxic site only) was determined. Three major groups of protists (flagellates, amoebae, and ciliates) were found at both sites during the experiments, with flagellate abundance greatly dominating the others. Following bacterial injections, concentrations up to 5000 and 3000 protists per ml were observed at the oxic and suboxic sites, respectively. However, removal of bacteria in groundwater by predation, estimated with a mass balance approach, was apparently minimal. Elevated hydraulic gradients during the injections may explain the estimated low impact of predation. The abundance of virus-like particles increased as much as six-fold in the month following injection of DA001 at the oxic site, yet plaque assays revealed no evidence supporting lytic infection of the injected bacteria.

Anoxic and oxic removal of humic acids with Fe@Fe2O3 core-shell nanowires: a comparative study.

PubMed

Wu, Hao; Ai, Zhihui; Zhang, Lizhi

2014-04-01

In this study we comparatively investigate the removal of humic acids with Fe@Fe2O3 core-shell nanowires under anoxic and oxic conditions. The products of humic acids after reacting with Fe@Fe2O3 core-shell nanowires under anoxic and oxic conditions were carefully examined with three-dimensional excitation emission matrix fluorescence spectroscopy and gas chromatography mass spectrometry. It was found that humic acids were removed by Fe@Fe2O3 core-shell nanowires via adsorption under anoxic condition. Langmuir adsorption isotherm was applicable to describe the adsorption processes. Kinetics of humic acids adsorption onto Fe@Fe2O3 core-shell nanowires was found to follow pseudo-second-order rate equation. By contrast, the oxic removal of humic acids with Fe@Fe2O3 core-shell nanowires involved adsorption and subsequent oxidation of humic acids because Fe@Fe2O3 core-shell nanowires could activate molecular oxygen to produce reactive oxygen species to oxidize humic acids. This subsequent oxidation of humic acids could improve the oxic removal rate to 2.5 times that of anoxic removal, accompanying with about 8.4% of mineralization. This study provides a new method for humic acids removal and also sheds light on the effects of humic acids on the pollutant removal by nano zero-valent iron. Copyright © 2014 Elsevier Ltd. All rights reserved.

Exploring Metabolic Activities of Deeply Buried Microbial Communities in Oxic Sediments Underlying Oligotrophic Open Ocean Gyres

NASA Astrophysics Data System (ADS)

Ziebis, W.; Patel, A.; Krupke, A.; Ferdelman, T. G.

2012-12-01

The vast majority of scientific drilling expeditions have focused on continental margins where oxygen is depleted within the surface (1 m) layer of the sediment and buried organic carbon sustains anaerobic microbial communities. IODP expeditions 329 (South Pacific Gyre) and 336 (Mid-Atlantic Ridge - North Pond) took place in oligotrophic open ocean regions, which constitute 48% of the world ocean. These expeditions have revealed that unlike continental margins the seafloor underneath oligotrophic ocean gyres is oxic. Within the South Pacific Gyre (SPG) dissolved oxygen persists throughout the sediment cover and reaches the basement even at the sites with thickest sediment cover (62 and 75 mbsf). North Pond is a sedimented pond (< 300 m sediment cover) located on the flank of the Mid-Atlantic Ridge underlying the oligotrophic central Atlantic. Here, oxygen diffuses upward from the basaltic aquifer underlying the sediment package in addition to deep oxygen penetration from the overlying water. Oxygen is the main electron acceptor available for sub-seafloor microbial activity in these vast oligotrophic open ocean regions. Microbial cells are present and active in the organic poor sediments, albeit numbers are near or below the detection limit (<103 cm-3 sediment) in the extremely organic-poor sediment of the SPG (below 2 -15 m sediment depth, depending on the location). However, we have very limited knowledge on the microbial community compositions and metabolic activities. Even the dominance of bacteria or archaea remains largely elusive. It has been suggested that while archaea dominate in the anoxic sediments of continental margins bacteria might be more abundant in the oxic seafloor underlying oligotrophic ocean gyres where aerobic respiration prevails. Experiments were conducted with sediment samples from the SPG and North Pond to explore the pattern of microbial diversity and metabolic activity using a suite of radio and stable isotopes in combination with single cell analyses. Our goal was to track the uptake and turnover of metabolically important elements (C, N, P) and to compare metabolic activities (heterotrophy / autotrophy) between sites and with depth. Labeling of cells using fluorescent oligonucleotide probes (HISH and CARD-FISH) in combination with nanoSIMS has thus far revealed a clear dominance of bacteria in SPG sub-seafloor sediments, which showed a high uptake of nitrogen (ammonium). Current experiments using cell extractions and cell encapsulations followed by incubations with radiotracers will further reveal carbon turnover pathways of specific microorganisms.

Sources of core and intact branched tetraether membrane lipids in the lacustrine environment: Anatomy of Lake Challa and its catchment, equatorial East Africa

NASA Astrophysics Data System (ADS)

Buckles, Laura K.; Weijers, Johan W. H.; Verschuren, Dirk; Sinninghe Damsté, Jaap S.

2014-09-01

The MBT/CBT palaeotemperature proxy uses the distribution of branched glycerol dialkyl glycerol tetraethers (brGDGTs), membrane lipids that are supposed to derive from soil bacteria, to reconstruct mean annual air temperature (MAAT). Applied successfully in coastal marine sediments, its extension to lake-sediment records with potentially high time resolution would greatly expand its utility. Over the last years, however, studies have indicated the presence of additional sources of brGDGTs within lake systems. To constrain the factors influencing the MBT/CBT palaeotemperature proxy in lakes, detailed investigation of brGDGT fluxes in a modern lake system is necessary to identify their potential sources. This study concentrates on Lake Challa, a permanently stratified crater lake in equatorial East Africa with limited catchment area. An almost 3-year time series of approximately monthly samples of settling particles, supplemented with a depth profile of suspended particulate matter (SPM) and sets of profundal surface-sediment and catchment soil samples, were analysed for both the 'living' intact polar lipids (IPLs) and 'fossil' core lipids (CLs) of GDGTs. We found that brGDGTs are produced in oxic, suboxic and anoxic zones of the water column, and in substantial amounts compared to influxes from catchment soils. Additional in situ production within the lake sediments is most probable, but cannot be definitely confirmed at this time. These lacustrine brGDGTs display a different response to temperature variation than soil-derived brGDGTs, signifying either a different physiological adaptation to changing conditions within the water column and/or a different composition of the respective bacterial communities. Using this specific relationship with temperature, a local calibration based on brGDGT distributions in SPM generates relatively accurate water temperature estimates from settling particles but fails for surface sediments.

'Low-acid' sulfide oxidation using nitrate-enriched groundwater

NASA Astrophysics Data System (ADS)

Donn, Michael; Boxall, Naomi; Reid, Nathan; Meakin, Rebecca; Gray, David; Kaksonen, Anna; Robson, Thomas; Shiers, Denis

2016-04-01

Acid drainage (AMD/ARD) is undoubtedly one of the largest environmental, legislative and economic challenges facing the mining industry. In Australia alone, at least 60m is spent on AMD related issues annually, and the global cost is estimated to be in the order of tens of billions US. Furthermore, the challenge of safely and economically storing or treating sulfidic wastes will likely intensify because of the trend towards larger mines that process increasingly higher volumes of lower grade ores and the associated sulfidic wastes and lower profit margins. While the challenge of managing potentially acid forming (PAF) wastes will likely intensify, the industrial approaches to preventing acid production or ameliorating the effects has stagnated for decades. Conventionally, PAF waste is segregated and encapsulated in non-PAF tips to limit access to atmospheric oxygen. Two key limitations of the 'cap and cover' approach are: 1) the hazard (PAF) is not actually removed; only the pollutant linkage is severed; and, 2) these engineered structures are susceptible to physical failure in short-to-medium term, potentially re-establishing that pollutant linkage. In an effort to address these concerns, CSIRO is investigating a passive, 'low-acid' oxidation mechanism for sulfide treatment, which can potentially produce one quarter as much acidity compared with pyrite oxidation under atmospheric oxygen. This 'low-acid' mechanism relies on nitrate, rather than oxygen, as the primary electron accepter and the activity of specifically cultured chemolithoautotrophic bacteria and archaea communities. This research was prompted by the observation that, in deeply weathered terrains of Australia, shallow (oxic to sub-oxic) groundwater contacting weathering sulfides are commonly inconsistent with the geochemical conditions produced by ARD. One key characteristic of these aquifers is the natural abundance of nitrate on a regional scale, which becomes depleted around the sulfide bodies, and where pH remains neutral. The "low-acid" oxidation of sulfides with nitrate as an electron acceptor has been demonstrated at the laboratory scale. In 90-day microcosm respirometry experiments, we exposed a mixture of pulverized quartz and pyrite -rich ore to natural, high-nitrate groundwater and inoculated the microcosms with a culture of aerobic and anaerobic nitrate-dependent iron and sulfur-oxidising microorganisms, which were enriched from ore, groundwater and activated waste water. Incubations were performed under both oxic and anoxic conditions, in addition to abiotic controls. Initial results show that oxidation of the sulfides under nitrate-rich and microbially enhanced conditions does produce less acid than the same material under oxic conditions, and to some degree can match the models as long as oxygen ingress can be controlled. These results are the focus of further research into how this process can be enhanced and whether it can be applied in the field. Nitrate-driven oxidation of sulfides could potentially be used as a new approach to reduce acid generation and leaching of contaminants from waste dumps, in a passive or actively managed process designed to deplete and/or ameliorate (i.e. through surface passivation) the mineralogical hazard. Developing our understanding of biological aspects of these processes may also allow testing of longer-term "bio-caps" for various tailings and dump materials.

Water chemistry of Lake Quilotoa (Ecuador) and assessment of natural hazards

NASA Astrophysics Data System (ADS)

Aguilera, E.; Chiodini, G.; Cioni, R.; Guidi, M.; Marini, L.; Raco, B.

2000-04-01

A geochemical survey carried out in November 1993 revealed that Lake Quilotoa was composed by a thin (˜14 m) oxic epilimnion overlying a ˜200 m-thick anoxic hypolimnion. Dissolved CO2 concentrations reached 1000 mg/kg in the lower stratum. Loss of CO2 from epilimnetic waters, followed by calcite precipitation and a consequent lowering in density, was the apparent cause of the stratification. The Cl, SO4 and HCO3 contents of Lake Quilotoa are intermediate between those of acid-SO4-Cl Crater lakes and those of neutral-HCO3 Crater lakes, indicating that Lake Quilotoa has a 'memory' of the inflow and absorption of HC1- and S-bearing volcanic (magmatic) gases. The Mg/Ca ratios of the lake waters are governed by dissolution of local volcanic rocks or magmas, but K/Na ratios were likely modified by precipitation of alunite, a typical mineral in acid-SO4-Cl Crater lakes. The constant concentrations of several conservative chemical species from lake surface to lake bottom suggest that physical, chemical and biological processes did not have enough time, after the last overturn, to cause significant changes in the contents of these chemical species. This lapse of time might be relatively large, but it cannot be established on the basis of available data. Besides, the lake may not be close to steady state. Mixing of Lake Quilotoa waters could presently be triggered by either cooling epilimnetic waters by ˜4°C or providing heat to hypolimnetic waters or by seismic activity. Although Quilotoa lake contains a huge amount of dissolved CO2(˜3×1011 g), at present the risk of a dangerous limnic eruption seems to be nil even though some gas exsolution might occur if deep lake waters were brought to the surface. Carbon dioxide could build up to higher levels in deep waters than at present without any volcanic re-awakening, due to either a large inflow of relatively cool CO2-rich gases, or possibly a long interval between overturns. Periodical geochemical surveys of Lake Quilotoa are, therefore, recommended.

Coordinated Analyses of Antarctic Sediments as Mars Analog Materials Using Reflectance Spectroscopy and Current Flight-Like Instruments for CheMin, SAM and MOMA

NASA Technical Reports Server (NTRS)

Bishop, Janice L.; Franz, Heather B.; Goetz, Walter; Blake, David F.; Freissinet, Caroline; Steininger, Harald; Goesmann, Fred; Brinckerhoff, William B.; Getty, Stephanie; Pinnick, Veronica T.;

Anaerobic Oxidation of Methane in a French meromictic lake (Lake Pavin): Who is responsible?

NASA Astrophysics Data System (ADS)

Grossi, V.; Attard, E.; Birgel, D.; Schaeffer, P.; Jézéquel, D.; Lehours, A.

2012-12-01

Methane is an important greenhouse gas and its biogeochemical cycle is of primary significance to the global carbon cycle. The Anaerobic Oxidation of Methane (AOM) has been estimated to be responsible for >90% of methane consumption. This biogeochemical process has been increasingly documented during the last two decades but the underlying microbial processes and their key agents remain incompletely understood. Freshwater lakes account for 2-10% of the total emissions of methane and are therefore an important part of the global methane cycle. Lake Pavin is a French meromictic crater lake with unusual hydrological characteristics: its morphology (depth >92m, mean diameter 750m) induce that waters below 60m are never mixed with overlying waters and remain permanently anoxic. The deep anoxic waters of Lake Pavin contain high concentrations (i.e. 4 mM) of methane but, contrary to other aquatic systems, almost no methane escapes from the lake. Previous biogeochemical and modeling studies suggest that methane is preferentially consumed within the oxic-anoxic transition zone (ca. 55-60 m depth) but that ca. 30% of methane oxidation occurs in the anoxic part of the lake. Phylogenetic (16S rRNA) analyses showed that ANME generally involved in AOM (ANME-1, -2 and -3) are not present in Lake Pavin. Other archaeal groups that do not have any cultured representatives so far appear well represented in the anoxic parts of the lake but their implication in AOM is not demonstrated. The analysis of lipid biomarkers using GC-MS and LC-MS revealed the presence of a low diversity of archaeal-specific biomarkers in the superficial sediments and in the anoxic waters of the lake. Archaeol and caldarcheaol (GDGT-0) are the two main archaeal core lipids detected; other biomarkers generally present in ANME such as pentamethylicosane or hydroxyarchaeol are not present. However, the stable carbon isotopic composition of archaeol (δ13C = -18‰) and of the biphytane chain of GDGT-0 (δ13C = -31‰) released following the chemical degradation of ether bonds with HI, argue against an origin from archaea involved in AOM. Intriguingly, the only 13C-depleted (-66‰<δ13C<-53‰) lipid biomarkers detected in the superficial sediments and in the anoxic waters of Lake Pavin are bacterial hopanoids (diploptene, diplopterol, C32 homohopanols and homohopanoic acid). Such 13C-depleted hopanoids are generally thought to be specific of aerobic methanotrophic bacteria but the recent discovery of hopanoids in cultures of strictly anaerobic bacteria allows envisaging AOM in Lake Pavin as a bacterially-driven process. The analysis of lipid biomarkers from the different redox zones of the water column (oxic, transition oxic-anoxic, fully anoxic) is currently being investigated and should help assessing the unconventional anaerobic methane consumers of Lake Pavin.

Thallium-isotopic compositions of euxinic sediments as a proxy for global manganese-oxide burial

NASA Astrophysics Data System (ADS)

Owens, Jeremy D.; Nielsen, Sune G.; Horner, Tristan J.; Ostrander, Chadlin M.; Peterson, Larry C.

2017-09-01

Thallium (Tl) isotopes are a new and potentially powerful paleoredox proxy that may track bottom water oxygen conditions based on the global burial flux of manganese oxides. Thallium has a residence time of ∼20 thousand years, which is longer than the ocean mixing time, and it has been inferred that modern oxic seawater is conservative with respect to both concentration and isotopes. Marine sources of Tl have nearly identical isotopic values. Therefore, the Tl sinks, adsorption onto manganese oxides and low temperature oceanic crust alteration (the dominant seawater output), are the primary controls of the seawater isotopic composition. For relatively short-term, ∼million years, redox events it is reasonable to assume that the dominant mechanism that alters the Tl isotopic composition of seawater is associated with manganese oxide burial because large variability in low temperature ocean crust alteration is controlled by long-term, multi-million years, average ocean crust production rates. This study presents new Tl isotope data for an open ocean transect in the South Atlantic, and depth transects for two euxinic basins (anoxic and free sulfide in the water column), the Cariaco Basin and Black Sea. The Tl isotopic signature of open ocean seawater in the South Atlantic was found to be homogeneous with ε205Tl = -6.0 ± 0.3 (±2 SD, n = 41) while oxic waters from Cariaco and the Black Sea are -5.6 and -2.2, respectively. Combined with existing data from the Pacific and Arctic Oceans, our Atlantic data establish the conservatism of Tl isotopes in the global ocean. In contrast, partially- and predominantly-restricted basins reveal Tl isotope differences that vary between open-ocean (-6) and continental material (-2) ε205Tl, scaling with the degree of restriction. Regardless of the differences between basins, Tl is quantitatively removed from their euxinic waters below the chemocline. The burial of Tl in euxinic sediments is estimated to be an order of magnitude less than each of the modern ocean outputs and imparts no isotopic fractionation. Thallium removal into pyrite appears to be associated with a small negative fractionation between -1 and -3 ε205Tl, which renders Tl-depleted waters below the chemocline enriched in isotopically-heavy Tl. Due to the quantitative removal of Tl from euxinic seawater, Tl isotope analyses of the authigenic fraction of underlying euxinic sediments from both the Black Sea and Cariaco Basin capture the Tl isotope value of the oxic portion of their respective water column with no net isotope fractionation. Since the Tl isotope composition of seawater is largely dictated by the relative fraction of Mn-oxide burial versus oceanic crust alteration, we contend that the Tl isotope composition of authigenic Tl in black shales, deposited under euxinic conditions but well-connected to the open ocean, can be utilized to reconstruct the Tl isotope composition of seawater, and thus to reconstruct the global history of Mn-oxide burial.

Groundwater Surface Water Interactions in a Gold-Mined Dredged Floodplain of the Merced River

NASA Astrophysics Data System (ADS)

Sullivan, L.; Conklin, M. H.; Ghezzehei, T. A.

2012-12-01

The Merced River, originating in the Sierra Nevada, California, drains a watershed with an area of ~3,305 km2. Merced River has been highly altered due to diversions, mechanically dredged mining, and damming. A year of groundwater-surface water interactions were studied to elucidate the hydrological connection between the Main Canal, an unlined canal that contains Merced River water flows parallel to the river with an average elevation of 89m, the highly conductive previously dredged floodplain, and the Merced River with an average elevation of 84m. Upstream of the study reach, located in an undredged portion, of the floodplain are two fish farms that have been operating for approximately 40 years. This study reach has been historically important for salmon spawning and rearing, where more than 50% of the Chinook salmon of the Merced River spawn. Currently salmon restoration is focusing gravel augmentation and adding side channel and ignoring groundwater influences. Exchanges between the hyporheic and surrounding surface, groundwater, riparian, and alluvial floodplain habitats occur over a wide range of spatial and temporal scales. Pressure transducers were installed in seven wells and four ponds located in the dredged floodplain. All wells were drilled to the Mehrten Formation, a confining layer, and screened for last 3m. These groundwater well water levels as well as the surface water elevations of the Main Canal and the Merced River were used to determine the direction of sublateral surface flows using Groundwater Vistas as a user interface for MODFLOW. The well and pond waters and seepage from the river banks were sampled for anion/cation, dissolved organic carbon, total nitrogen, total iron, and total dissolved iron concentrations to determine water sources and the possibility of suboxic water. Field analysis indicated that water in all wells and ponds exhibit low dissolved oxygen, high conductivity rates, and oxidation/reduction potentials that switched from oxidizing to reductive during the course of the monitoring. Chemical analysis indicates that there are three sources of water for this floodplain: the Merced River and Main Canal, (which are chemically very similar), the waters from the fish hatchery, and precipitation. The well closest to the fish hatcheries had C:N ratio of 1:1, highly carbon-limited system. MODFLOW particle tracer experiments were performed, results indicate that that travel time between the Main Canal and Merced River are approximately 10-15 years. The hydraulic gradient set up by the groundwater connection between Main Canal and the Merced River, insures that any effluent released by the fish farms will be transported to the Merced River. Conclusions of the study are that the waters that seep from the Main Canal to the Merced River in this area can be sub-oxic, which is not conducive to salmon spawning and are detrimental to the developing salmonid embryo. Due to the causal connections between the hydrological system of the Merced River floodplain and the riverine system, habitat rehabilitation must target not only the surface water but also important subsurface hydrological components.

Linking microbial heterotrophic activity and sediment lithology in oxic, oligotrophic sub-seafloor sediments of the north atlantic ocean.

PubMed

Picard, Aude; Ferdelman, Timothy G

2011-01-01

Microbial heterotrophic activity was investigated in oxic sub-seafloor sediments at North Pond, a sediment pond situated at 23°N on the western flank of the Mid-Atlantic Ridge. The North Pond sediments underlie the oligotrophic North Atlantic Gyre at 4580-m water depth and cover a 7-8 million-year-old basaltic crust aquifer through which seawater flows. Discrete samples for experimentation were obtained from up to ~9 m-long gravity cores taken at 14 stations in the North Pond area. Potential respiration rates were determined in sediment slurries incubated under aerobic conditions with (14)C-acetate. Microbial heterotrophic activity, as defined by oxidation of acetate to CO(2) (with O(2) as electron acceptor), was detected in all 14 stations and all depths sampled. Potential respiration rates were generally low (<0.2 nmol of respired acetate cm(-3) d(-1)) in the sediment, but indicate that microbial heterotrophic activity occurs in deep-sea, oxic, sub-seafloor sediments. Furthermore, discernable differences in activity existed between sites and within given depth profiles. At seven stations, activity was increased by several orders of magnitude at depth (up to ~12 nmol of acetate respired cm(-3) d(-1)). We attempted to correlate the measures of activity with high-resolution color and element stratigraphy. Increased activities at certain depths may be correlated to variations in the sediment geology, i.e., to the presence of dark clay-rich layers, of sandy layers, or within clay-rich horizons presumably overlying basalts. This would suggest that the distribution of microbial heterotrophic activity in deeply buried sediments may be linked to specific lithologies. Nevertheless, high-resolution microbial examination at the level currently enjoyed by sedimentologists will be required to fully explore this link.

Linking Microbial Heterotrophic Activity and Sediment Lithology in Oxic, Oligotrophic Sub-Seafloor Sediments of the North Atlantic Ocean

PubMed Central

Picard, Aude; Ferdelman, Timothy G.

2011-01-01

Microbial heterotrophic activity was investigated in oxic sub-seafloor sediments at North Pond, a sediment pond situated at 23°N on the western flank of the Mid-Atlantic Ridge. The North Pond sediments underlie the oligotrophic North Atlantic Gyre at 4580-m water depth and cover a 7–8 million-year-old basaltic crust aquifer through which seawater flows. Discrete samples for experimentation were obtained from up to ~9 m-long gravity cores taken at 14 stations in the North Pond area. Potential respiration rates were determined in sediment slurries incubated under aerobic conditions with 14C-acetate. Microbial heterotrophic activity, as defined by oxidation of acetate to CO2 (with O2 as electron acceptor), was detected in all 14 stations and all depths sampled. Potential respiration rates were generally low (<0.2 nmol of respired acetate cm−3 d−1) in the sediment, but indicate that microbial heterotrophic activity occurs in deep-sea, oxic, sub-seafloor sediments. Furthermore, discernable differences in activity existed between sites and within given depth profiles. At seven stations, activity was increased by several orders of magnitude at depth (up to ~12 nmol of acetate respired cm−3 d−1). We attempted to correlate the measures of activity with high-resolution color and element stratigraphy. Increased activities at certain depths may be correlated to variations in the sediment geology, i.e., to the presence of dark clay-rich layers, of sandy layers, or within clay-rich horizons presumably overlying basalts. This would suggest that the distribution of microbial heterotrophic activity in deeply buried sediments may be linked to specific lithologies. Nevertheless, high-resolution microbial examination at the level currently enjoyed by sedimentologists will be required to fully explore this link. PMID:22207869

Removal of surfactants nonylphenol ethoxylates from municipal sewage-comparison of an A/O process and biological aerated filters.

PubMed

Gao, Dawen; Li, Zhe; Guan, Junxue; Li, Yifan; Ren, Nanqi

2014-02-01

The concentrations of nonylphenol ethoxylates (NPnEO, n=1 to 2) and nonylphenol (NP) in water and sludge samples were measured from a full scale sewage treatment plant (STP) with an Anaerobic/Oxic (A/O) and a Biological Aerated Filter (BAF) process. The A/O process was found to exhibit improved performance in comparison to the BAF process. Mean values of NP, NP1EO and NP2EO concentrations in influents from the STP were similar, ranging from 1.8 to 2.0×10(3)ngL(-1). In the A/O process, the removal efficiency of NP, NP1EO and NP2EO from the aqueous phase was 78%, 84%, and 89%, respectively. In contrast, the removal efficiencies of NP, NP1EO, and NP2EO were relatively lower for the BAF process, at 55%, 76%, and 79%, respectively. High concentrations of NP, NP1EO and NP2EO detected in the sludge samples had a maximum value of 2.7μgg(-1) dw, which indicates that improvement in the overall elimination of NP, NP1EO and NP2EO may be associated with adsorption by the sludge. To further investigate the fate of NP, NP1EO and NP2EO in the STP, our research assessed the degradation characteristics of NP by calculating its transformational loss in the STP. The results demonstrate that the quantity of NP measured in the effluent from the oxic unit increased by 32%, which indicates that NP1EO and NP2EO may undergo degradation in the oxic conditions. Copyright © 2013 Elsevier Ltd. All rights reserved.

Abundance of genes involved in mercury methylation in oceanic environments

NASA Astrophysics Data System (ADS)

Palumbo, A. V.; Podar, M.; Gilmour, C. C.; Brandt, C. C.; Brown, S. D.; Crable, B. R.; Weighill, D.; Jacobson, D. A.; Somenahally, A. C.; Elias, D. A.

2016-02-01

The distribution and diversity of genes involved in mercury methylation in oceanic environments is of interest in determining the source of mercury in ocean environments and may have predictive value for mercury methylation rates. The highly conserved hgcAB genes involved in mercury methylation provide an avenue for evaluating the genetic potential for mercury methylation. The genes are sporadically present in a few diverse groups of bacteria and Archaea including Deltaproteobacteria, Firmicutes and Archaea and of over 7000 sequenced species they are only present in about 100 genomes. Examination of sequence data from methylators and non-methylators indicates that these genes are associated with other genes involved in metal transformations and transport. We examined hgcAB presence in over 3500 microbial metagenomes (from all environments) and found the hgcAB genes were present in anaerobic oceanic environments but not in aerobic layers of the open ocean. The genes were common in sediments from marine, coastal and estuarine sources as well as polluted environments. The genes were rare, found in 7 of 138 samples, in metagenomes from the pelagic water column including profiles though the oxygen minimum zone. Other oxic and sub-oxic coastal waters also demonstrated a lack of hgcAB genes including the OMZ in the Eastern North Pacific Ocean. There were some unique hgcA like unique sequences found in metagenomes from depth in the Pacific and Southern Atlantic Ocean. Coastal "dead zone" waters may be important sources of MeHg as the hgcAB genes were abundant in the anoxic waters of a stratified fjord. The genes were absent in microbiomes from vertebrates but were in invertebrate microbiomes However, oceanic species were underrepresented in these samples. Climate change could provide an additional flux of MeHg to the oceans as we found the most abundant representation of hgcAB genes in arctic permafrost. Thus warming could increase flux of methyl mercury to arctic waters.

Multiple sulfur isotope records at the end-Guadalupian (Permian) at Chaotian, China: Implications for a role of bioturbation in the Phanerozoic sulfur cycle

NASA Astrophysics Data System (ADS)

Saitoh, Masafumi; Ueno, Yuichiro; Matsu'ura, Fumihiro; Kawamura, Tetsuya; Isozaki, Yukio; Yao, Jianxin; Ji, Zhansheng; Yoshida, Naohiro

2017-03-01

A recent study on quadruple sulfur isotopes (32S, 33S, 34S, and 36S) of sedimentary pyrite suggested that the end-Guadalupian extinction was caused by shoaling of the sulfidic deep-water. This scenario is based on the assumption that sulfur isotopic compositions of pyrite from hosting sediments were controlled by benthos activities, thus by the redox conditions of the sedimentary environments. Nonetheless, the relationship between the sulfur isotope records and redox conditions, reconstructed from litho- and bio-facies, are poorly known. In order to examine the effect of bioturbation in sediments, quadruple sulfur isotopic compositions of sedimentary pyrite from the end-Guadalupian succession in Chaotian, South China, were analyzed. Black mudstones of deep-water facies immediately below the extinction horizon have consistently high Δ33S values of ca. +0.079‰, clearly suggesting a sulfate reduction in the anoxic water column. Our new data are consistent with the emergence of a sulfidic deep-water mass prior to the end-Guadalupian extinction; the upwelling of the toxic deep-water may have contributed to the extinction. In contrast, shallow-marine bioclastic limestones with burrows deposited under oxic conditions have negative Δ33S values. This anomalous isotopic signal indicates the mixing of two distinct types of pyrite; one generated during the sulfate reduction in an open system and the other in a closed system. We interpret that bioturbation supplied sulfate in the sediments and promoted sulfate reduction and in-situ sulfide precipitation within the sediments. The negative Δ33S values of oxic sediments in Chaotian are inconsistent with the previous model and demonstrate that the sedimentary sulfur cycle associated with bioturbation was more complicated than previously thought. Our study also implies that, more generally, the role of bioturbation in increasing seawater sulfate concentration in the Phanerozoic may have been overestimated in the previous studies, because bioturbation may have enhanced sulfide burial or sulfur output from the oceans.

Assessment of the microbial community in a constructed wetland that receives acid coal mine drainage

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nicomrat, D.; Dick, W.A.; Tuovinen, O.H.

2006-01-15

Constructed wetlands are used to treat acid drainage from surface or underground coal mines. However, little is known about the microbial communities in the receiving wetland cells. The purpose of this work was to characterize the microbial population present in a wetland that was receiving acid coal mine drainage (AMD). Samples were collected from the oxic sediment zone of a constructed wetland cell in southeastern Ohio that was treating acid drainage from an underground coal mine seep. Samples comprised Fe(Ill) precipitates and were pretreated with ammonium oxalate to remove interfering iron, and the DNA was extracted and purified by agarosemore » gel electrophoresis prior to amplification of portions of the 16S rRNA gene. Amplified products were separated by denaturing gradient gel electrophoresis and DNA from seven distinct bands was excised from the gel and sequenced. The sequences were matched to sequences in the GenBank bacterial 16S rDNA database. The DNA in two of the bands yielded matches with Acidithiobacillus ferrooxidans and the DNA in each of the remaining five bands was consistent with one of the following microorganisms: Acidithiobacillus thiooxidans, strain TRA3-20 (a eubacterium), strain BEN-4 (an arsenite-oxidizing bacterium), an Alcaligenes sp., and a Bordetella sp. Low bacterial diversity in these samples reflects the highly inorganic nature of the oxic sediment layer where high abundance of iron- and sulfur-oxidizing bacteria would be expected. The results we obtained by molecular methods supported our findings, obtained using culture methods, that the dominant microbial species in an acid receiving, oxic wetland are A. thiooxidans and A. ferrooxidans.« less

Tracing the Cycling and Fate of the Explosive 2,4,6-Trinitrotoluene in Coastal Marine Systems with a Stable Isotopic Tracer, (15)N-[TNT].

PubMed

Smith, Richard W; Vlahos, Penny; Böhlke, J K; Ariyarathna, Thivanka; Ballentine, Mark; Cooper, Christopher; Fallis, Stephen; Groshens, Thomas J; Tobias, Craig

2015-10-20

2,4,6-Trinitrotoluene (TNT) has been used as a military explosive for over a hundred years. Contamination concerns have arisen as a result of manufacturing and use on a large scale; however, despite decades of work addressing TNT contamination in the environment, its fate in marine ecosystems is not fully resolved. Here we examine the cycling and fate of TNT in the coastal marine systems by spiking a marine mesocosm containing seawater, sediments, and macrobiota with isotopically labeled TNT ((15)N-[TNT]), simultaneously monitoring removal, transformation, mineralization, sorption, and biological uptake over a period of 16 days. TNT degradation was rapid, and we observed accumulation of reduced transformation products dissolved in the water column and in pore waters, sorbed to sediments and suspended particulate matter (SPM), and in the tissues of macrobiota. Bulk δ(15)N analysis of sediments, SPM, and tissues revealed large quantities of (15)N beyond that accounted for in identifiable derivatives. TNT-derived N was also found in the dissolved inorganic N (DIN) pool. Using multivariate statistical analysis and a (15)N mass balance approach, we identify the major transformation pathways of TNT, including the deamination of reduced TNT derivatives, potentially promoted by sorption to SPM and oxic surface sediments.

Tracing the cycling and fate of the explosive 2,4,6-trinitrotoluene in coastal marine systems with a stable isotopic tracer, 15N-[TNT

USGS Publications Warehouse

Smith, Richard W.; Vlahos, Penny; Böhlke, John Karl; Ariyarathna, Thivanka; Ballentine, Mark; Cooper, Christopher; Fallis, Stephen; Groshens, Thomas J.; Tobias, Craig

2015-01-01

2,4,6-Trinitrotoluene (TNT) has been used as a military explosive for over a hundred years. Contamination concerns have arisen as a result of manufacturing and use on a large scale; however, despite decades of work addressing TNT contamination in the environment, its fate in marine ecosystems is not fully resolved. Here we examine the cycling and fate of TNT in the coastal marine systems by spiking a marine mesocosm containing seawater, sediments, and macrobiota with isotopically labeled TNT (15N-[TNT]), simultaneously monitoring removal, transformation, mineralization, sorption, and biological uptake over a period of 16 days. TNT degradation was rapid, and we observed accumulation of reduced transformation products dissolved in the water column and in pore waters, sorbed to sediments and suspended particulate matter (SPM), and in the tissues of macrobiota. Bulk δ15N analysis of sediments, SPM, and tissues revealed large quantities of 15N beyond that accounted for in identifiable derivatives. TNT-derived N was also found in the dissolved inorganic N (DIN) pool. Using multivariate statistical analysis and a 15N mass balance approach, we identify the major transformation pathways of TNT, including the deamination of reduced TNT derivatives, potentially promoted by sorption to SPM and oxic surface sediments.

Porewater methane transport within the gas vesicles of diurnally migrating Chaoborus spp.: An energetic advantage

NASA Astrophysics Data System (ADS)

McGinnis, Daniel F.; Flury, Sabine; Tang, Kam W.; Grossart, Hans-Peter

2017-03-01

Diurnally-migrating Chaoborus spp. reach populations of up to 130,000 individuals m-2 in lakes up to 70 meters deep on all continents except Antarctica. Linked to eutrophication, migrating Chaoborus spp. dwell in the anoxic sediment during daytime and feed in the oxic surface layer at night. Our experiments show that by burrowing into the sediment, Chaoborus spp. utilize the high dissolved gas partial pressure of sediment methane to inflate their tracheal sacs. This mechanism provides a significant energetic advantage that allows the larvae to migrate via passive buoyancy rather than more energy-costly swimming. The Chaoborus spp. larvae, in addition to potentially releasing sediment methane bubbles twice a day by entering and leaving the sediment, also transport porewater methane within their gas vesicles into the water column, resulting in a flux of 0.01-2 mol m-2 yr-1 depending on population density and water depth. Chaoborus spp. emerging annually as flies also result in 0.1-6 mol m-2 yr-1 of carbon export from the system. Finding the tipping point in lake eutrophication enabling this methane-powered migration mechanism is crucial for ultimately reconstructing the geographical expansion of Chaoborus spp., and the corresponding shifts in the lake’s biogeochemistry, carbon cycling and food web structure.

Geochemistry of Dissolved Trace Metals in the Waters of Bahia Magdalena, Baja California Sur, Pacific Coast, Mexico

NASA Astrophysics Data System (ADS)

Suresh Babu, S.

2016-12-01

Forty two samples were acquired from the surface and bottom water profiles along 5 transects spread over Bahia Magdalena lagoon, Baja California Sur to assess the behavior of trace metals in a high influenced upwelling region on the Pacific coast. To elaborate the fate of metals, also the physico-chemical parameters (pH, temperature, salinity, conductivity, dissolved oxygen). Determination of the concentrations of trace metals (Fe, Mn, Cr, Cu, Co, Pb, Ni, Zn, Cd As, Hg) were measured using Atomic absorption spectrometry. The results demonstrated high values of As, Ni and Co which is attributed to the local geology and phosphate deposits. Low values of Fe and Mn are attested to the oxic conditions of the lagoon which are responsible for the oxidation of Fe and Mn. The region witnesses raised temperatures (28.92ºC) and salinities of 35.2 PSU for its arid climatic conditions and high rates of evaporation. In general, the region presented minor quantities of dissolved trace metals due to dispersion and high intense interaction with the open sea. The results were also compared with other studies to understand the enrichment pattern in this side of the pacific coast which experiences various geothermal activities and upwelling phenomenon.

Long-term in situ oxidation of biogenic uraninite in an alluvial aquifer: impact of dissolved oxygen and calcium.

PubMed

Lezama-Pacheco, Juan S; Cerrato, José M; Veeramani, Harish; Alessi, Daniel S; Suvorova, Elena; Bernier-Latmani, Rizlan; Giammar, Daniel E; Long, Philip E; Williams, Kenneth H; Bargar, John R

2015-06-16

Oxidative dissolution controls uranium release to (sub)oxic pore waters from biogenic uraninite produced by natural or engineered processes, such as bioremediation. Laboratory studies show that uraninite dissolution is profoundly influenced by dissolved oxygen (DO), carbonate, and solutes such as Ca(2+). In complex and heterogeneous subsurface environments, the concentrations of these solutes vary in time and space. Knowledge of dissolution processes and kinetics occurring over the long-term under such conditions is needed to predict subsurface uranium behavior and optimize the selection and performance of uraninite-based remediation technologies over multiyear periods. We have assessed dissolution of biogenic uraninite deployed in wells at the Rifle, CO, DOE research site over a 22 month period. Uraninite loss rates were highly sensitive to DO, with near-complete loss at >0.6 mg/L over this period but no measurable loss at lower DO. We conclude that uraninite can be stable over decadal time scales in aquifers under low DO conditions. U(VI) solid products were absent over a wide range of DO values, suggesting that dissolution proceeded through complexation and removal of oxidized surface uranium atoms by carbonate. Moreover, under the groundwater conditions present, Ca(2+) binds strongly to uraninite surfaces at structural uranium sites, impacting uranium fate.

Characterization of U(VI)-carbonato ternary complexes on hematite: EXAFS and electrophoretic mobility measurements

USGS Publications Warehouse

Bargar, John R.; Reitmeyer, Rebecca; Lenhart, John J.; Davis, James A.

2000-01-01

We have measured U(VI) adsorption on hematite using EXAFS spectroscopy and electrophoresis under conditions relevant to surface waters and aquifers (0.01 to 10 μM dissolved uranium concentrations, in equilibrium with air, pH 4.5 to 8.5). Both techniques suggest the existence of anionic U(VI)-carbonato ternary complexes. Fits to EXAFS spectra indicate that U(VI) is simultaneously coordinated to surface FeO6 octahedra and carbonate (or bicarbonate) ligands in bidentate fashions, leading to the conclusion that the ternary complexes have an inner-sphere metal bridging (hematite-U(VI)-carbonato) structure. Greater than or equal to 50% of adsorbed U(VI) was comprised of monomeric hematite-U(VI)-carbonato ternary complexes, even at pH 4.5. Multimeric U(VI) species were observed at pH ≥ 6.5 and aqueous U(VI) concentrations approximately an order of magnitude more dilute than the solubility of crystalline β-UO2(OH)2. Based on structural constraints, these complexes were interpreted as dimeric hematite-U(VI)-carbonato ternary complexes. These results suggest that Fe-oxide-U(VI)-carbonato complexes are likely to be important transport-limiting species in oxic aquifers throughout a wide range of pH values.

An efficient process for wastewater treatment to mitigate free nitrous acid generation and its inhibition on biological phosphorus removal

PubMed Central

Zhao, Jianwei; Wang, Dongbo; Li, Xiaoming; Yang, Qi; Chen, Hongbo; Zhong, Yu; An, Hongxue; Zeng, Guangming

2015-01-01

Free nitrous acid (FNA), which is the protonated form of nitrite and inevitably produced during biological nitrogen removal, has been demonstrated to strongly inhibit the activity of polyphosphate accumulating organisms (PAOs). Herein we reported an efficient process for wastewater treatment, i.e., the oxic/anoxic/oxic/extended-idle process to mitigate the generation of FNA and its inhibition on PAOs. The results showed that this new process enriched more PAOs which thereby achieved higher phosphorus removal efficiency than the conventional four-step (i.e., anaerobic/oxic/anoxic/oxic) biological nutrient removal process (41 ± 7% versus 30 ± 5% in abundance of PAOs and 97 ± 0.73% versus 82 ± 1.2% in efficiency of phosphorus removal). It was found that this new process increased pH value but decreased nitrite accumulation, resulting in the decreased FNA generation. Further experiments showed that the new process could alleviate the inhibition of FNA on the metabolisms of PAOs even under the same FNA concentration. PMID:25721019

Incineration of tannery sludge under oxic and anoxic conditions: study of chromium speciation.

PubMed

Kavouras, P; Pantazopoulou, E; Varitis, S; Vourlias, G; Chrissafis, K; Dimitrakopulos, G P; Mitrakas, M; Zouboulis, A I; Karakostas, Th; Xenidis, A

2015-01-01

A tannery sludge, produced from physico-chemical treatment of tannery wastewaters, was incinerated without any pre-treatment process under oxic and anoxic conditions, by controlling the abundance of oxygen. Incineration in oxic conditions was performed at the temperature range from 300°C to 1200°C for duration of 2h, while in anoxic conditions at the temperature range from 400°C to 600°C and varying durations. Incineration under oxic conditions at 500°C resulted in almost total oxidation of Cr(III) to Cr(VI), with CaCrO4 to be the crystalline phase containing Cr(VI). At higher temperatures a part of Cr(VI) was reduced, mainly due to the formation of MgCr2O4. At 1200°C approximately 30% of Cr(VI) was reduced to Cr(III). Incineration under anoxic conditions substantially reduced the extent of oxidation of Cr(III) to Cr(VI). Increase of temperature and duration of incineration lead to increase of Cr(VI) content, while no chromium containing crystalline phase was detected. Copyright © 2014 Elsevier B.V. All rights reserved.

Metagenomic insights into the microbiota profiles and bioaugmentation mechanism of organics removal in coal gasification wastewater in an anaerobic/anoxic/oxic system by methanol.

PubMed

Xu, Weichao; Zhang, Yuxiu; Cao, Hongbin; Sheng, Yuxing; Li, Haibo; Li, Yuping; Zhao, He; Gui, Xuefei

2018-05-18

Coal gasification wastewater is a typical high phenol-containing, toxic and refractory industrial wastewater. Here, lab-scale anaerobic-anoxic-oxic system was employed to treat real coal gasification wastewater, and methanol was added to oxic tank as the co-substrate to enhance the removal of refractory organic pollutants. The results showed that the average COD removal in oxic effluent increased from 24.9% to 36.0% by adding methanol, the total phenols concentration decreased from 54.4 to 44.9 mg/L. GC-MS analysis revealed that contents of phenolic components and polycyclic aromatic hydrocarbons (PAHs) were decreased compared to the control and their degradation intermediates were observed. Microbial community revealed that methanol increased the abundance of phenolics and PAHs degraders such as Comamonas, Burkholderia and Sphingopyxis. Moreover, functional analysis revealed the relative abundance of functional genes associated with toluene, benzoate and PAHs degradation pathways was higher than that of control based on KEGG database. Copyright © 2018. Published by Elsevier Ltd.

Abundant Trimethylornithine Lipids and Specific Gene Sequences Are Indicative of Planctomycete Importance at the Oxic/Anoxic Interface in Sphagnum-Dominated Northern Wetlands.

PubMed

Moore, Eli K; Villanueva, Laura; Hopmans, Ellen C; Rijpstra, W Irene C; Mets, Anchelique; Dedysh, Svetlana N; Sinninghe Damsté, Jaap S

2015-09-01

Northern wetlands make up a substantial terrestrial carbon sink and are often dominated by decay-resistant Sphagnum mosses. Recent studies have shown that planctomycetes appear to be involved in degradation of Sphagnum-derived debris. Novel trimethylornithine (TMO) lipids have recently been characterized as abundant lipids in various Sphagnum wetland planctomycete isolates, but their occurrence in the environment has not yet been confirmed. We applied a combined intact polar lipid (IPL) and molecular analysis of peat cores collected from two northern wetlands (Saxnäs Mosse [Sweden] and Obukhovskoye [Russia]) in order to investigate the preferred niche and abundance of TMO-producing planctomycetes. TMOs were present throughout the profiles of Sphagnum bogs, but their concentration peaked at the oxic/anoxic interface, which coincided with a maximum abundance of planctomycete-specific 16S rRNA gene sequences. The sequences detected at the oxic/anoxic interface were affiliated with the Isosphaera group, while sequences present in the anoxic peat layers were related to an uncultured planctomycete group. Pyrosequencing-based analysis identified Planctomycetes as the major bacterial group at the oxic/anoxic interface at the Obukhovskoye peat (54% of total 16S rRNA gene sequence reads), followed by Acidobacteria (19% reads), while in the Saxnäs Mosse peat, Acidobacteria were dominant (46%), and Planctomycetes contributed to 6% of the total reads. The detection of abundant TMO lipids in planctomycetes isolated from peat bogs and the lack of TMO production by cultures of acidobacteria suggest that planctomycetes are the producers of TMOs in peat bogs. The higher accumulation of TMOs at the oxic/anoxic interface and the change in the planctomycete community with depth suggest that these IPLs could be synthesized as a response to changing redox conditions at the oxic/anoxic interface. Copyright © 2015, American Society for Microbiology. All Rights Reserved.

Abundant Trimethylornithine Lipids and Specific Gene Sequences Are Indicative of Planctomycete Importance at the Oxic/Anoxic Interface in Sphagnum-Dominated Northern Wetlands

PubMed Central

Villanueva, Laura; Hopmans, Ellen C.; Rijpstra, W. Irene C.; Mets, Anchelique; Dedysh, Svetlana N.

2015-01-01

Northern wetlands make up a substantial terrestrial carbon sink and are often dominated by decay-resistant Sphagnum mosses. Recent studies have shown that planctomycetes appear to be involved in degradation of Sphagnum-derived debris. Novel trimethylornithine (TMO) lipids have recently been characterized as abundant lipids in various Sphagnum wetland planctomycete isolates, but their occurrence in the environment has not yet been confirmed. We applied a combined intact polar lipid (IPL) and molecular analysis of peat cores collected from two northern wetlands (Saxnäs Mosse [Sweden] and Obukhovskoye [Russia]) in order to investigate the preferred niche and abundance of TMO-producing planctomycetes. TMOs were present throughout the profiles of Sphagnum bogs, but their concentration peaked at the oxic/anoxic interface, which coincided with a maximum abundance of planctomycete-specific 16S rRNA gene sequences. The sequences detected at the oxic/anoxic interface were affiliated with the Isosphaera group, while sequences present in the anoxic peat layers were related to an uncultured planctomycete group. Pyrosequencing-based analysis identified Planctomycetes as the major bacterial group at the oxic/anoxic interface at the Obukhovskoye peat (54% of total 16S rRNA gene sequence reads), followed by Acidobacteria (19% reads), while in the Saxnäs Mosse peat, Acidobacteria were dominant (46%), and Planctomycetes contributed to 6% of the total reads. The detection of abundant TMO lipids in planctomycetes isolated from peat bogs and the lack of TMO production by cultures of acidobacteria suggest that planctomycetes are the producers of TMOs in peat bogs. The higher accumulation of TMOs at the oxic/anoxic interface and the change in the planctomycete community with depth suggest that these IPLs could be synthesized as a response to changing redox conditions at the oxic/anoxic interface. PMID:26150465

Reactivity of Dazomet, a Hydraulic Fracturing Additive: Hydrolysis and Interaction with Pyrite

NASA Astrophysics Data System (ADS)

Consolazio, N.; Lowry, G. V.; Karamalidis, A.; Hakala, A.

2015-12-01

The Marcellus Shale is currently the largest shale gas formation in play across the world. The low-permeability formation requires hydraulic fracturing to be produced. In this process, millions of gallons of water are blended with chemical additives and pumped into each well to fracture the reservoir rock. Although additives account for less than 2% of the fracking fluid mixture, they amount to hundreds of tons per frack job. The environmental properties of some of these additives have been studied, but their behavior under downhole conditions is not widely reported in the peer-reviewed literature. These compounds and their reaction products may return to the surface as produced or waste water. In the event of a spill or release, this water has the potential to contaminate surface soil and water. Of these additives, biocides may present a formidable challenge to water quality. Biocides are toxic compounds (by design), typically added to the Marcellus Shale to control bacteria in the well. An assessment of the most frequently used biocides indicated a need to study the chemical dazomet under reservoir conditions. The Marcellus Shale contains significant deposits of pyrite. This is a ubiquitous mineral within black shales that is known to react with organic compounds in both oxic and anoxic settings. Thus, the objective of our study was to determine the effect of pyrite on the hydrolysis of dazomet. Liquid chromatography-triple quadrupole mass spectrometry (LC-QQQ) was used to calculate the loss rate of aqueous dazomet. Gas chromatography-mass spectrometry (GC-MS) was used to identify the reaction products. Our experiments show that in water, dazomet rapidly hydrolyses in water to form organic and inorganic transformation products. This reaction rate was unaffected when performed under anoxic conditions. However, with pyrite we found an appreciable increase in the removal rate of dazomet. This was accompanied by a corresponding change in the distribution of observed reaction products. Our results indicate the need to determine specific mineral-additive interactions to evaluate the potential risks of chemical use in hydraulic fracturing.

Oxygen intrusion into anoxic fjords leads to increased methylmercury availability

NASA Astrophysics Data System (ADS)

Veiteberg Braaten, Hans Fredrik; Pakhomova, Svetlana; Yakushev, Evgeniy

2013-04-01

Mercury (Hg) appears in the oxic surface waters of the oceans at low levels (sub ng/L). Because inorganic Hg can be methylated into the toxic and bioaccumulative specie methylmercury (MeHg) levels can be high at the top of the marine food chain. Even though marine sea food is considered the main risk driver for MeHg exposure to people most research up to date has focused on Hg methylation processes in freshwater systems. This study identifies the mechanisms driving formation of MeHg during oxygen depletion in fjords, and shows how MeHg is made available in the surface water during oxygen intrusion. Studies of the biogeochemical structure in the water column of the Norwegian fjord Hunnbunn were performed in 2009, 2011 and 2012. In autumn of 2011 mixing flushing events were observed and lead to both positive and negative effects on the ecosystem state in the fjord. The oxygenated water intrusions lead to a decrease of the deep layer concentrations of hydrogen sulfide (H2S), ammonia and phosphate. On the other hand the intrusion also raised the H2S boundary from 8 m to a shallower depth of just 4 m. Following the intrusion was also observed an increase at shallower depths of nutrients combined with a decrease of pH. Before flushing events were observed concentrations of total Hg (TotHg) increased from 1.3 - 1.7 ng/L in the surface layer of the fjord to concentrations ranging from 5.2 ng/L to 6.4 ng/L in the anoxic zone. MeHg increased regularly from 0.04 ng/L in the surface water to a maximum concentration of 5.2 ng/L in the deeper layers. This corresponds to an amount of TotHg present as MeHg ranging from 2.1 % to 99 %. The higher concentrations of MeHg in the deeper layer corresponds to an area where no oxygen is present and concentrations of H2S exceeds 500 µM, suggesting a production of MeHg in the anoxic area as a result of sulphate reducing bacteria activity. After flushing the concentrations of TotHg showed a similar pattern ranging from 0.6 ng/L in the surface layer to 6.5 ng/L at maximum depth (10 m). However, the pattern of MeHg concentrations in the water column changed with relatively high concentrations present already at 4.5 m depth (2.2 ng/L). The environmental consequence of this oxygen intrusion is the appearance in shallower water of toxic MeHg formed in the anoxic layer. As a result of this, MeHg can possibly undergo transport from the anoxic fjord to the surrounding areas.

Nitrate reduction mechanisms and rates in an unconfined eogenetic karst aquifer in two sites with different redox potential

NASA Astrophysics Data System (ADS)

Henson, W. R.; Huang, L.; Graham, W. D.; Ogram, A.

2017-05-01

This study integrates push-pull tracer tests (PPTT) with microbial characterization of extracted water via quantitative polymerase chain reaction (qPCR) and reverse transcriptase qPCR (RT-qPCR) of selected functional N transformation genes to quantify nitrate reduction mechanisms and rates in sites with different redox potential in a karst aquifer. PPTT treatments with nitrate (AN) and nitrate-fumarate (ANC) were executed in two wells representing anoxic and oxic geochemical end-members. Oxic aquifer zero-order nitrate loss rates (mmol L-1 h-1) were similar for AN and ANC treatment, ranging from 0.03 ± 0.01 to 0.05 ± 0.01. Anoxic aquifer zero-order nitrate loss rates ranged from 0.03 ± 0.02 (AN) to 0.13 ± 0.02 (ANC). Microbial characterization indicates mechanisms influencing these rates were dissimilatory nitrate reduction to ammonium (DNRA) at the anoxic site with AN treatment, assimilatory reduction of nitrate to ammonium (ANRA) with ANC treatment in the water column at both sites, and additional documented nitrate reduction that occurred in unsampled biofilms. With carbon treatment, total numbers of microbes (16S rRNA genes) significantly increased (fourteenfold to thirtyfold), supporting stimulated growth with resulting ANRA. Decreased DNRA gene concentrations (nrfA DNA) and increased DNRA activity ratio (nrfA-cDNA/DNA) supported the assertion that DNRA occurred in the anoxic zone with AN and ANC treatment. Furthermore, decreased DNRA gene copy numbers at the anoxic site with ANC treatment suggests that DNRA microbes in the anoxic site are chemolithoautotrophic. Increased RT-qPCR denitrification gene expression (nirK and nirS) was not observed in water samples, supporting that any observed NO3-N loss due to denitrification may be occurring in unsampled microbial biofilms.

Benthic nutrient fluxes in the Eastern Gotland Basin (Baltic Sea) with particular focus on microbial mat ecosystems

NASA Astrophysics Data System (ADS)

Noffke, A.; Sommer, S.; Dale, A. W.; Hall, P. O. J.; Pfannkuche, O.

2016-06-01

Benthic fluxes and water column distributions of dissolved inorganic nitrogen (DIN) and total dissolved phosphate (PO43 -) were measured in situ at 7 sites across a redox gradient from oxic to anoxic bottom waters in the Eastern Gotland Basin (Baltic Sea). The study area was divided into the oxic zone (60 to ca. 80 m water depth, O2 > 30 μM), the hypoxic transition zone (HTZ, ca. 80 to 120 m, O2 < 30 μM) and the deep anoxic and sulfidic basin (> ca. 120 m). Sediments in the HTZ were covered by mats of vacuolated sulfur bacteria. Ammonium (NH4+) fluxes in the deep basin and the HTZ were elevated at 0.6 mmol m- 2 d- 1 and 1 mmol m- 2 d- 1, respectively. Nitrate (NO3-) fluxes were directed into the sediment at all stations in the HTZ and were zero in the deep basin. PO43 - release was highest in the HTZ at 0.23 mmol m- 2 d- 1, with a further release of 0.2 mmol m- 2 d- 1 in the deep basin. Up-scaling the benthic fluxes to the Baltic Proper equals 109 kt yr- 1 of PO43 - and 266 kt yr- 1 of DIN. This is eight- and two-fold higher than the total external load of P (14 kt yr- 1) and DIN (140 kt yr- 1) in 2006 (HELCOM 2009b). The HTZ makes an important contribution to the internal nutrient loading in the Baltic Proper, releasing 70% of P (76 kt yr- 1) and 75% of DIN (200 kt yr- 1) despite covering only 51% of area.

Chemical Evolution of Groundwater Near a Sinkhole Lake, Northern Florida: 2. Chemical Patterns, Mass Transfer Modeling, and Rates of Mass Transfer Reactions

NASA Astrophysics Data System (ADS)

Katz, Brian G.; Plummer, L. Niel; Busenberg, Eurybiades; Revesz, Kinga M.; Jones, Blair F.; Lee, Terrie M.

1995-06-01

Chemical patterns along evolutionary groundwater flow paths in silicate and carbonate aquifers were interpreted using solute tracers, carbon and sulfur isotopes, and mass balance reaction modeling for a complex hydrologic system involving groundwater inflow to and outflow from a sinkhole lake in northern Florida. Rates of dominant reactions along defined flow paths were estimated from modeled mass transfer and ages obtained from CFC-modeled recharge dates. Groundwater upgradient from Lake Barco remains oxic as it moves downward, reacting with silicate minerals in a system open to carbon dioxide (CO2), producing only small increases in dissolved species. Beneath and downgradient of Lake Barco the oxic groundwater mixes with lake water leakage in a highly reducing, silicate-carbonate mineral environment. A mixing model, developed for anoxic groundwater downgradient from the lake, accounted for the observed chemical and isotopic composition by combining different proportions of lake water leakage and infiltrating meteoric water. The evolution of major ion chemistry and the 13C isotopic composition of dissolved carbon species in groundwater downgradient from the lake can be explained by the aerobic oxidation of organic matter in the lake, anaerobic microbial oxidation of organic carbon, and incongruent dissolution of smectite minerals to kaolinite. The dominant process for the generation of methane was by the CO2 reduction pathway based on the isotopic composition of hydrogen (δ2H(CH4) = -186 to -234‰) and carbon (δ13C(CH4) = -65.7 to -72.3‰). Rates of microbial metabolism of organic matter, estimated from the mass transfer reaction models, ranged from 0.0047 to 0.039 mmol L-1 yr-1 for groundwater downgradient from the lake.

Spectroscopic characterization of DOM and the nitrogen removal mechanism during wastewater reclamation plant.

PubMed

Wang, Lei; Li, Ying-Jun; Xiong, Ying; Tan, Wen-Bing; Zhang, Lie-Yu; Li, Xiang; Wang, Xiao-Shu; Xu, Jian-Feng; Li, Tong-Tong; Wang, Jin-Sheng; Cai, Ming-Xuan; Xi, Bei-Dou; Wang, Di-Hua

2017-01-01

The performance of the Sha-he wastewater reclamation plant was evaluated in this study. To remove residual nitrogen after Anaerobic-Anoxic-Oxic (A2O) treatment, three multistage Anoxic-Oxic (A/O) were added to investigate the nitrogen removal efficiency and its mechanism. In addition, the constituents and evolution of dissolved organic matter (DOM) during wastewater reclamation was also investigated using a method combining fluorescence spectroscopy with fluorescence regional integration (FRI). The results suggested that multistage A/O treatment can effectively improve the nitrogen removal ability under low concentrations of carbon sources. The total nitrogen (TN) exhibits significantly positive correlation with fulvic acid-like materials and humic acid-like materials. The correlation coefficient for TN and fulvic acid-like substances (R2 = 0.810, P < 0.01) removal was greater than that of humic acid-like substances (R2 = 0.636, P < 0.05). The results indicate that nitrogen removal may be achieved with the fulvic-like and humic-like substances, and the removal effects were higher by fulvic acid-like substances than humic-like substances, mostly due to that the latter were relatively more difficult to be utilized as carbon source during the nitrogen removal process. The effluent water quality of biological treatment reached the first grade A standard of "Cities sewage treatment plant pollutant discharge standard" (GB18918-2002). In addition, the effluent from the membrane bioreactor reached the "Standards of reclaimed water quality" (SL368-2006).

Quality of bottom material and elutriates in the lower Willamette River, Portland Harbor, Oregon

USGS Publications Warehouse

Fuhrer, Gregory J.

1989-01-01

In October 1983 the U.S. Geological Survey, in cooperation with the U.S. Army Corp of Engineers, collected bottom-material and water samples from Portland Harbor, Oregon to determine concentrations of trace metals and organic compounds in elutriate-test filtrate and bottom material. Of the trace metals examined in bottom material, concentrations of cadmium slightly exceed those of local rocks, whereas lead and zinc exceedance is substantially larger. Of the organochlorine compounds examined in bottom material chlordane, DDD, DDE, DDT, dieldrin, and polychlorinated biphenyls (PCB's) were detected and quantified in at least 30% of the samples tested. A large DDT concentration (2,700 microgram/kilogram) near Doane Lake outlet is indicative of recent contamination. Polychlorinated biphenyls are ubiquitous in bottom sediments; median concentrations are nearly 65 micrograms/kilogram and as large as 550 microgram/kilogram. PCB loading to the Columbia River from Willamette River suspended sediment has been estimated to be 72 kilograms/year, nearly five times the PCB dredge load of 15 kilogram/year. The acid and base-neutral extractable di-n-butyl phthalate and bis (2-ethylhexyl)phthalate occur in sediments of Terminal No. 2 in concentrations as large as 1,965 and 2,200 micrograms/kilogram, respectively. Of the trace metals examined in both standard and oxic elutriate-test filtrate, only copper concentration in an oxic elutriate-test filtrate (19 micrograms/L) exceeded the water quality criteria (5.7 micrograms/L). (USGS)

Spectroscopic characterization of DOM and the nitrogen removal mechanism during wastewater reclamation plant

PubMed Central

Wang, Lei; Li, Ying-Jun; Xiong, Ying; Tan, Wen-Bing; Zhang, Lie-Yu; Li, Xiang; Wang, Xiao-Shu; Xu, Jian-feng; Li, Tong-Tong; Wang, Jin-Sheng; Cai, Ming-Xuan; Xi, Bei-Dou; Wang, Di-Hua

2017-01-01

The performance of the Sha-he wastewater reclamation plant was evaluated in this study. To remove residual nitrogen after Anaerobic-Anoxic-Oxic (A2O) treatment, three multistage Anoxic-Oxic (A/O) were added to investigate the nitrogen removal efficiency and its mechanism. In addition, the constituents and evolution of dissolved organic matter (DOM) during wastewater reclamation was also investigated using a method combining fluorescence spectroscopy with fluorescence regional integration (FRI). The results suggested that multistage A/O treatment can effectively improve the nitrogen removal ability under low concentrations of carbon sources. The total nitrogen (TN) exhibits significantly positive correlation with fulvic acid-like materials and humic acid-like materials. The correlation coefficient for TN and fulvic acid-like substances (R2 = 0.810, P < 0.01) removal was greater than that of humic acid-like substances (R2 = 0.636, P < 0.05). The results indicate that nitrogen removal may be achieved with the fulvic-like and humic-like substances, and the removal effects were higher by fulvic acid-like substances than humic-like substances, mostly due to that the latter were relatively more difficult to be utilized as carbon source during the nitrogen removal process. The effluent water quality of biological treatment reached the first grade A standard of “Cities sewage treatment plant pollutant discharge standard” (GB18918-2002). In addition, the effluent from the membrane bioreactor reached the “Standards of reclaimed water quality” (SL368-2006). PMID:29149172

Structural Characterization of Biogenic Manganese Oxides Produced in Sea Water

NASA Astrophysics Data System (ADS)

Webb, S. M.; Bargar, J. R.; Tebo, B. M.

2003-12-01

Manganese oxides have been coined as the "scavengers of the sea" and play important roles in both marine and freshwater systems. Natural manganese oxide nanoparticles and grain coatings are ubiquitous in the environment and profoundly impact the quality of sediments via their ability to degrade and sequester contaminants. These oxides are believed to form dominantly via oxidation of Mn(II) by marine and freshwater bacteria and have extremely high sorptive capacities for heavy metals. We have used XANES, EXAFS, and synchrotron (SR)-XRD techniques to study biogenic manganese oxides produced by spores of the marine Bacillus sp., strain SG-1 in seawater as a function of reaction time under fully in-situ conditions. The primary biogenic solid-phase Mn oxide product is a hexagonal layered phyollomanganate with an oxidation state similar to that in delta-MnO2. XRD data show the biooxides to have a phyllomanganate 10 basal plane spacing, suggesting the interlayer is hydrated and contains calcium. As the experiment continues, the initial biooxide changes to show triclinic symmetry. Fits to these EXAFS spectra suggest the octahedral layers have low Mn octahedral site vacancies in the lattice and the latyers bend to accommodate Jahn-Teller distortions creating the change in symmetry. The oxides observed in this study as models of Mn(II) bio-oxidation may be representative of the most abundant manganese oxide phase suspended in the oxic and sub-oxic zones of the oceanic water column.

Interpreting Precambrian δ15N: lessons from a new modern analogue, the volcanic crater lake Dziani Dzaha

NASA Astrophysics Data System (ADS)

Ader, M.; Cadeau, P.; Jezequel, D.; Chaduteau, C.; Fouilland, E.; Bernard, C.; Leboulanger, C.

2017-12-01

Precambrian nitrogen biogeochemistry models rely on δ15N signatures in sedimentary rocks, but some of the underlying assumptions still need to be more robustly established. Especially when measured δ15N values are above 3‰. Several processes have been proposed to explain these values: non-quantitative reduction of nitrate to N2O/N2 (denitrification), non-quantitative oxidation of ammonium to N2O/N2, or ammonia degassing to the atmosphere. The denitrification hypothesis implies oxygenation of part the water column, allowing nitrate to accumulate. The ammonium oxidation hypothesis implies a largely anoxic water column, where ammonium can accumulates, with limited oxygenation of surface waters. This hypothesis is currently lacking modern analogues to be supported. We propose here that the volcanic crater lake Dziani Dzaha (Mayotte, Indian Ocean) might be one of them, on the basis of several analogies including: permanently anoxic conditions at depth in spite of seasonal mixing; nitrate content below detection limit in the oxic surface waters; accumulation of ammonium at depth during the stratified season; primary productivity massively dominated by cyanobacteria. One aspect may restrict the analogy: the pH value of 9-9.5. In this lake, δ15N values of primary producers and ammonium range from 6 to 9‰ and are recorded with a positive offset in the sediments (9<δ15N<13‰). Because N-sources to the system present more negative δ15N values, such positive values can only be achieved if 14N-enriched N is lost from the lake. Although NH3 degassing might play a small role, the main pathway envisaged for this N-loss is NH4+ oxidation to N2O/N2. If confirmed, this would provide strong support for the hypothesis that positive δ15N values in Precambrian rocks may indicate dominantly anoxic oceans, devoid of nitrate, in which ammonium was partly oxidized to N2O/N2.

Effects of Reduced Sulfur Compounds on Pd-catalytic Hydrodechlorination of TCE in Groundwater by Cathodic H2 under Electrochemically-induced Oxidizing Conditions

PubMed Central

Yuan, Songhu; Chen, Mingjie; Mao, Xuhui; Alshawabkeh, Akram N.

2014-01-01

Reduced sulfur compounds (RSCs) poison Pd catalysts for catalytic hydrodechlorination of contaminants in anoxic groundwater. This study investigates the effects of RSCs on Pd-catalytic hydrodechlorination of trichloroethylene (TCE) in oxic groundwater. Water electrolysis in an undivided electrolytic cell is used to produce H2 for TCE hydrodechlorination under oxidizing conditions. TCE is efficiently hydrodechlorinated to ethane, with significant accumulation of H2O2 under acidic conditions. Presence of sulfide at concentrations less than 93.8 μM moderately inhibits TCE hydrodechlorination and H2O2 production. Presence of sulfite at low concentrations (≤ 1 mM) significantly enhances TCE decay, while at high concentration (3 mM) inhibits initially and enhances afterwards when sulfite concentration declines to less than 1 mM. Using radical scavenging experiments and electron spin resonance assay, SO3•− which is generated from sulfite under oxidizing conditions is validated as the new reactive species contributing to the enhancement. This study reveals a distinct mechanism of effect of sulfite on TCE hydrodechlorination by Pd and H2 in oxic groundwater and presents an alternative approach to increasing resistance of Pd to RSCs poisoning. PMID:23962132

The reactivity of Fe(II) associated with goethite formed during short redox cycles toward Cr(VI) reduction under oxic conditions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tomaszewski, Elizabeth J.; Lee, Seungyeol; Rudolph, Jared

Chromium (Cr) is a toxic metal that causes a myriad of health problems and enters the environment as a result of anthropogenic activities and/or natural processes. The toxicity and solubility of chromium is linked to its oxidation state; Cr(III) is poorly soluble and relatively nontoxic, while Cr(VI) is soluble and a known carcinogen. Solid Fe(II) in iron-bearing minerals, such as pyrite, magnetite, and green rusts, reduce the oxidation state of chromium, reducing its toxicity and mobility. However, these minerals are not the only potential sources of solid-associated Fe(II) available for Cr(VI) reduction. For example, ferric (Fe(III)) (hydr)oxides, such as goethitemore » or hematite, can have Fe(II) in the solid without phase transformation; however, the reactivity of Fe(II) within Fe(III) (hydr)oxides with contaminants, has not been previously investigated. Here, we cyclically react goethite with dissolved Fe(II) followed by dissolved O2, leading to the formation of reactive Fe(II) associated with goethite. In separate reactors, the reactivity of this Fe(II) is probed under oxic conditions, by exposure to chromate (CrO42 -) after either one, two, three or four redox cycles. Cr is not present during redox cycling; rather, it is introduced to a subset of the solid after each oxidation half-cycle. Analysis of X-ray absorption near edge structure (XANES) spectra reveals that the extent of Cr(VI) reduction to Cr(III) depends not only on solid Fe(II) content but also surface area and mean size of ordered crystalline domains, determined by BET surface area analysis and X-ray diffraction (XRD), respectively. Shell-by-shell fitting of the extended X-ray absorption fine structure (EXAFS) spectra demonstrates chromium forms both single and double corner sharing complexes on the surface of goethite, in addition to sorbed Cr(III) species. Finally, transmission electron microscope (TEM) imaging and X-ray energy-dispersive spectroscopy (EDS) illustrate that Cr preferentially localizes on the (100) face of goethite, independent of the number of redox cycles goethite undergoes. This work demonstrates that under oxic conditions, solid Fe(II) associated with goethite resulting from rapid redox cycling is reactive and available for electron transfer to Cr(VI), suggesting Fe(III) (hydr)oxides may act as reservoirs of reactive electron density, even in oxygen saturated environments.« less

Radiobiological description of the LET dependence of the cell survival of oxic and anoxic cells irradiated by carbon ions.

PubMed

Antonovic, L; Brahme, A; Furusawa, Y; Toma-Dasu, I

2013-01-01

Light-ion radiation therapy against hypoxic tumors is highly curative due to reduced dependence on the presence of oxygen in the tumor at elevated linear energy transfer (LET) towards the Bragg peak. Clinical ion beams using spread-out Bragg peak (SOBP) are characterized by a wide spectrum of LET values. Accurate treatment optimization requires a method that can account for influence of the variation in response for a broad range of tumor hypoxia, absorbed doses and LETs. This paper presents a parameterization of the Repairable Conditionally-Repairable (RCR) cell survival model that can describe the survival of oxic and hypoxic cells over a wide range of LET values, and investigates the relationship between hypoxic radiation resistance and LET. The biological response model was tested by fitting cell survival data under oxic and anoxic conditions for V79 cells irradiated with LETs within the range of 30-500 keV/µm. The model provides good agreement with experimental cell survival data for the range of LET investigated, confirming the robustness of the parameterization method. This new version of the RCR model is suitable for describing the biological response of mixed populations of oxic and hypoxic cells and at the same time taking into account the distribution of doses and LETs in the incident beam and its variation with depth in tissue. The model offers a versatile tool for the selection of LET and dose required in the optimization of the therapeutic effect, without severely affecting normal tissue in realistic tumors presenting highly heterogeneous oxic and hypoxic regions.

Simultaneous denitrification and denitrifying phosphorus removal in a full-scale anoxic-oxic process without internal recycle treating low strength wastewater.

PubMed

Wang, Qibin; Chen, Qiuwen

2016-01-01

Performance of a full-scale anoxic-oxic activated sludge treatment plant (4.0×10(5) m(3)/day for the first-stage project) was followed during a year. The plant performed well for the removal of carbon, nitrogen and phosphorus in the process of treating domestic wastewater within a temperature range of 10.8°C to 30.5°C. Mass balance calculations indicated that COD utilization mainly occurred in the anoxic phase, accounting for 88.2% of total COD removal. Ammonia nitrogen removal occurred 13.71% in the anoxic zones and 78.77% in the aerobic zones. The contribution of anoxic zones to total nitrogen (TN) removal was 57.41%. Results indicated that nitrogen elimination in the oxic tanks was mainly contributed by simultaneous nitrification and denitrification (SND). The reduction of phosphorus mainly took place in the oxic zones, 61.46% of the total removal. Denitrifying phosphorus removal was achieved biologically by 11.29%. Practical experience proved that adaptability to gradually changing temperature of the microbial populations was important to maintain the plant overall stability. Sudden changes in temperature did not cause paralysis of the system just lower removal efficiency, which could be explained by functional redundancy of microorganisms that may compensate the adverse effects of temperature changes to a certain degree. Anoxic-oxic process without internal recycling has great potential to treat low strength wastewater (i.e., TN<35 mg/L) as well as reducing operation costs. Copyright © 2015. Published by Elsevier B.V.

Microbial responses to chitin and chitosan in oxic and anoxic agricultural soil slurries

NASA Astrophysics Data System (ADS)

Wieczorek, A. S.; Hetz, S. A.; Kolb, S.

2014-06-01

Microbial degradation of chitin in soil substantially contributes to carbon cycling in terrestrial ecosystems. Chitin is globally the second most abundant biopolymer after cellulose and can be deacetylated to chitosan or can be hydrolyzed to N,N'-diacetylchitobiose and oligomers of N-acetylglucosamine by aerobic and anaerobic microorganisms. Which pathway of chitin hydrolysis is preferred by soil microbial communities is unknown. Supplementation of chitin stimulated microbial activity under oxic and anoxic conditions in agricultural soil slurries, whereas chitosan had no effect. Thus, the soil microbial community likely was more adapted to chitin as a substrate. In addition, this finding suggested that direct hydrolysis of chitin was preferred to the pathway that starts with deacetylation. Chitin was apparently degraded by aerobic respiration, ammonification, and nitrification to carbon dioxide and nitrate under oxic conditions. When oxygen was absent, fermentation products (acetate, butyrate, propionate, hydrogen, and carbon dioxide) and ammonia were detected, suggesting that butyric and propionic acid fermentation, along with ammonification, were likely responsible for anaerobic chitin degradation. In total, 42 different chiA genotypes were detected of which twenty were novel at an amino acid sequence dissimilarity of less than 50%. Various chiA genotypes responded to chitin supplementation and affiliated with a novel deep-branching bacterial chiA genotype (anoxic conditions), genotypes of Beta- and Gammaproteobacteria (oxic and anoxic conditions), and Planctomycetes (oxic conditions). Thus, this study provides evidence that detected chitinolytic bacteria were catabolically diverse and occupied different ecological niches with regard to oxygen availability enabling chitin degradation under various redox conditions on community level.

Microbial responses to chitin and chitosan in oxic and anoxic agricultural soil slurries

NASA Astrophysics Data System (ADS)

Wieczorek, A. S.; Hetz, S. A.; Kolb, S.

2014-02-01

Chitin is the second most abundant biopolymer in terrestrial ecosystems and is subject to microbial degradation. Chitin can be deacetylated to chitosan or can be hydrolyzed to N,N'-diacetylchitobiose and oligomers of N-acetylglucosamine by aerobic and anaerobic microorganisms. Which pathway of chitin hydrolysis is preferred by soil microbial communities has previously been unknown. Supplementation of chitin stimulated microbial activity under oxic and anoxic conditions in agricultural soil slurries, whereas chitosan had no effect. Thus, the soil microbial community likely was more adapted to chitin as a substrate. In addition, this finding suggested that direct hydrolysis of chitin was preferred to the pathway that starts with deacetylation. Chitin was apparently degraded by aerobic respiration, ammonification, and nitrification to carbon dioxide and nitrate under oxic conditions. When oxygen was absent, fermentation products (acetate, butyrate, propionate, hydrogen, carbon dioxide) and ammonia were detected, suggesting that butyric and propionic acid fermentation were along with ammonification likely responsible for apparent anaerobic chitin degradation. In total, 42 different chiA genotypes were detected of which twenty were novel at an amino acid sequence dissimilarity of >50%. Various chiA genotypes responded to chitin supplementation and affiliated with a novel deep-branching bacterial chiA genotype (anoxic conditions), genotypes of Beta- and Gammaproteobacteria (oxic and anoxic conditions), and Planctomycetes (oxic conditions). Thus, this study provides evidence that detected chitinolytic bacteria were catabolically diverse and occupied different ecological niches with regard to oxygen availability enabling chitin degradation under various redox conditions at the level of the community.

Meteorological drivers of hypolimnetic anoxia in a eutrophic, north temperate lake

USGS Publications Warehouse

Snortheim, Craig A.; Hanson, Paul C.; McMahon, Katherine D.; Read, Jordan S.; Carey, Cayelan C.; Dugan, Hilary

2017-01-01

Oxygen concentration is both an indicator and driver of water quality in lakes. Decreases in oxygen concentration leads to altered ecosystem function as well as harmful consequences for aquatic biota, such as fishes. The responses of oxygen dynamics in lakes to climate-related drivers, such as temperature and wind speed, are well documented for lake surface waters. However, much less is known about how the oxic environment of bottom waters, especially the timing and magnitude of anoxia in eutrophic lakes, responds to changes in climate drivers. Understanding how important ecosystem states, such as hypolimnetic anoxia, may respond to differing climate scenarios requires a model that couples physical-biological conditions and sufficiently captures the density stratification that leads to strong oxygen gradients. Here, we analyzed the effects of changes in three important meteorological drivers (air temperature, wind speed, and relative humidity) on hypolimnetic anoxia in a eutrophic, north temperate lake using the anoxic factor as an index that captures both the temporal and spatial extent of anoxia. Air temperature and relative humidity were found to have a positive correlation with anoxic factor, while wind speed had a negative correlation. Air temperature was found to have the greatest potential impact of the three drivers on the anoxic factor, followed by wind speed and then relative humidity. Across the scenarios of climate variability, variation in the simulated anoxic factor was primarily due to changes in the timing of onset and decay of stratification. Given the potential for future changes in climate, especially increases in air temperature, this study provides important insight into how these changes will alter lake water quality.

Impacts of Freshets on Hyporheic Exchange Flow under Neutral Conditions

NASA Astrophysics Data System (ADS)

Singh, T.; Wu, L.; Worman, A. L. E.; Hannah, D. M.; Krause, S.; Gomez-Velez, J. D.

2016-12-01

Hyporheic zones (HZs) are characterized by the exchange of water, solutes, momentum and energy between streams and aquifers. Hyporheic exchange flow (HEF) is driven by pressure gradients along the sediment-water interface, which in turn are caused by interactions between channel flow and bed topography. With this in mind, changes in channel flow can have significant effects in the hydrodynamic and transport characteristics of HZs. While previous research has improved our understanding of the drivers and controls of HEF, little attention has been paid to the potential impacts of transient dynamic hydrologic forcing, such as freshets. In this study, we use a two-dimensional, homogeneous flow and transport model with a time-varying pressure distribution at the sediment-water interface to explore the dynamic development of HZ characteristics in response to discharge fluctuations (i.e., freshets). With this model, we explore a wide range of plausible scenarios for discharge and bed geometry. Our modelling results show that a single freshet alters the spatial extent and penetration of the HZ, though quantitatively different, when investigated using hydrological (streamlines/flow field) and geochemical (>90% of surface water in streambed) approaches of HZ. We summarize the results of a detailed sensitivity analysis where the effects of hydraulic geometry (slope, amplitude of the streambed), flood characteristics (duration, skewness and magnitude of the flood wave) and biogeochemical timescales (time-scale for oxygen consumption) on the HZ's extent, mean age, and oxic/anoxic zonation are explored. Taking into consideration these multiple morphological characteristics along with variable hydrological controls has clear potential to facilitate process understanding and upscaling.

Microbial community phylogenetic and trait diversity declines with depth in a marine oxygen minimum zone.

PubMed

Bryant, Jessica A; Stewart, Frank J; Eppley, John M; DeLong, Edward F

2012-07-01

Oxygen minimum zones (OMZs) are natural physical features of the world's oceans. They create steep physiochemical gradients in the water column, which most notably include a dramatic draw down in oxygen concentrations over small vertical distances (<100 m). Microbial communities within OMZs play central roles in ocean and global biogeochemical cycles, yet we still lack a fundamental understanding of how microbial biodiversity is distributed across OMZs. Here, we used metagenomic sequencing to investigate microbial diversity across a vertical gradient in the water column during three seasons in the Eastern Tropical South Pacific (ETSP) OMZ. Based on analysis of small subunit ribosomal RNA (SSU rRNA) gene fragments, we found that both taxonomic and phylogenetic diversity declined steeply along the transition from oxygen-rich surface water to the permanent OMZ. We observed similar declines in the diversity of protein-coding gene categories, suggesting a decrease in functional (trait) diversity with depth. Metrics of functional and trait dispersion indicated that microbial communities are phylogenetically and functionally more overdispersed in oxic waters, but clustered within the OMZ. These dispersion patterns suggest that community assembly drivers (e.g., competition, environmental filtering) vary strikingly across the oxygen gradient. To understand the generality of our findings, we compared OMZ results to two marine depth gradients in subtropical oligotrophic sites and found that the oligotrophic sites did not display similar patterns, likely reflecting unique features found in the OMZ. Finally, we discuss how our results may relate to niche theory, diversity-energy relationships and stress gradients.

THERMICANUS AEGYPTIUS GEN. NOV., SP. NOV., ISOLATED FROM OXIC SOIL, A FERMENTATIVE MICROAEROPHILE THAT GROWS COMMENSALLY WITH THE THERMOPHILIC ACETOGEN MOORELLA THERMOACETICA

EPA Science Inventory

A thermophilic, fermentative microaerophile (ET-5b) and a thermophilic acetogen (ET-5a) were coisolated from oxic soil obtained from Egypt. The 16S rRNA gene sequence of ET-5a was 99.8% identical to that of the classic acetogen Moorella thermoacetica. Further analyses confirmed t...

Enhanced reduction of excess sludge and nutrient removal in a pilot-scale A2O-MBR-TAD system.

PubMed

Ventura, J S; Seo, S; Chung, I; Yeom, I; Kim, H; Oh, Y; Jahng, D

2011-01-01

In this study, a pilot scale anaerobic-anoxic-oxic (A2O) process with submerged membrane (MBR) in the oxic tank was coupled with thermophilic aerobic digestion (TAD) reactor and was operated for longer than 600 days to treat real domestic wastewater. Regardless of the varying conditions of the system, the A2O-MBR-TAD process removed MLSS, TCOD, BOD, TN, TP, and E. coli about 99%, 96%, 96%, 70%, 83%, and 99%, respectively. The additional TP removal of the system was due to the precipitating agent directly added in the oxic reactor, without which TP removal was about 56%. In the TAD reactor, receiving MLSS from the oxic tank (MBR), about 25% of TSS and VSS were solubilized during 2 days of retention. The effluent of the TAD reactor was recycled into the anoxic tank of A2O-MBR to provide organic carbon for denitrification and cryptic growth. By controlling the flowrate of wasting stream from the MBR, sludge production decreased to almost zero. From these results, it was concluded that the A2O-MBR-TAD process could be a reliable option for excellent effluent quality and near zero-sludge production.

Using Cl/Br ratios and other indicators to assess potential impacts on groundwater quality from septic systems: A review and examples from principal aquifers in the United States

NASA Astrophysics Data System (ADS)

Katz, Brian G.; Eberts, Sandra M.; Kauffman, Leon J.

2011-02-01

SummaryA detailed review was made of chemical indicators used to identify impacts from septic tanks on groundwater quality. Potential impacts from septic tank leachate on groundwater quality were assessed using the mass ratio of chloride-bromide (Cl/Br), concentrations of selected chemical constituents, and ancillary information (land use, census data, well depth, soil characteristics) for wells in principal aquifers of the United States. Chemical data were evaluated from 1848 domestic wells in 19 aquifers, 121 public-supply wells in 6 aquifers, and associated monitoring wells in four aquifers and their overlying hydrogeologic units. Based on previously reported Cl/Br ratios, statistical comparisons between targeted wells (where Cl/Br ratios range from 400 to 1100 and Cl concentrations range from 20 to 100 mg/L) and non-targeted wells indicated that shallow targeted monitoring and domestic wells (<20 m depth below land surface) had a significantly ( p < 0.05) higher median percentage of houses with septic tanks (1990 census data) than non-targeted wells. Higher ( p = 0.08) median nitrate-N concentration (3.1 mg/L) in oxic (dissolved oxygen concentrations >0.5 mg/L) shallow groundwater from target domestic wells, relative to non-target wells (1.5 mg/L), corresponded to significantly higher potassium, boron, chloride, dissolved organic carbon, and sulfate concentrations, which may also indicate the influence of septic-tank effluent. Impacts on groundwater quality from septic systems were most evident for the Eastern Glacial Deposits aquifer and the Northern High Plains aquifer that were associated with the number of housing units using septic tanks, high permeability of overlying sediments, mostly oxic conditions, and shallow wells. Overall, little or no influence from septic systems were found for water samples from the deeper public-supply wells. The Cl/Br ratio is a useful first-level screening tool for assessing possible septic tank influence in water from shallow wells (<20 m) with the range of 400-1100. The use of this ratio would be enhanced with information on other chloride sources, temporal variability of chloride and bromide concentrations in shallow groundwater, knowledge of septic-system age and maintenance, and the use of multiple tracers (combination of additional chemical and microbiological indicators).

Arsenic Redistribution Between Sediments and Water Near a Highly Contaminated Source

DOE Office of Scientific and Technical Information (OSTI.GOV)

Keimowitz,A.; Zheng, Y.; Chillrud, S.

2005-01-01

Mechanisms controlling arsenic partitioning between sediment, groundwater, porewaters, and surface waters were investigated at the Vineland Chemical Company Superfund site in southern New Jersey. Extensive inorganic and organic arsenic contamination at this site (historical total arsenic >10 000 {micro}g L{sup -1} or >130 {micro}M in groundwater) has spread downstream to the Blackwater Branch, Maurice River, and Union Lake. Stream discharge was measured in the Blackwater Branch, and water samples and sediment cores were obtained from both the stream and the lake. Porewaters and sediments were analyzed for arsenic speciation as well as total arsenic, iron, manganese, and sulfur, and theymore » indicate that geochemical processes controlling mobility of arsenic were different in these two locations. Arsenic partitioning in the Blackwater Branch was consistent with arsenic primarily being controlled by sulfur, whereas in Union Lake, the data were consistent with arsenic being controlled largely by iron. Stream discharge and arsenic concentrations indicate that despite large-scale groundwater extraction and treatment, >99% of arsenic transport away from the site results from continued discharge of high arsenic groundwater to the stream, rather than remobilization of arsenic in stream sediments. Changing redox conditions would be expected to change arsenic retention on sediments. In sulfur-controlled stream sediments, more oxic conditions could oxidize arsenic-bearing sulfide minerals, thereby releasing arsenic to porewaters and streamwaters; in iron-controlled lake sediments, more reducing conditions could release arsenic from sediments via reductive dissolution of arsenic-bearing iron oxides.« less

Effects of redox conditions on the adsorption of dissolved organic matter to soil minerals and differently aged paddy soils

NASA Astrophysics Data System (ADS)

Sauerwein, Meike; Hanke, Alexander; Kaiser, Klaus; Kalbitz, Karsten

2010-05-01

Effects of redox conditions on the adsorption of dissolved organic matter to soil minerals and differently aged paddy soils Meike Sauerwein1, Alexander Hanke2, Klaus Kaiser3, Karsten Kalbitz2 1) Dept. of Soil Ecology, Bayreuth Centre of Ecology and Environmental Research (BayCEER), University of Bayreuth, 95440 Bayreuth, Germany, meike.sauerwein@gmail.com 2) Institute of ecosystem dynamics and biodiversity, University of Amsterdam, 1018 WV, Netherlands, a.hanke@uva.nl, k.kalbitz@uva.nl 3) Soil Sciences, Martin Luther University Halle, 06099 Halle, Germany, klaus.kaiser@landw.uni-halle.de Current knowledge on dissolved organic matter (DOM) in soils is based mainly on observations and experiments in aerobic environments. Adsorption to soil minerals is an important mechanism of DOM retention and stabilization against microbial decay under oxic conditions. Under anoxic conditions where hydrous iron oxides, the potential main adsorbents of DOM, possibly dissolve, the importance of adsorption seems questionable. Therefore, we studied the adsorption of DOM to selected soil minerals and to mineral soils under oxic and anoxic conditions. In detail, we tested the following hypotheses: 1. Minerals and soils adsorb less DOM under anoxic conditions than under oxic ones. 2. The reduced adsorption under anoxic conditions is result of the smaller adsorption to hydrous Fe oxides whereas adsorption to clay minerals and Al hydroxides is not sensitive to changes in redox conditions 3. DOM adsorption will increase with the number of redox cycles, thus time of soil formation, due to increasing contents of poorly crystalline Fe oxides. This will, however, cause a stronger sensitivity to redox changes as poor crystalline Fe oxides are more reactive. 4. Aromatic compounds, being preferentially adsorbed under oxic conditions, will be less strongly adsorbed under anoxic conditions. We chose paddy soils as models because their periodically and regular exposure to changing redox cycles, with anoxic conditions during the rice growing period and oxic conditions during harvest and growth of other crops. Soils of a unique chronosequence of paddy soils (50, 300, 700 and 2000 years) in China were studied in direct comparison to non-paddy soils of the same age. In additions, selected soil minerals (goethite, ferrihydrite, amorphous Al hydroxide, hydrobiotite, nontronite and ripodolite), differing in their response to changes in redox conditions, were studied in order to indentify those mineral constituents responsible for redox-induced changes in DOM adsorption to the test soils. The DOM for the adsorption was extracted from composted rice straw as a surrogate for DOM percolating in paddy soils. Batch adsorption experiments were carried out with DOM pre-incubated to give oxic and anoxic conditions and maintaining these redox conditions during the whole procedure. The redox potential resulting from anoxic pre-incubation was about 100 mV, thus in the range of Fe reduction. Besides of dissolved organic carbon (DOC), we determined changes in the composition of DOM by the specific UV absorbance. We also analyzed main cations, anions and redox-sensitive elements to give a comprehensive picture of the effects of changing redox conditions on the dynamics of organic C, N, P, S, Fe and Al. First results indicated indeed less adsorption of DOM to Fe oxides under anoxic than under oxic conditions, with a more pronounced effect for ferrihydrite than for goethite. Maximum adsorption of DOM was more than 50% larger under oxic than under anoxic conditions. The effect was less pronounced but still detectable for clay minerals such as hydrobiotite, nontronite, and ripodolite. The specific UV absorbance of DOM contact with minerals was 20-50% stronger under anoxic than under oxic conditions. These changes in DOM composition indicated that preferential adsorption of aromatic compounds might be limited to aerated soils. We conclude that adsorption, although less strong than under oxic conditions, is an important mechanism of DOM retention also under anoxic conditions. Decreasing amounts of adsorbed DOM and changes in its composition might result in a less effective sorptive stabilization against microbial decay under anoxic than under oxic conditions.

Intensification and deepening of the Arabian Sea Oxygen Minimum Zone in response to increase in Indian monsoon wind intensity

NASA Astrophysics Data System (ADS)

Lachkar, Zouhair; Smith, Shafer; Levy, Marina

2017-04-01

The decline in oxygen supply to the ocean associated with global warming of sea-surface temperatures is expected to expand the oxygen minimum zones (OMZs). This global trend can be attenuated or amplified by regional processes. In the Arabian Sea, the World's thickest OMZ is highly vulnerable to changes in the Indian monsoon wind. Evidence from paleo records and future climate projections indicate strong variations of the Indian monsoon wind intensity over climatic timescales. Yet, the response of the OMZ to these wind changes remains poorly understood and its amplitude and timescale unexplored. Here, we investigate the impacts of perturbations in Indian monsoon wind intensity (from -50% to +50%) on the size and intensity of the Arabian Sea OMZ, and examine the biogeochemical and ecological implications of these changes. To this end, we conducted a series of eddy-resolving simulations of the Arabian Sea using the Regional Oceanic Modeling System (ROMS) coupled to a nitrogen based Nutrient-Phytoplankton-Zooplankton-Detritus (NPZD) ecosystem model that includes a representation of the O2 cycle. We show that the Arabian Sea productivity increases and its OMZ expands and deepens in response to monsoon wind intensification. These responses are dominated by the perturbation of the summer monsoon wind, whereas the changes in the winter monsoon wind play a secondary role. While the productivity responds quickly and nearly linearly to wind increase (i.e., on a timescale of years), the OMZ response is much slower (i.e., a timescale of decades). Our analysis reveals that the OMZ expansion at depth is driven by increased oxygen biological consumption, whereas its surface weakening is induced by increased lateral ventilation. The enhanced lateral ventilation favors episodic intrusions of oxic waters in the lower epipelagic zone (100-200m) of the western and central Arabian Sea, leading to intermittent expansions of habitats and a more frequent alternation of hypoxic and oxic conditions there. The increased productivity and deepening of the OMZ also lead to a strong intensification of denitrification at depth, resulting in a substantial amplification of fixed nitrogen depletion in the Arabian Sea. We conclude that changes in the Indian monsoon can affect, on longer timescales, the large-scale biogeochemical cycles of nitrogen and carbon, with a positive feedback on climate change in the case of stronger winds.

Integrated carbon, sulfur, and nitrogen isotope chemostratigraphy of the Ediacaran Lantian Formation in South China: Spatial gradient, ocean redox oscillation, and fossil distribution.

PubMed

Wang, W; Guan, C; Zhou, C; Peng, Y; Pratt, L M; Chen, X; Chen, L; Chen, Z; Yuan, X; Xiao, S

2017-07-01

The Ediacaran Doushantuo Formation in South China is a prime target for geobiological investigation because it offers opportunities to integrate chemostratigraphic and paleobiological data. Previous studies were mostly focused on successions in shallow-water shelf facies, but data from deep-water successions are needed to fully understand basinal redox structures. Here, we report δ 13 C carb , δ 13 C org , δ 34 S pyr , δ 34 S CAS , and δ 15 N sed data from a drill core of the fossiliferous Lantian Formation, which is a deep-water equivalent of the Doushantuo Formation. Our data confirm a large (>10‰) spatial gradient in δ 13 C carb in the lower Doushantuo/Lantian formations, but this gradient is probably due to the greater sensitivity of carbonate-poor deep-water sediments to isotopic mixing with 13 C-depleted carbonate cements. A pronounced negative δ 13 C carb excursion (EN3) in the upper Doushantuo/Lantian formations, however, is spatially consistent and may be an equivalent of the Shuram excursion. δ 34 S pyr is more negative in deeper-water facies than in shallow-water facies, particularly in the lower Doushantuo/Lantian formations, and this spatial pattern is interpreted as evidence for ocean redox stratification: Pyrite precipitated in euxinic deep waters has lower δ 34 S pyr than that formed within shallow-water sediments. The Lantian Formation was probably deposited in oscillating oxic and euxinic conditions. Euxinic black shales have higher TOC and TN contents, but lower δ 34 S pyr and δ 15 N sed values. In euxinic environments, pyrite was predominantly formed in the water column and organic nitrogen was predominantly derived from nitrogen fixation or NH 4 + assimilation because of quantitative denitrification, resulting in lower δ 34 S pyr and δ 15 N sed values. Benthic macroalgae and putative animals occur exclusively in euxinic black shales. If preserved in situ, these organisms must have lived in brief oxic episodes punctuating largely euxinic intervals, only to be decimated and preserved when the local environment switched back to euxinia again. Thus, taphonomy and ecology were the primary factors controlling the stratigraphic distribution of macrofossils in the Lantian Formation. © 2017 John Wiley & Sons Ltd.

Adsorption characteristics of Bisphenol-A on tailored activated carbon in aqueous solutions.

PubMed

Yan, Liang; Lv, Di; Huang, Xinwen; Shi, Huixiang; Zhang, Geshan

2016-10-01

The adsorption behavior of pharmaceuticals and personal care product, Bisphenol-A (BPA), according to four coal-based and four wood-based granular activated carbons modified using outgassing treatment, acidic treatment or alkaline treatment was studied. The adsorption isotherm results indicated that carbon surface acidity played a very important role in the adsorption of BPA. It was found that increasing surface acidity would increase the hydrogen bonding effects and increase adsorption of BPA on activated carbon. The acidic modified sample (F600-A and OLC-A) represented the best adsorption capacity, and the equilibrium adsorption amounts reached 346.42 and 338.55 mg/g, respectively. Further, effects of surface charge and surface basicity were examined. It was found that the adsorbed amount of BPA decreased with the increase of surface charge. Finally, there appeared to be a significant oligomerization phenomenon with BPA molecules onto the surface of activated carbon. OLC and OLC-OG, which have higher micropore percentages, are very effective in hampering the oligomerization of BPA under oxic conditions.

Peeking under the Iron Curtain: Development of a Microcosm for Imaging the Colonization of Steel Surfaces by Mariprofundus sp. Strain DIS-1, an Oxygen-Tolerant Fe-Oxidizing Bacterium

PubMed Central

Adaktylou, Irini J.; Emerson, David

2016-01-01

ABSTRACT Microbially influenced corrosion (MIC) is a major cause of damage to steel infrastructure in the marine environment. Despite their ability to grow directly on Fe(II) released from steel, comparatively little is known about the role played by neutrophilic iron-oxidizing bacteria (FeOB). Recent work has shown that FeOB grow readily on mild steel (1018 MS) incubated in situ or as a substrate for pure cultures in vitro; however, details of how they colonize steel surfaces are unknown yet are important for understanding their effects. In this study, we combine a novel continuously upwelling microcosm with confocal laser scanning microscopy (CLSM) to determine the degree of colonization of 1018 MS by the marine FeOB strain DIS-1. 1018 MS coupons were incubated with sterile seawater (pH 8) inoculated with strain DIS-1. Incubations were performed both under oxic conditions and in an anoxic-to-oxic gradient. Following incubations of 1 to 10 days, the slides were removed from the microcosms and stained to visualize both cells and stalk structures. Stained coupons were visualized by CLSM after being mounted in a custom frame to preserve the three-dimensional structure of the biofilm. The incubation of 1018 MS coupons with strain DIS-1 under oxic conditions resulted in initial attachment of cells within 2 days and nearly total coverage of the coupon with an ochre film within 5 days. CLSM imaging revealed a nonadherent biofilm composed primarily of the Fe-oxide stalks characteristic of strain DIS-1. When incubated with elevated concentrations of Fe(II), DIS-1 colonization of 1018 MS was inhibited. IMPORTANCE These experiments describe the growth of a marine FeOB in a continuous culture system and represent direct visualizations of steel colonization by FeOB. We anticipate that these experiments will lay the groundwork for studying the mechanisms by which FeOB colonize steel and help to elucidate the role played by marine FeOB in MIC. These observations of the interaction between an FeOB, strain DIS-1, and steel suggest that this experimental system will provide a useful model for studying the interactions between microbes and solid substrates. PMID:27637877

Peeking under the Iron Curtain: Development of a Microcosm for Imaging the Colonization of Steel Surfaces by Mariprofundus sp. Strain DIS-1, an Oxygen-Tolerant Fe-Oxidizing Bacterium.

PubMed

Mumford, Adam C; Adaktylou, Irini J; Emerson, David

2016-11-15

Microbially influenced corrosion (MIC) is a major cause of damage to steel infrastructure in the marine environment. Despite their ability to grow directly on Fe(II) released from steel, comparatively little is known about the role played by neutrophilic iron-oxidizing bacteria (FeOB). Recent work has shown that FeOB grow readily on mild steel (1018 MS) incubated in situ or as a substrate for pure cultures in vitro; however, details of how they colonize steel surfaces are unknown yet are important for understanding their effects. In this study, we combine a novel continuously upwelling microcosm with confocal laser scanning microscopy (CLSM) to determine the degree of colonization of 1018 MS by the marine FeOB strain DIS-1. 1018 MS coupons were incubated with sterile seawater (pH 8) inoculated with strain DIS-1. Incubations were performed both under oxic conditions and in an anoxic-to-oxic gradient. Following incubations of 1 to 10 days, the slides were removed from the microcosms and stained to visualize both cells and stalk structures. Stained coupons were visualized by CLSM after being mounted in a custom frame to preserve the three-dimensional structure of the biofilm. The incubation of 1018 MS coupons with strain DIS-1 under oxic conditions resulted in initial attachment of cells within 2 days and nearly total coverage of the coupon with an ochre film within 5 days. CLSM imaging revealed a nonadherent biofilm composed primarily of the Fe-oxide stalks characteristic of strain DIS-1. When incubated with elevated concentrations of Fe(II), DIS-1 colonization of 1018 MS was inhibited. These experiments describe the growth of a marine FeOB in a continuous culture system and represent direct visualizations of steel colonization by FeOB. We anticipate that these experiments will lay the groundwork for studying the mechanisms by which FeOB colonize steel and help to elucidate the role played by marine FeOB in MIC. These observations of the interaction between an FeOB, strain DIS-1, and steel suggest that this experimental system will provide a useful model for studying the interactions between microbes and solid substrates. Copyright © 2016, American Society for Microbiology. All Rights Reserved.

A 150-year record of phytoplankton community succession controlled by hydroclimatic variability in a tropical lake

NASA Astrophysics Data System (ADS)

Afrifa Yamoah, Kweku; Callac, Nolwenn; Fru, Ernest Chi; Wohlfarth, Barbara; Wiech, Alan; Chabangborn, Akkaneewut; Smittenberg, Rienk H.

2016-07-01

Climate and human-induced environmental change promote biological regime shifts between alternate stable states, with implications for ecosystem resilience, function, and services. While these effects have been shown for present-day ecosystems, the long-term response of microbial communities has not been investigated in detail. This study assessed the decadal variations in phytoplankton communities in a ca. 150 year long sedimentary archive of Lake Nong Thale Prong (NTP), southern Thailand using a combination of bulk geochemical analysis, quantitative polymerase chain reaction (qPCR) and lipid biomarkers techniques including compound-specific hydrogen isotope analysis as a proxy for precipitation. Relatively drier and by inference warmer conditions from ca. 1857 to 1916 Common Era (CE) coincided with a dominance of the green algae Botryococcus braunii, indicating lower nutrient levels in the oxic lake surface waters, possibly related to lake water stratification. A change to higher silica (Si) input around 1916 CE was linked to increased rainfall and concurs with an abrupt takeover by diatom blooms lasting for 50 years. These were increasingly outcompeted by cyanobacteria from the 1970s onwards, most likely because of increased levels of anthropogenic phosphate and a reduction in rainfall. Our results showcase that the multi-proxy approach applied here provides an efficient way to track centennial-scale limnological, geochemical and microbial change, as influenced by hydroclimatic and anthropogenic forcing.

Oxygenation of Ediacaran Ocean recorded by iron isotopes

NASA Astrophysics Data System (ADS)

Fan, Haifeng; Zhu, Xiangkun; Wen, Hanjie; Yan, Bin; Li, Jin; Feng, Lianjun

2014-09-01

The increase in atmospheric oxygen during the late Neoproterozoic Era (ca. 800-542 Ma) may have stimulated the oxygenation of the deep oceans and the evolution of macroscopic multicellular organisms. However, the mechanism and magnitude of Neoproterozoic oxygenation remain uncertain. We present Fe isotopes, Fe species and other geochemical data for two sections of the Doushantuo Formation (ca. 635-551 Ma) deposited after the Nantuo glacial episode in the Yangtze Gorge area, South China. It is highlighted that highly positive δ56Fe values reflect a lower oxidation rate of Fe(II)aq under ferruginous conditions, and in turn near zero δ56Fe values indicate oxidizing conditions. Our study suggests that during the deposition of the bottom of Member II of the Doushantuo Formation the shallow seawater was oxic, but the deep water was characterized by ferruginous conditions, which is consistent with a redox chemical stratification model. Subsequent anoxic conditions under shallow seawater, represented by positive δ56Fe and negative δ13Ccarb excursions, should be ascribed to the upwelling of Fe(II)aq and dissolved organic carbon (DOC)-rich anoxic deep seawater. The oxidation of Fe (II)aq and DOC-rich anoxic deep seawater upon mixing with oxic shallow water provides an innovative explanation for the well-known negative δ13Ccarb excursions (ENC2) and positive δ56Fe excursions in the middle of Doushantuo Formation. Meanwhile, the upwelling Fe (II)aq- and DOC-rich anoxic deep seawater could increase photosynthetic activity. The balance between oxygen consumption and production was most important criteria for the oxygenation of Early Ediacaran Ocean and diversity of eukaryotic organisms.

Identifying changes in dissolved organic matter content and characteristics by fluorescence spectroscopy coupled with self-organizing map and classification and regression tree analysis during wastewater treatment.

PubMed

Yu, Huibin; Song, Yonghui; Liu, Ruixia; Pan, Hongwei; Xiang, Liancheng; Qian, Feng

2014-10-01

The stabilization of latent tracers of dissolved organic matter (DOM) of wastewater was analyzed by three-dimensional excitation-emission matrix (EEM) fluorescence spectroscopy coupled with self-organizing map and classification and regression tree analysis (CART) in wastewater treatment performance. DOM of water samples collected from primary sedimentation, anaerobic, anoxic, oxic and secondary sedimentation tanks in a large-scale wastewater treatment plant contained four fluorescence components: tryptophan-like (C1), tyrosine-like (C2), microbial humic-like (C3) and fulvic-like (C4) materials extracted by self-organizing map. These components showed good positive linear correlations with dissolved organic carbon of DOM. C1 and C2 were representative components in the wastewater, and they were removed to a higher extent than those of C3 and C4 in the treatment process. C2 was a latent parameter determined by CART to differentiate water samples of oxic and secondary sedimentation tanks from the successive treatment units, indirectly proving that most of tyrosine-like material was degraded by anaerobic microorganisms. C1 was an accurate parameter to comprehensively separate the samples of the five treatment units from each other, indirectly indicating that tryptophan-like material was decomposed by anaerobic and aerobic bacteria. EEM fluorescence spectroscopy in combination with self-organizing map and CART analysis can be a nondestructive effective method for characterizing structural component of DOM fractions and monitoring organic matter removal in wastewater treatment process. Copyright © 2014 Elsevier Ltd. All rights reserved.

Microbial processes of the carbon and sulfur cycles in an ice-covered, iron-rich meromictic lake Svetloe (Arkhangelsk region, Russia).

PubMed

Savvichev, Alexander S; Kokryatskaya, Natalia M; Zabelina, Svetlana A; Rusanov, Igor I; Zakharova, Elena E; Veslopolova, Elena F; Lunina, Olga N; Patutina, Ekaterina O; Bumazhkin, Boris K; Gruzdev, Denis S; Sigalevich, Pavel A; Pimenov, Nikolay V; Kuznetsov, Boris B; Gorlenko, Vladimir M

2017-02-01

Biogeochemical, isotope geochemical and microbiological investigation of Lake Svetloe (White Sea basin), a meromictic freshwater was carried out in April 2014, when ice thickness was ∼0.5 m, and the ice-covered water column contained oxygen to 23 m depth. Below, the anoxic water column contained ferrous iron (up to 240 μμM), manganese (60 μM), sulfide (up to 2 μM) and dissolved methane (960 μM). The highest abundance of microbial cells revealed by epifluorescence microscopy was found in the chemocline (redox zone) at 23-24.5 m. Oxygenic photosynthesis exhibited two peaks: the major one (0.43 μmol C L -1  day -1 ) below the ice and the minor one in the chemocline zone, where cyanobacteria related to Synechococcus rubescens were detected. The maximum of anoxygenic photosynthesis (0.69 μmol C L -1  day -1 ) at the oxic/anoxic interface, for which green sulfur bacteria Chlorobium phaeoclathratiforme were probably responsible, exceeded the value for oxygenic photosynthesis. Bacterial sulfate reduction peaked (1.5 μmol S L -1  day -1 ) below the chemocline zone. The rates of methane oxidation were as high as 1.8 μmol CH 4  L -1  day -1 at the oxi/anoxic interface and much lower in the oxic zone. Small phycoerythrin-containing Synechococcus-related cyanobacteria were probably involved in accumulation of metal oxides in the redox zone. © 2016 Society for Applied Microbiology and John Wiley & Sons Ltd.

Three-dimensional flow and trace metal mobility in shallow Chalk groundwater, Dorset, United Kingdom

NASA Astrophysics Data System (ADS)

Schürch, Marc; Edmunds, W. Michael; Buckley, David

2004-06-01

The three-dimensional groundwater flow and the hydrogeochemical regime have been determined in the Bere Stream valley, North Dorset Downs, southern England. The dual porosity characteristics of the Portsdown Chalk have been established using geophysical and hydrochemical borehole logging. Chemical properties have been established using major and trace element analyses of depth samples and groundwaters. The study site is located at the unconfined-confined boundary of the Chalk aquifer, where it is overflowing in the observation boreholes. The Chalk dips locally at about 5 m/km to the south-east under Palaeogene confining beds and three distinctive flow horizons may be recognised. The Chalk groundwater is of Ca-HCO 3 type and three separate geochemical groundwater zones were also determined with depth, having different oxygen levels and trace element characteristics. (1) A shallow O 2-rich zone with around 80% dissolved O 2 and low trace element concentrations. (2) A mixing and transition zone with significant concentrations of trace elements and high trace metal concentrations at its base: manganese 29 μg/l, nickel 55 μg/l, cadmium 146 μg/l, and zinc 214 μg/l. (3) A deeper zone with depleted oxygen (5-20% dissolved O 2) and with longer water residence times shown by higher Mg/Ca and K/Na ratios as well as higher Sr and F. The groundwater geochemistry in the Chalk aquifer is dominated by incongruent reactions with the fine-grained carbonate sediments, which release trace element impurities to the water. Some of the metals are co-precipitated with Mn- and Fe-oxide phases on fissure surfaces, whilst producing a purer calcite. During subsequent recrystallisation to purer iron- and manganese-oxides on fissure surfaces under specific geochemical and hydrodynamic conditions, trace metals are released into the fissure water. The results demonstrate the need to monitor quality stratification and the changes in the groundwater baseline chemistry in areas close to the redox boundary which, in the dual porosity Chalk is likely to be a diffuse zone with exchange between oxygen poor matrix waters and more oxic water flowing through the fissures.

ORCHIDEE-PEAT (revision 4596), a model for northern peatland CO2, water, and energy fluxes on daily to annual scales

NASA Astrophysics Data System (ADS)

Qiu, Chunjing; Zhu, Dan; Ciais, Philippe; Guenet, Bertrand; Krinner, Gerhard; Peng, Shushi; Aurela, Mika; Bernhofer, Christian; Brümmer, Christian; Bret-Harte, Syndonia; Chu, Housen; Chen, Jiquan; Desai, Ankur R.; Dušek, Jiří; Euskirchen, Eugénie S.; Fortuniak, Krzysztof; Flanagan, Lawrence B.; Friborg, Thomas; Grygoruk, Mateusz; Gogo, Sébastien; Grünwald, Thomas; Hansen, Birger U.; Holl, David; Humphreys, Elyn; Hurkuck, Miriam; Kiely, Gerard; Klatt, Janina; Kutzbach, Lars; Largeron, Chloé; Laggoun-Défarge, Fatima; Lund, Magnus; Lafleur, Peter M.; Li, Xuefei; Mammarella, Ivan; Merbold, Lutz; Nilsson, Mats B.; Olejnik, Janusz; Ottosson-Löfvenius, Mikaell; Oechel, Walter; Parmentier, Frans-Jan W.; Peichl, Matthias; Pirk, Norbert; Peltola, Olli; Pawlak, Włodzimierz; Rasse, Daniel; Rinne, Janne; Shaver, Gaius; Schmid, Hans Peter; Sottocornola, Matteo; Steinbrecher, Rainer; Sachs, Torsten; Urbaniak, Marek; Zona, Donatella; Ziemblinska, Klaudia

2018-02-01

Peatlands store substantial amounts of carbon and are vulnerable to climate change. We present a modified version of the Organising Carbon and Hydrology In Dynamic Ecosystems (ORCHIDEE) land surface model for simulating the hydrology, surface energy, and CO2 fluxes of peatlands on daily to annual timescales. The model includes a separate soil tile in each 0.5° grid cell, defined from a global peatland map and identified with peat-specific soil hydraulic properties. Runoff from non-peat vegetation within a grid cell containing a fraction of peat is routed to this peat soil tile, which maintains shallow water tables. The water table position separates oxic from anoxic decomposition. The model was evaluated against eddy-covariance (EC) observations from 30 northern peatland sites, with the maximum rate of carboxylation (Vcmax) being optimized at each site. Regarding short-term day-to-day variations, the model performance was good for gross primary production (GPP) (r2 = 0.76; Nash-Sutcliffe modeling efficiency, MEF = 0.76) and ecosystem respiration (ER, r2 = 0.78, MEF = 0.75), with lesser accuracy for latent heat fluxes (LE, r2 = 0.42, MEF = 0.14) and and net ecosystem CO2 exchange (NEE, r2 = 0.38, MEF = 0.26). Seasonal variations in GPP, ER, NEE, and energy fluxes on monthly scales showed moderate to high r2 values (0.57-0.86). For spatial across-site gradients of annual mean GPP, ER, NEE, and LE, r2 values of 0.93, 0.89, 0.27, and 0.71 were achieved, respectively. Water table (WT) variation was not well predicted (r2 < 0.1), likely due to the uncertain water input to the peat from surrounding areas. However, the poor performance of WT simulation did not greatly affect predictions of ER and NEE. We found a significant relationship between optimized Vcmax and latitude (temperature), which better reflects the spatial gradients of annual NEE than using an average Vcmax value.

Magnetic signatures of Heinrich-like detrital layers in the Quaternary of the North Atlantic

NASA Astrophysics Data System (ADS)

Channell, J. E. T.; Hodell, D. A.

2013-05-01

Magnetic parameters are useful for distinguishing North Atlantic Heinrich-like detrital layers from background sediments. Here we compare magnetic properties with XRF scanning data back to 700 ka and 1.3 Ma at IODP Sites U1302-U1303 and U1308, respectively. Multi-domain magnetite, with grain sizes >20 µm, is characteristic of both Ca- and Si-rich detrital layers, as defined by XRF core scanning, confirming the contribution of ice rafting. Reflectance spectra and magnetic parameters distinguish Ca- and Si-rich IRD layers due the presence of high coercivity hematite in Si-rich layers. Heinrich layer 6 (H6) at Site U1302-U1303 is unlike other detrital layers, being marked by a 45-cm thick homogeneous cream-colored clay layer underlain by a thin (5-cm) graded coarse-sand. Comparison of Site U1302/03 and Site U1308 detrital layers implies a dominant Laurentide source for both Ca- and Si-rich detrital layers. At Site U1308, low benthic δ13C values during stadials are in-step with magnetic grain-size coarsening associated with Si-rich detrital layers back to 1.3 Ma, indicating a link between deep-sea ventilation and ice rafting. The surface-sediment tan-colored oxic layer (~2 m thick at Site U1308) yields magnetic hysteresis ratios that are offset from the single-domain to multi-domain (SD-MD) magnetite mixing-line in hysteresis-ratio diagrams. This offset is attributed to maghemite grain-coatings, that form on magnetite in surface sediment, and undergo dissolution as they pass through the oxic/anoxic boundary.

Developing the Molybdenum Isotopic Proxy in Marine Barite

NASA Astrophysics Data System (ADS)

Erhardt, A. M.; Paytan, A.; Aggarwal, J.

2006-12-01

Molybdenum isotope ratios in seawater fluctuate in response to changing redox conditions and can provide clues into the degree of global ocean anoxia. The isotopic ratio of molybdenum has been shown to be sensitive to the relative proportion of oxic, suboxic, and euxinic environments. Deposition in oxic environments is isotopically light (~ -1.6‰ for δ^{97/95}Mo) relative to an average crustal source (0‰). Conversely, euxinic environments have been shown to be consistently heavier (~1.3‰) than the oxic sink through time, with suboxic sediments falling between these two signals. Shifts in the relative proportion of each sink, relative to a constant source, would alter the isotopic ratio of seawater over long time scales. Previously, this seawater value, and hence the degree of global anoxia, could only be inferred through mass balance calculations. We seek to quantify the isotopic signature of seawater though time using a phase that directly records this ratio. Marine barite precipitates inorganically in the water column directly from seawater, potentially providing a direct record of seawater characteristics. Molybdenum is a trace constituent of barite, with the molybdate ion substituting for sulfate at concentrations of about 1 ppm. To accurately determine the molybdenum isotopic ratio at these low concentrations (<15 ng per sample), modifications to existing measurement techniques are required. We will present the variations made to existing separation and mass-spectrometry techniques and the calibration of these new methods. The modifications were undertaken to reduce molybdenum blank to below 1 ng per analysis, to quantitatively remove interfering zirconium and to measure precise and reproducible isotope values. Preliminary data will be presented to illustrate potential applications for this new paleoredox proxy. This technique will allow for the measurement of molybdenum isotopic ratios at low concentrations, expanding the breath of compounds and signals that potentially record changes in planetary materials.

Surviving anoxia in marine sediments: The metabolic response of ubiquitous benthic foraminifera (Ammonia tepida).

PubMed

LeKieffre, Charlotte; Spangenberg, Jorge E; Mabilleau, Guillaume; Escrig, Stéphane; Meibom, Anders; Geslin, Emmanuelle

2017-01-01

High input of organic carbon and/or slowly renewing bottom waters frequently create periods with low dissolved oxygen concentrations on continental shelves and in coastal areas; such events can have strong impacts on benthic ecosystems. Among the meiofauna living in these environments, benthic foraminifera are often the most tolerant to low oxygen levels. Indeed, some species are able to survive complete anoxia for weeks to months. One known mechanism for this, observed in several species, is denitrification. For other species, a state of highly reduced metabolism, essentially a state of dormancy, has been proposed but never demonstrated. Here, we combined a 4 weeks feeding experiment, using 13C-enriched diatom biofilm, with correlated TEM and NanoSIMS imaging, plus bulk analysis of concentration and stable carbon isotopic composition of total organic matter and individual fatty acids, to study metabolic differences in the intertidal species Ammonia tepida exposed to oxic and anoxic conditions. Strongly contrasting cellular-level dynamics of ingestion and transfer of the ingested biofilm components were observed between the two conditions. Under oxic conditions, within a few days, intact diatoms were ingested, degraded, and their components assimilated, in part for biosynthesis of different cellular components: 13C-labeled lipid droplets formed after a few days and were subsequently lost (partially) through respiration. In contrast, in anoxia, fewer diatoms were initially ingested and these were not assimilated or metabolized further, but remained visible within the foraminiferal cytoplasm even after 4 weeks. Under oxic conditions, compound specific 13C analyses showed substantial de novo synthesis by the foraminifera of specific polyunsaturated fatty acids (PUFAs), such as 20:4(n-6). Very limited PUFA synthesis was observed under anoxia. Together, our results show that anoxia induced a greatly reduced rate of heterotrophic metabolism in Ammonia tepida on a time scale of less than 24 hours, these observations are consistent with a state of dormancy.

Surviving anoxia in marine sediments: The metabolic response of ubiquitous benthic foraminifera (Ammonia tepida)

PubMed Central

Spangenberg, Jorge E.; Mabilleau, Guillaume; Escrig, Stéphane; Meibom, Anders; Geslin, Emmanuelle

2017-01-01

High input of organic carbon and/or slowly renewing bottom waters frequently create periods with low dissolved oxygen concentrations on continental shelves and in coastal areas; such events can have strong impacts on benthic ecosystems. Among the meiofauna living in these environments, benthic foraminifera are often the most tolerant to low oxygen levels. Indeed, some species are able to survive complete anoxia for weeks to months. One known mechanism for this, observed in several species, is denitrification. For other species, a state of highly reduced metabolism, essentially a state of dormancy, has been proposed but never demonstrated. Here, we combined a 4 weeks feeding experiment, using 13C-enriched diatom biofilm, with correlated TEM and NanoSIMS imaging, plus bulk analysis of concentration and stable carbon isotopic composition of total organic matter and individual fatty acids, to study metabolic differences in the intertidal species Ammonia tepida exposed to oxic and anoxic conditions. Strongly contrasting cellular-level dynamics of ingestion and transfer of the ingested biofilm components were observed between the two conditions. Under oxic conditions, within a few days, intact diatoms were ingested, degraded, and their components assimilated, in part for biosynthesis of different cellular components: 13C-labeled lipid droplets formed after a few days and were subsequently lost (partially) through respiration. In contrast, in anoxia, fewer diatoms were initially ingested and these were not assimilated or metabolized further, but remained visible within the foraminiferal cytoplasm even after 4 weeks. Under oxic conditions, compound specific 13C analyses showed substantial de novo synthesis by the foraminifera of specific polyunsaturated fatty acids (PUFAs), such as 20:4(n-6). Very limited PUFA synthesis was observed under anoxia. Together, our results show that anoxia induced a greatly reduced rate of heterotrophic metabolism in Ammonia tepida on a time scale of less than 24 hours, these observations are consistent with a state of dormancy. PMID:28562648

North-Seeking Magnetotactic Gammaproteobacteria in the Southern Hemisphere

PubMed Central

Leão, Pedro; Teixeira, Lia C. R. S.; Cypriano, Jefferson; Farina, Marcos; Abreu, Fernanda; Bazylinski, Dennis A.

2016-01-01

ABSTRACT Magnetotactic bacteria (MTB) comprise a phylogenetically diverse group of prokaryotes capable of orienting and navigating along magnetic field lines. Under oxic conditions, MTB in natural environments in the Northern Hemisphere generally display north-seeking (NS) polarity, swimming parallel to the Earth's magnetic field lines, while those in the Southern Hemisphere generally swim antiparallel to magnetic field lines (south-seeking [SS] polarity). Here, we report a population of an uncultured, monotrichously flagellated, and vibrioid MTB collected from a brackish lagoon in Brazil in the Southern Hemisphere that consistently exhibits NS polarity. Cells of this organism were mainly located below the oxic-anoxic interface (OAI), suggesting it is capable of some type of anaerobic metabolism. Magnetosome crystalline habit and composition were consistent with elongated prismatic magnetite (Fe3O4) particles. Phylogenetic analysis based on 16S rRNA gene sequencing indicated that this organism belongs to a distinct clade of the Gammaproteobacteria class. The presence of NS MTB in the Southern Hemisphere and the previously reported finding of SS MTB in the Northern Hemisphere reinforce the idea that magnetotaxis is more complex than we currently understand and may be modulated by factors other than O2 concentration and redox gradients in sediments and water columns. IMPORTANCE Magnetotaxis is a navigational mechanism used by magnetotactic bacteria to move along geomagnetic field lines and find an optimal position in chemically stratified sediments. For that, magnetotactic bacteria swim parallel to the geomagnetic field lines under oxic conditions in the Northern Hemisphere, whereas those in the Southern Hemisphere swim antiparallel to magnetic field lines. A population of uncultured vibrioid magnetotactic bacteria was discovered in a brackish lagoon in the Southern Hemisphere that consistently swim northward, i.e., the opposite of the overwhelming majority of other Southern Hemisphere magnetotactic bacteria. This finding supports the idea that magnetotaxis is more complex than previously thought. PMID:27401974

Mineralogical, geochemical, and magnetic signatures of surface sediments from the Canadian Beaufort Shelf and Amundsen Gulf (Canadian Arctic)

NASA Astrophysics Data System (ADS)

Gamboa, Adriana; Montero-Serrano, Jean-Carlos; St-Onge, Guillaume; Rochon, André; Desiage, Pierre-Arnaud

2017-02-01

Mineralogical, geochemical, magnetic, and siliciclastic grain-size signatures of 34 surface sediment samples from the Mackenzie-Beaufort Sea Slope and Amundsen Gulf were studied in order to better constrain the redox status, detrital particle provenance, and sediment dynamics in the western Canadian Arctic. Redox-sensitive elements (Mn, Fe, V, Cr, Zn) indicate that modern sedimentary deposition within the Mackenzie-Beaufort Sea Slope and Amundsen Gulf took place under oxic bottom-water conditions, with more turbulent mixing conditions and thus a well-oxygenated water column prevailing within the Amundsen Gulf. The analytical data obtained, combined with multivariate statistical (notably, principal component and fuzzy c-means clustering analyses) and spatial analyses, allowed the division of the study area into four provinces with distinct sedimentary compositions: (1) the Mackenzie Trough-Canadian Beaufort Shelf with high phyllosilicate-Fe oxide-magnetite and Al-K-Ti-Fe-Cr-V-Zn-P contents; (2) Southwestern Banks Island, characterized by high dolomite-K-feldspar and Ca-Mg-LOI contents; (3) the Central Amundsen Gulf, a transitional zone typified by intermediate phyllosilicate-magnetite-K-feldspar-dolomite and Al-K-Ti-Fe-Mn-V-Zn-Sr-Ca-Mg-LOI contents; and (4) mud volcanoes on the Canadian Beaufort Shelf distinguished by poorly sorted coarse-silt with high quartz-plagioclase-authigenic carbonate and Si-Zr contents, as well as high magnetic susceptibility. Our results also confirm that the present-day sedimentary dynamics on the Canadian Beaufort Shelf is mainly controlled by sediment supply from the Mackenzie River. Overall, these insights provide a basis for future studies using mineralogical, geochemical, and magnetic signatures of Canadian Arctic sediments in order to reconstruct past variations in sediment inputs and transport pathways related to late Quaternary climate and oceanographic changes.

Rapid and sensitive Nitrosomonas europaea biosensor assay for quantification of bioavailable ammonium sensu strictu in soil.

PubMed

Nguyen, Minh Dong; Risgaard-Petersen, Nils; Sørensen, Jan; Brandt, Kristian K

2011-02-01

Knowledge on bioavailable ammonium sensu strictu (i.e., immediately available for cellular uptake) in soil is required to understand nutrient uptake processes in microorganisms and thus of vital importance for plant production. We here present a novel ammonium biosensor approach based on the lithoautotrophic ammonia-oxidizing bacterium Nitrosomonas europaea transformed with a luxAB sensor plasmid. Bioluminescence-based ammonium detection was achieved within 10 min with a quantification limit in liquid samples of ∼20 μM and a linear response range up to 400 μM. Biosensor and conventional chemical quantification of ammonium in soil solutions agreed well across a range of sample and assay conditions. The biosensor was subsequently applied for a solid phase-contact assay allowing for direct interaction of biosensor cells with soil particle-associated (i.e., exchangeable plus fixed) ammonium. The assay successfully quantified bioavailable ammonium even in unfertilized soil and demonstrated markedly higher ratios of bioavailable ammonium to water- or 2 M KCl-exchangeable ammonium in anoxic soil than in corresponding oxic soil. Particle-associated ammonium contributed by at least 74% and 93% of the total bioavailable pool in oxic and anoxic soil, respectively. The N. europaea biosensor should have broad relevance for environmental monitoring of bioavailable ammonium and processes depending on ammonium bioavailability.

Rare earth element geochemistry characteristics of seawater and porewater from deep sea in western Pacific.

PubMed

Deng, Yinan; Ren, Jiangbo; Guo, Qingjun; Cao, Jun; Wang, Haifeng; Liu, Chenhui

2017-11-28

Deep-sea sediments contain high concentrations of rare earth element (REE) which have been regarded as a huge potential resource. Understanding the marine REE cycle is important to reveal the mechanism of REE enrichment. In order to determine the geochemistry characteristics and migration processes of REE, seawater, porewater and sediment samples were systematically collected from the western Pacific for REE analysis. The results show a relatively flat REE pattern and the HREE (Heavy REE) enrichment in surface and deep seawater respectively. The HREE enrichment distribution patterns, low concentrations of Mn and Fe and negative Ce anomaly occur in the porewater, and high Mn/Al ratios and low U concentrations were observed in sediment, indicating oxic condition. LREE (Light REE) and MREE (Middle REE) enrichment in upper layer and depletion of MREE in deeper layer were shown in porewater profile. This study suggests that porewater flux in the western Pacific basin is a minor source of REEs to seawater, and abundant REEs are enriched in sediments, which is mainly caused by the extensive oxic condition, low sedimentation rate and strong adsorption capacity of sediments. Hence, the removal of REEs of porewater may result in widespread REE-rich sediments in the western Pacific basin.

Porewater dynamics of silver, lead and copper in coastal sediments and implications for benthic metal fluxes

USGS Publications Warehouse

Kalnejais, Linda H.; Martin, W. R.; Bothner, Michael H.

2015-01-01

To determine the conditions that lead to a diffusive release of dissolved metals from coastal sediments, porewater profiles of Ag, Cu, and Pb have been collected over seven years at two contrasting coastal sites in Massachusetts, USA. The Hingham Bay (HB) site is a contaminated location in Boston Harbor, while the Massachusetts Bay (MB) site is 11 km offshore and less impacted. At both sites, the biogeochemical cycles include scavenging by Fe-oxyhydroxides and release of dissolved metals when Fe-oxyhydroxides are reduced. Important differences in the metal cycles at the two sites, however, result from different redox conditions. Porewater sulfide and seasonal variation in redox zone depth is observed at HB, but not at MB. In summer, as the conditions become more reducing at HB, trace metals are precipitated as sulfides and are no longer associated with Fe-oxyhydroxides. Sulfide precipitation close to the sediment–water interface limits the trace metal flux in summer and autumn at HB, while in winter, oxidation of the sulfide phases drives high benthic fluxes of Cu and Ag, as oxic conditions return. The annual diffusive flux of Cu at HB is found to be significant and contributes to the higher than expected water column Cu concentrations observed in Boston Harbor. At MB, due to the lower sulfide concentrations, the association of trace metals with Fe-oxyhydroxides occurs throughout the year, leading to more stable fluxes. A surface enrichment of solid phase trace metals was found at MB and is attributed to the persistent scavenging by Fe-oxyhydroxides. This process is important, particularly at sites that are less reducing, because it maintains elevated metal concentrations at the surface despite the effects of bioturbation and sediment accumulation, and because it may increase the persistence of metal contamination in surface sediments.

Assessing the solubility controls on vanadium in groundwater, northeastern San Joaquin Valley, CA

USGS Publications Warehouse

Wright, Michael T.; Stollenwerk, Kenneth G.; Belitz, Kenneth

2014-01-01

The solubility controls on vanadium (V) in groundwater were studied due to concerns over possible harmful health effects of ingesting V in drinking water. Vanadium concentrations in the northeastern San Joaquin Valley ranged from 25 μg/L) and lowest in samples collected from anoxic groundwater (70% 2VO4−. Adsorption/desorption reactions with mineral surfaces and associated oxide coatings were indicated as the primary solubility control of V5+ oxyanions in groundwater. Environmental data showed that V concentrations in oxic groundwater generally increased with increasing groundwater pH. However, data from adsorption isotherm experiments indicated that small variations in pH (7.4–8.2) were not likely as an important a factor as the inherent adsorption capacity of oxide assemblages coating the surface of mineral grains. In suboxic groundwater, accurate SM modeling was difficult since Eh measurements of source water were not measured in this study. Vanadium concentrations in suboxic groundwater decreased with increasing pH indicating that V may exist as an oxycationic species [e.g. V(OH)3+]. Vanadium may complex with dissolved inorganic and organic ligands under suboxic conditions, which could alter the adsorption behavior of V in groundwater. Speciation modeling did not predict the existence of V-inorganic ligand complexes and organic ligands were not collected as part of this study. More work is needed to determine processes governing V solubility under suboxic groundwater conditions. Under anoxic groundwater conditions, SM predicts that aqueous V exists as the uncharged V(OH)3 molecule. However, exceedingly low V concentrations show that V is sparingly soluble in anoxic conditions. Results indicated that V may be precipitating as V3+- or mixed V3+/Fe3+-oxides in anoxic groundwater, which is consistent with results of a previous study. The fact that V appears insoluble in anoxic (Fe reducing) redox conditions indicates that the behavior of V is different than arsenic (As) in aquifer systems where the reductive dissolution of Fe-oxides with As adsorbed to the surface is a well-documented mechanism for increasing As concentrations in groundwater. This hypothesis is supported by the relation of V to As concentrations in oxic versus anoxic redox conditions. Sequential extraction procedures (SEP) applied to aquifer material showed that the greatest amount of V was recovered by the nitric acid (HNO3) extract (37–71%), followed by the oxalate-ascorbic acid extract (19–60%) and the oxalate extract (3–14%). These results indicate that V was not associated with the solid phase as an easily exchangeable fraction. Although the total amount of V recovered was greatest for the HNO3 extract that targets V adsorbed to sorption sites of crystalline Al, Fe and Mn oxides, the greatest V saturation of sorption sites appeared to occur on the amorphous and poorly crystalline oxide solid phases targeted by the oxalate and oxalate-ascorbic acid extracts respectively. Adsorption isotherm experiments showed no correlation between V sorption and any of the fractions identified by the SEP. This lack of correlation indicates the application of an SEP alone is not adequate to estimate the sorption characteristics of V in an aquifer system.

Nitrogen removal in Northern peatlands treating mine wastewaters

NASA Astrophysics Data System (ADS)

Palmer, Katharina; Karlsson, Teemu; Turunen, Kaisa; Liisa Räisänen, Marja; Backnäs, Soile

2015-04-01

Natural peatlands can be used as passive purification systems for mine wastewaters. These treatment peatlands are well-suited for passive water treatment as they delay the flow of water, and provide a large filtration network with many adsorptive surfaces on plant roots or soil particles. They have been shown to remove efficiently harmful metals and metalloids from mine waters due to variety of chemical, physical and biological processes such as adsorption, precipitation, sedimentation, oxidation and reduction reactions, as well as plant uptake. Many factors affect the removal efficiency such as inflow water quality, wetland hydrology, system pH, redox potential and temperature, the nature of the predominating purification processes, and the presence of other components such as salts. However, less attention has been paid to nitrogen (N) removal in peatlands. Thus, this study aimed to assess the efficiency of N removal and seasonal variation in the removal rate in two treatment peatlands treating mine dewatering waters and process effluent waters. Water sampling from treatment peatland inflow and outflow waters as well as pore waters in peatland were conducted multiple times during 2012-2014. Water samples were analysed for total N, nitrate-N and ammonium-N. Additionally, an YSI EXO2 device was used for continuous nitrate monitoring of waters discharged from treatment peatlands to the recipient river during summer 2014. The results showed that the oxic conditions in upper peat layer and microbial activity in treatment peatlands allowed the efficient oxidation of ammonium-N to nitrite-N and further to nitrate-N during summer time. However, the slow denitrification rate restricts the N removal as not all of the nitrate produced during nitrification is denitrified. In summer time, the removal rate of total N varied between 30-99 % being highest in late summer. N removal was clearly higher for treatment peatland treating process effluent waters than for peatland treating dewatering waters probably due to more oxidizing conditions. During winter time there is not enough microbial activity to maintain oxidation of ammonium-N to nitrate-N. However, almost 20 % of N may be removed during winter season due to nitrate denitrification.

Early Cambrian oxygen minimum zone-like conditions at Chengjiang

NASA Astrophysics Data System (ADS)

Hammarlund, Emma U.; Gaines, Robert R.; Prokopenko, Maria G.; Qi, Changshi; Hou, Xian-Guang; Canfield, Donald E.

2017-10-01

The early Cambrian succession at Chengjiang contains the most diverse Cambrian fossil assemblage yet described, and contributes significantly to our understanding of the diversification of metazoans in the Cambrian ;explosion;. The Cambrian Period occupies a transitional episode of global ocean chemistry, following the oxygenation of the surface ocean and of shallow marine environments during the Ediacaran Period, but prior to the establishment of a predominantly oxygenated deep ocean in the mid-Paleozoic. Despite recent attention, a detailed understanding of the chemical conditions that prevailed in early Cambrian marine settings and the relationship of those conditions to early metazoan ecosystems is still emerging. Here, we report multi-proxy geochemical data from two drill cores through the early Cambrian (Series 2) Yu'anshan Formation of Yunnan, China. Results reveal dynamic water-column chemistry within the succession, which progressively shifted from euxinic to oxic conditions during deposition of the Yu'anshan Formation. The Chengjiang biota occurs in strata that appear to have been deposited under an oxygen-depleted water column that may have supported denitrification, as in modern oxygen-minimum zones. The oxygenated benthic environments in which the Chengjiang biota thrived were proximal to, but sharply separated from, the open ocean by a persistent anoxic water mass that occupied a portion of the outer shelf. Oxygen depletion in the lower water column developed dynamically in response to nutrient availability and possibly at lower thresholds of productivity due to lower atmospheric oxygen concentrations in Cambrian. These findings suggest that the frequent development of oxygen-limiting conditions in continental margin settings provided an environmental barrier that may have affected biogeographic, ecological and evolutionary development of early metazoan communities.

Effect of abalone farming on sediment geochemistry in the Shallow Sea near Wando, South Korea

NASA Astrophysics Data System (ADS)

Kang, Jeongwon; Lee, Yeon Gyu; Jeong, Da Un; Lee, Jung Sick; Choi, Yang Ho; Shin, Yun Kyung

2015-12-01

Wando County has grown up to 93% of the total abalone produced in South Korea since the late 1990s; however, this production has been decreasing in recent years. The objectives of this study were to understand the potential contamination risks of abalone farming and to examine the influence of intensive abalone farming on sediment quality by analyzing grain-size composition, organic matter (total organic carbon (TOC), total nitrogen (TN), total sulfur (TS)) and heavy metal content, pH, and 210Pb geochronology. The results of organic matter analysis from surface and core sediment (length: 64 cm) showed that the area around the abalone farm had oxic marine-to-brackish conditions, but that the area directly below an abalone cage (location 7) had reductive conditions, with a C/S ratio of ~2. The average TN levels in the surface and core sediments were 0.25% and 0.29%, respectively, and this was predominantly due to the use of seaweed for feed. The low sediment pH (surface, 7.23; core, 7.04), indicates that acidification of the bottom sediment has gradually increased since the initiation of abalone farming and is likely due to the continuous accumulation of uneaten feed and feces. Heavy metal pollution was not apparent based on the examination of EF and Igeo, although the excess metal flux of Ni, Pb, Cu, Co, As, and Cd increased toward surface of the sediment core. These sediment changes may be caused by the rapid accumulation (sedimentation rate: 1.45 cm/year) of sludge discharged from the abalone farm and may be controlled by tidal currents, physiography, water depth, and tidal ranges.

Vanadium accumulation in carbonaceous rocks: A review of geochemical controls during deposition and diagenesis

USGS Publications Warehouse

Breit, G.N.; Wanty, R.B.

1991-01-01

Published data relevant to the geochemistry of vanadium were used to evaluate processes and conditions that control vanadium accumulation in carbonaceous rocks. Reduction, adsorption, and complexation of dissolved vanadium favor addition of vanadium to sediments rich in organic carbon. Dissolved vanadate (V(V)) species predominate in oxic seawater and are reduced to vanadyl ion (V(IV)) by organic compounds or H2S. Vanadyl ion readily adsorbs to particle surfaces and is added to the sediment as the particles settle. The large vanadium concentrations of rocks deposited in marine as compared to lacustrine environments are the result of the relatively large amount of vanadium provided by circulating ocean water compared to terrestrial runoff. Vanadium-rich carbonaceous rocks typically have high contents of organically bound sulfur and are stratigraphically associated with phosphate-rich units. A correspondence between vanadium content and organically bound sulfur is consistent with high activities of H2S during sediment deposition. Excess H2S exited the sediment into bottom waters and favored reduction of dissolved V(V) to V(IV) or possibly V(III). The stratigraphic association of vanadiferous and phosphatic rocks reflects temporal and spatial shifts in bottom water chemistry from suboxic (phosphate concentrated) to more reducing (euxinic?) conditions that favor vanadium accumulation. During diagenesis some vanadium-organic complexes migrate with petroleum out of carbonaceous rocks, but significant amounts of vanadium are retained in refractory organic matter or clay minerals. As carbon in the rock evolves toward graphite during metamorphism, vanadium is incorporated into silicate minerals. ?? 1991.

Metatranscriptomic analysis of prokaryotic communities active in sulfur and arsenic cycling in Mono Lake, California, USA.

PubMed

Edwardson, Christian F; Hollibaugh, James T

2017-10-01

This study evaluates the transcriptionally active, dissimilatory sulfur- and arsenic-cycling components of the microbial community in alkaline, hypersaline Mono Lake, CA, USA. We sampled five depths spanning the redox gradient (10, 15, 18, 25 and 31 m) during maximum thermal stratification. We used custom databases to identify transcripts of genes encoding complex iron-sulfur molybdoenzyme (CISM) proteins, with a focus on arsenic (arrA, aioA and arxA) and sulfur cycling (dsrA, aprA and soxB), and assigned them to taxonomic bins. We also report on the distribution of transcripts related to the ars arsenic detoxification pathway. Transcripts from detoxification pathways were not abundant in oxic surface waters (10 m). Arsenic cycling in the suboxic and microaerophilic zones of the water column (15 and 18 m) was dominated by arsenite-oxidizing members of the Gammaproteobacteria most closely affiliated with Thioalkalivibrio and Halomonas, transcribing arxA. We observed a transition to arsenate-reducing bacteria belonging to the Deltaproteobacteria and Firmicutes transcribing arsenate reductase (arrA) in anoxic bottom waters of the lake (25 and 31 m). Sulfur cycling at 15 and 18 m was dominated by Gammaproteobacteria (Thioalkalivibrio and Thioalkalimicrobium) oxidizing reduced S species, with a transition to sulfate-reducing Deltaproteobacteria at 25 and 31 m. Genes related to arsenic and sulfur oxidation from Thioalkalivibrio were more highly transcribed at 15 m relative to other depths. Our data highlight the importance of Thioalkalivibrio to arsenic and sulfur biogeochemistry in Mono Lake and identify new taxa that appear capable of transforming arsenic.

Mechanisms of interaction between arsenian pyrite and aqueous arsenite under anoxic and oxic conditions

NASA Astrophysics Data System (ADS)

Qiu, Guohong; Gao, Tianyu; Hong, Jun; Luo, Yao; Liu, Lihu; Tan, Wenfeng; Liu, Fan

2018-05-01

Pyrite affects the conversion and migration processes of arsenic in soils and waters. Adsorption and redox reactions of arsenite (As(III)) occur on the surface of pyrite, and the interaction processes are influenced by the arsenic incorporated into pyrite. This work examined the effects of arsenic content, pH and oxygen on the interaction between arsenian pyrite and aqueous As(III) and investigated the underlying mechanisms. The results indicated that arsenic incorporation led to a high content of Fe(III) in pyrite, and that As(III) was mainly adsorbed on pyrite surface and part of As(III) was oxidized to As(V) by the newly formed intermediates including hydroxyl radicals and hydrogen peroxide. The oxidation rate increased with increasing arsenic content in the pyrite and the presence of air (oxygen), and first decreased and then increased with increasing pH from 3.0 to 11.0. Hydroxyl radicals and hydrogen peroxide significantly contributed to the oxidation of pyrite and aqueous As(III) in acidic and alkaline solutions, respectively. Although pyrite oxidation increased with increasing arsenic content as indicated by the elevated concentrations of elemental S and SO42-, the percentage of released arsenic in total arsenic of the arsenian pyrite decreased due to the adsorption of arsenic on the surface of newly formed ferric (hydr)oxides, especially the ferric arsenate precipitate formed in high pH solutions. The present study enables a better understanding of the important interaction process of dissolved arsenite and natural pyrites in the study of groundwater contamination, arsenic migration/sequestration, and acid mine drainage formation.

A deep oxic ecosystem in the subseafloor South Pacific Gyre

NASA Astrophysics Data System (ADS)

D'Hondt, S. L.; Inagaki, F.; Alvarez Zarikian, C. A.; Integrated Ocean Drilling Program Expedition 329 Shipboard Scientific Party

2011-12-01

Scientific ocean drilling has demonstrated the occurrence of rich microbial communities, abundant active cells and diverse anaerobic activities in anoxic subseafloor sediment. Buried organic matter from the surface photosynthetic world sustains anaerobic heterotrophs in anoxic sediment as deeply buried as 1.6 km below the seafloor. However, these studies have been mostly restricted to the organic-rich sediment of continental margins and biologically productive regions. IODP Expedition 329 discovered that subseafloor habitat and life are fundamentally different in the vast expanse of organic-poor sediment that underlies Earth's largest oceanic province, the South Pacific Gyre (SPG). Dissolved O2 and dissolved major nutrients (C, N, P) are present throughout the entire sediment sequence and the upper basaltic basement of the SPG. The drilled sediment is up to 75 m thick. Although heterotrophic O2 reduction (aerobic respiration) persists for millions of years in SPG sediment (which accumulates very slowly), it falls below minimum detection just a few meters to tens of meters beneath the SPG seafloor. Cell concentrations approach minimum detection at similar depths, but are intermittently detectable throughout the entire sediment sequence. In situ radiolysis of water may be a significant source of energy for the microbes that inhabit the deepest (oldest) sediment.

Degradation of trichloroethylene in aqueous solution by rGO supported nZVI catalyst under several oxic environments.

PubMed

Gu, Mengbin; Farooq, Usman; Lu, Shuguang; Zhang, Xiang; Qiu, Zhaofu; Sui, Qian

2018-05-05

The reduced graphene oxide (rGO) supported nano zero-valent iron (nZVI) (nZVI-rGO) was synthesized successfully and applied in the several oxic environments to remove trichloroethylene (TCE). The nZVI-rGO had a better catalytic performance than bare nZVI for the TCE removal. Both aggregation of nZVI and agglomeration of rGO were in part prevented by loading the nZVI nanoparticles on the rGO sheet. Among all the oxic environments, the better removal of TCE was followed as the order of PMS > SPS > H 2 O 2 . Chemical scavenger tests were carried out to identify the reactive oxygen species (ROSs) generated in the removal of TCE, showing that in PMS and SPS systems, SO 4 - and HO were main radicals responsible for TCE removal, while HO and O 2 - were main radicals in H 2 O 2 system. The possible mechanisms were proposed with nZVI-rGO under several oxic environments. The recyclability of nZVI-rGO, dechlorination and mineralization of TCE were investigated. These fundamental data confirmed the effectiveness of nZVI-rGO to remove TCE and could help selecting the suitable oxidants to use with nZVI-rGO in the actual field groundwater remediation. Copyright © 2018 Elsevier B.V. All rights reserved.

Aquatic fulvic acids in microbially based ecosystems: results from two desert lakes in Antarctica

USGS Publications Warehouse

McKnight, Diane M.; Aiken, G.R.; Smith, R.L.

1991-01-01

These lakes receive very limited input of organic material from the surrounding barren desert, but they sustain algal and bacterial populations under permanent ice cover. One lake has an extensive anoxic zone and high salinities; the other is oxic and has low salinities. Despite these differences, fulvic acids from both lakes had similar elemental compositions, carbon distributions, and amino acid contents, indicating that the chemistry of microbially derived fulvic acvids is not strongly influenced by chemical conditions in the water column. Compared to fulvic acids from other natural waters, these fulvic acids have low C:N atomic ratios (19-25) and low contents of aromatic carbons (5-7% of total carbon atoms); they are most similar to marine fulvic acids. -from Authors

Nitrate reduction mechanisms and rates in an unconfined eogenetic karst aquifer in two sites with different redox potential

USGS Publications Warehouse

Henson, Wesley; Huang, Laibin; Graham, Wendy D.; Ogram, Andrew

2017-01-01

This study integrates push-pull tracer tests (PPTT) with microbial characterization of extracted water via quantitative polymerase chain reaction (qPCR) and reverse transcriptase qPCR (RT-qPCR) of selected functional N transformation genes to quantify nitrate reduction mechanisms and rates in sites with different redox potential in a karst aquifer. PPTT treatments with nitrate (AN) and nitrate-fumarate (ANC) were executed in two wells representing anoxic and oxic geochemical end-members. Oxic aquifer zero-order nitrate loss rates (mmol L−1 h−1) were similar for AN and ANC treatment, ranging from 0.03 ± 0.01 to 0.05 ± 0.01. Anoxic aquifer zero-order nitrate loss rates ranged from 0.03 ± 0.02 (AN) to 0.13 ± 0.02 (ANC). Microbial characterization indicates mechanisms influencing these rates were dissimilatory nitrate reduction to ammonium (DNRA) at the anoxic site with AN treatment, assimilatory reduction of nitrate to ammonium (ANRA) with ANC treatment in the water column at both sites, and additional documented nitrate reduction that occurred in unsampled biofilms. With carbon treatment, total numbers of microbes (16S rRNA genes) significantly increased (fourteenfold to thirtyfold), supporting stimulated growth with resulting ANRA. Decreased DNRA gene concentrations (nrfA DNA) and increased DNRA activity ratio (nrfA-cDNA/DNA) supported the assertion that DNRA occurred in the anoxic zone with AN and ANC treatment. Furthermore, decreased DNRA gene copy numbers at the anoxic site with ANC treatment suggests that DNRA microbes in the anoxic site are chemolithoautotrophic. Increased RT-qPCR denitrification gene expression (nirK and nirS) was not observed in water samples, supporting that any observed NO3-N loss due to denitrification may be occurring in unsampled microbial biofilms.

How Redox Fluctuation Shapes Microbial Community Structure and Mineral-Organic Matter Relationships in a Humid Tropical Forest Soil

NASA Astrophysics Data System (ADS)

Campbell, A.; Bhattacharyya, A.; Lin, Y.; Tfaily, M. M.; Paša-Tolić, L.; Chu, R. K.; Silver, W. L.; Nico, P. S.; Pett-Ridge, J.

2016-12-01

Wet tropical soils can alternate frequently between fully oxygenated and anaerobic conditions, constraining both the metabolism of tropical soil microorganisms, and the mineral-organic matter relationships that regulate many aspects of soil C cycling. Tropical forests are predicted to experience a 2-5°C temperature increase and substantial differences in the amount and timing of rainfall in the coming half century. Yet we have a poor understanding of how soil microbial activity and C cycling in these systems will respond to changes in environmental variability caused by climate change. Using a 44 day redox manipulation and isotope tracing experiment with soils from the Luquillo Experimental Forest, Puerto Rico, we examined patterns of tropical soil microorganisms, metabolites and soil chemistry when soils were exposed to different redox regimes - static oxic, static anoxic, high frequency redox fluctuation (4 days oxic, 4 days anoxic), or low frequency redox fluctuation (8 days oxic, 4 days anoxic). Replicate microcosms were harvested throughout the incubation to understand how changes in redox oscillation frequency altered microbial community structure and activity, organic matter turnover and fate, and soil chemistry. While gross soil respiration was highest in static oxic soils, respiration derived from added litter was highest in static anoxic soils, suggesting that decomposition of preexisting SOM was limited by O2 availability in the anoxic treatment. Microbial communities responded to shifting O2 availability in the different treatments, resulting in significant differences in DOC concentration and molecular composition (measured by FTICR-MS). DOC and Fe2+ concentrations were positively correlated for all four redox treatments, and rapidly increased following oscillation from oxic to anoxic conditions. These results, along with parallel studies of biogeochemical responses (Fe speciation, pH, P availability), suggest a highly responsive microbial and geochemical system, where the frequency of low-redox events controls exchanges of C between mineral-sorbed and aqueous pools.

Geochemical controls of elevated arsenic concentrations in groundwater, Ester Dome, Fairbanks district, Alaska

USGS Publications Warehouse

Verplanck, P.L.; Mueller, S.H.; Goldfarb, R.J.; Nordstrom, D. Kirk; Youcha, E.K.

2008-01-01

Ester Dome, an upland area near Fairbanks, Alaska, was chosen for a detailed hydrogeochemical study because of the previously reported elevated arsenic in groundwater, and the presence of a large set of wells amenable to detailed sampling. Ester Dome lies within the Fairbanks mining district, where gold-bearing quartz veins, typically containing 2-3??vol.% sulfide minerals (arsenopyrite, stibnite, and pyrite), have been mined both underground and in open cuts. Gold-bearing veins on Ester Dome occur in shear zones and the sulfide minerals in these veins have been crushed to fine-grained material by syn- or post-mineralization movement. Groundwater at Ester Dome is circumneutral, Ca-HCO3 to Ca-SO4 type, and ranges from dilute (specific conductance of 48????S/cm) to more concentrated (specific conductance as high as 2070????S/cm). In general, solute concentrations increase down hydrologic gradient. Redox species indicate that the groundwaters range from oxic to sub-oxic (low dissolved oxygen, Fe(III) reduction, no SO4 reduction). Waters with the highest Fe concentrations, as high as 10.7??mg/L, are the most anoxic. Dissolved As concentrations range from < 1 to 1160????g/L, with a median value of 146????g/L. Arsenic concentrations are not correlated with specific conductance or Fe concentrations, suggesting that neither groundwater residence time, nor reductive dissolution of iron oxyhydroxides, control the arsenic chemistry. Furthermore, As concentrations do not covary with other constituents that form anions and oxyanions in solution (e.g., HCO3, Mo, F, or U) such that desorption of arsenic from clays or oxides also does not control arsenic mobility. Oxidation of arsenopyrite and dissolution of scorodite, in the near-surface environment appears to be the primary control of dissolved As in this upland area. More specifically, the elevated As concentrations are spatially associated with sulfidized shear zones and localities of gold-bearing quartz veins. Consistent with this interpretation, elevated dissolved Sb concentrations (as high as 59????g/L), also correlated with occurrences of hypogene sulfide minerals, were measured in samples with high dissolved As concentrations.

Surface complexation modeling for predicting solid phase arsenic concentrations in the sediments of the Mississippi River Valley alluvial aquifer, Arkansas, USA

USGS Publications Warehouse

Sharif, M.S.U.; Davis, R.K.; Steele, K.F.; Kim, B.; Hays, P.D.; Kresse, T.M.; Fazio, J.A.

2011-01-01

The potential health impact of As in drinking water supply systems in the Mississippi River Valley alluvial aquifer in the state of Arkansas, USA is significant. In this context it is important to understand the occurrence, distribution and mobilization of As in the Mississippi River Valley alluvial aquifer. Application of surface complexation models (SCMs) to predict the sorption behavior of As and hydrous Fe oxides (HFO) in the laboratory has increased in the last decade. However, the application of SCMs to predict the sorption of As in natural sediments has not often been reported, and such applications are greatly constrained by the lack of site-specific model parameters. Attempts have been made to use SCMs considering a component additivity (CA) approach which accounts for relative abundances of pure phases in natural sediments, followed by the addition of SCM parameters individually for each phase. Although few reliable and internally consistent sorption databases related to HFO exist, the use of SCMs using laboratory-derived sorption databases to predict the mobility of As in natural sediments has increased. This study is an attempt to evaluate the ability of the SCMs using the geochemical code PHREEQC to predict solid phase As in the sediments of the Mississippi River Valley alluvial aquifer in Arkansas. The SCM option of the double-layer model (DLM) was simulated using ferrihydrite and goethite as sorbents quantified from chemical extractions, calculated surface-site densities, published surface properties, and published laboratory-derived sorption constants for the sorbents. The model results are satisfactory for shallow wells (10.6. m below ground surface), where the redox condition is relatively oxic or mildly suboxic. However, for the deep alluvial aquifer (21-36.6. m below ground surface) where the redox condition is suboxic to anoxic, the model results are unsatisfactory. ?? 2011 Elsevier Ltd.

The Molecular Composition of Dissolved Organic Matter in Forest Soils as a Function of pH and Temperature

PubMed Central

Roth, Vanessa-Nina; Dittmar, Thorsten; Gaupp, Reinhard; Gleixner, Gerd

2015-01-01

We examined the molecular composition of forest soil water during three different seasons at three different sites, using electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FT-ICR-MS). We examined oxic soils and tested the hypothesis that pH and season correlate with the molecular composition of dissolved organic matter (DOM). We used molecular formulae and their relative intensity from ESI-FT-ICR-MS for statistical analysis. Applying unconstrained and constrained ordination methods, we observed that pH, dissolved organic carbon (DOC) concentration and season were the main factors correlating with DOM molecular composition. This result is consistent with a previous study where pH was a main driver of the molecular differences between DOM from oxic rivers and anoxic bog systems in the Yenisei River catchment. At a higher pH, the molecular formulae had a lower degree of unsaturation and oxygenation, lower molecular size and a higher abundance of nitrogen-containing compounds. These characteristics suggest a higher abundance of tannin connected to lower pH that possibly inhibited biological decomposition. Higher biological activity at a higher pH might also be related to the higher abundance of nitrogen-containing compounds. Comparing the seasons, we observed a decrease in unsaturation, molecular diversity and the number of nitrogen-containing compounds in the course of the year from March to November. Temperature possibly inhibited biological degradation during winter, which could cause the accumulation of a more diverse compound spectrum until the temperature increased again. Our findings suggest that the molecular composition of DOM in soil pore waters is dynamic and a function of ecosystem activity, pH and temperature. PMID:25793306

Isotopic Discrimination of Perchlorate Sources in Ground Water

NASA Astrophysics Data System (ADS)

Bohlke, J.; Hatzinger, P. B.; Sturchio, N. C.; Gu, B.; Jackson, W. A.; Abbene, I. J.

2007-12-01

Perchlorate has been detected in ground water and drinking water in many areas of the U.S. during the past decade. Sources of potential perchlorate enrichment in ground water include releases from past military activities, fireworks manufacture and display, fertilizer applications, discarded road flares, and local atmospheric deposition. Here we present analyses of stable isotopes (δ37Cl, δ18O, and Δ17O) of dissolved perchlorate, along with other supporting environmental tracer data, from selected occurrences in ground water in the U.S. The isotope data indicate that both synthetic and natural perchlorate are present in ground water, and that multiple sources are present locally in some areas. The sampled ground waters generally were oxic and the perchlorate isotopes generally were not affected substantially by biodegradation. In some areas, natural perchlorate, with Δ17O = +7 to +10 ‰, can be attributed to agricultural applications of atmospherically derived natural nitrate fertilizer imported from South America (Atacama Desert, Chile). In at least one agricultural area in New York, concentrations of perchlorate increase with depth and ground-water age, possibly because of decreasing application rates of Atacama nitrate fertilizer and(or) decreasing perchlorate concentrations in the imported fertilizer products in recent years.

Radiosensitization of mammalian cells by diamide

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vos, O.; Grant, G.A.; Budke, L.

1976-01-01

The effect of diamide on the radiosensitivity of T-cells was investigated under oxic and anoxic conditions. The compound was found to sensitize the cells under both conditions. Under oxic conditions, exposure for 10 min before and during irradiation to 0.1, 0.5, and 1.0 mm diamide produced dose-modifying factors of 0.81, 0.60, and 0.55, respectively. Under anoxic conditions exposure for 10 min before and during irradiation to 0.5 mm produced a dose-modifying factor of 0.34. When the cells in oxic conditions were exposed for just 20 min before irradiation, the sensitizing effect was smaller, but some sensitization effect was still apparentmore » after a 120 min interval between diamide treatment and irradiation. Diamide also sensitized the cells after irradiation but this effect was less than when it was present during irradiation. It is proposed that sensitization is due to lack of capacity for repair of radicals by hydrogen transfer and biochemical repair processes. (Author) (GRA)« less

Modeling of isotope fractionation at the catchment scale: How promising is compound specific isotope analysis (CSIA) as a tool for analyzing diffuse pollution by agrochemicals?

NASA Astrophysics Data System (ADS)

Lutz, S. R.; van Meerveld, H. J.; Waterloo, M. J.; Broers, H. P.; van Breukelen, B. M.

2012-04-01

Concentration measurements are indispensable for the assessment of subsurface and surface water pollution by agrochemicals such as pesticides. However, monitoring data is often ambiguous and easily misinterpreted as a decrease in concentration could be caused by transformation, dilution or changes in the application of the pesticide. In this context, compound specific isotope analysis (CSIA) has recently emerged as a complementary monitoring technique. It is based on the measurement of the isotopic composition (e.g. δ13C and δ2H) of the contaminant. Since transformation processes are likely accompanied by isotope fractionation, thus a change in this composition, CSIA offers the opportunity to gain additional knowledge about transport and degradation processes as well as to track pollutants back to their sources. Isotopic techniques have not yet been applied in a comprehensive way in the analysis of catchment-wide organic pollution. We therefore incorporated fractionation processes associated with the fate of pesticides into the numerical flow and solute transport model HydroGeoSphere in order to assess the feasibility of CSIA within the context of catchment monitoring. The model was set up for a hypothetical hillslope transect which drains into a river. Reactive solute transport was driven by two pesticides applications within one year and actual data for rainfall and potential evapotranspiration from a meteorological station in the Netherlands. Degradation of the pesticide was assumed to take place at a higher rate under the prevailing oxic conditions in the topsoil than in deeper, anoxic subsurface layers. In terms of CSIA, these two degradation pathways were associated with different strengths of isotope fractionation for both hydrogen and carbon atoms. By simulating changes in δ13C and δ2H, the share of the oxic and the anoxic reaction on the overall degradation could be assessed. Model results suggest that CSIA is suitable for assessing degradation of diffuse agrochemical pollutants in a relatively simple hydrological system. The simulated shifts in isotopic signals are within a range that could be detected with current isotope analytics. Concentrations in the stream vary significantly only for a short period during and after intense rainfall events. In contrast, CSIA values reveal longer response times such that isotopic shifts are likely to be detected in samples with a coarser temporal resolution. Rainfall events which result in fast lateral subsurface transport from the pollution source to the stream can be separated from those that lead to pollution migration through deeper subsurface zones with much longer travel times. Two-dimensional CSIA highlights an increasing importance of the oxic reaction in the topsoil during the wetter period of the year. In order to examine to which extent CSIA is applicable for more complex hydrological systems, it is projected to simulate isotope fractionation in a 3-dimensional catchment featuring additional processes such as migration from several pollution sources or in-stream degradation.

Oxic limestone drains for treatment of dilute, acidic mine drainage

USGS Publications Warehouse

Cravotta, Charles A.

1998-01-01

Limestone treatment systems can be effective for remediation of acidic mine drainage (AMD) that contains moderate concentrations of dissolved O2 , Fe3+ , or A13+ (1‐5 mg‐L‐1 ). Samples of water and limestone were collected periodically for 1 year at inflow, outflow, and intermediate points within underground, oxic limestone drains (OLDs) in Pennsylvania to evaluate the transport of dissolved metals and the effect of pH and Fe‐ and Al‐hydrolysis products on the rate of limestone dissolution. The influent was acidic and relatively dilute (pH <4; acidity < 90 mg‐L‐1 ) but contained 1‐4 mg‐L‐1 Of O2 , Fe3+ , A13+ , and Mn2+ . The total retention time in the OLDs ranged from 1.0 to 3.1 hours. Effluent remained oxic (02 >1 mg‐L‐1 ) but was near neutral (pH = 6.2‐7.0); Fe and Al decreased to less than 5% of influent concentrations. As pH increased near the inflow, hydrous Fe and Al oxides precipitated in the OLDs. The hydrous oxides, nominally Fe(OH)3 and AI(OH)3, were visible as loosely bound, orange‐yellow coatings on limestone near the inflow. As time elapsed, Fe(OH)3 and AI(OH)3 particles were transported downflow. During the first 6 months of the experiment, Mn 2+ was transported conservatively through the OLDs; however, during the second 6 months, concentrations of Mn in effluent decreased by about 50% relative to influent. The accumulation of hydrous oxides and elevated pH (>5) in the downflow part of the OLDs promoted sorption and coprecipitation of Mn as indicated by its enrichment relative to Fe in hydrous‐oxide particles and coatings on limestone. Despite thick (~1 mm) hydrous‐oxide coatings on limestone near the inflow, CaCO3 dissolution was more rapid near the inflow than at downflow points within the OLD where the limestone was not coated. The rate of limestone dissolution decreased with increased residence time, pH, and concentrations of Ca2+ and HCO3‐ and decreased PCO2. The following overall reaction shows alkalinity as an ultimate product of the iron hydrolysis reaction in an OLD:Fe2+ + 0.25 O2 +CaCO3 + 2.5 H2O --> Fe(OH)3 + 2 Ca2+ + 2 HCO3-where 2 moles of CaCO3 dissolve for each mole of Fe(OH)3 produced. Hence, in an OLD, rapidly dissolving limestone surfaces are not stable substrates for Fe(OH)3 attachment and armoring. Because overall efficiency is increased by combining neutralization and hydrolysis reactions, an OLD followed by a settling pond requires less land area than needed for a two‐stage treatment system consisting of an anoxic limestone drain an oxidation‐settling pond or wetland. To facilitate removal of hydrous‐oxide sludge, a perforated‐pipe subdrain can be installed within an OLD.

Vertical stratification of subsurface microbial community composition across geological formations at the Hanford Site.

PubMed

Lin, Xueju; Kennedy, David; Fredrickson, Jim; Bjornstad, Bruce; Konopka, Allan

2012-02-01

Microbial diversity in subsurface sediments at the Hanford Site 300 Area near Richland, Washington state (USA) was investigated by analysing 21 samples recovered from depths of 9-52 m. Approximately 8000 near full-length 16S rRNA gene sequences were analysed across geological strata that include a natural redox transition zone. These strata included the oxic coarse-grained Hanford formation, fine-grained oxic and anoxic Ringold Formation sediments, and the weathered basalt group. We detected 1233 and 120 unique bacterial and archaeal OTUs (operational taxonomic units at the 97% identity level) respectively. Microbial community structure and richness varied substantially across the different geological strata. Bacterial OTU richness (Chao1 estimator) was highest (> 700) in the upper Hanford formation, and declined to about 120 at the bottom of the Hanford formation. Just above the Ringold oxic-anoxic interface, richness was about 325 and declined to less than 50 in the deeper reduced zones. The deeper Ringold strata were characterized by a preponderance (c. 90%) of Proteobacteria. The bacterial community in the oxic sediments contained not only members of nine well-recognized phyla but also an unusually high proportion of three candidate divisions (GAL15, NC10 and SPAM). Additionally, 13 novel phylogenetic orders were identified within the Deltaproteobacteria, a clade rich in microbes that carry out redox transformations of metals that are important contaminants on the Hanford Site. © 2011 Society for Applied Microbiology and Blackwell Publishing Ltd.

Recent Advances in Understanding the Sources of Methylmercury to Coastal Waters

NASA Astrophysics Data System (ADS)

Mason, R. P.; Balcom, P.; Chen, C.; Gosnell, K. J.; Jonsson, S.; Mazrui, N.; Ortiz, V.; Seelen, E.; Schartup, A. T.; Sunderland, E. M.

2015-12-01

Understanding the sources of methylmercury (MeHg) to the food chain in coastal waters is important given the related health concerns from consumption of seafood containing elevated MeHg. While water column dissolved or particulate MeHg is the best predictor of bioaccumulation into pelagic organisms in coastal waters, there is debate concerning the dominant sources of MeHg to the water column, and how the relative importance of these sources vary with ecosystem characteristics. Potential sources include both external inputs from the watershed and offshore waters and internal sources (net methylation in sediments and the associated flux of MeHg to the water column and/or net MeHg production in the water column). We will report the results from our various studies in estuarine and coastal waters which have examined the distribution and partitioning of sediment and water column MeHg, and its formation and degradation, across a geographic range from Labrador, Canada to the Chesapeake Bay, USA. The ecosystems studied vary from shallow estuarine bays to deeper systems, and from salt wedge to tidally-dynamic systems. Additionally, both pristine and contaminated environments were examined. The studies examined the factors controlling the net production of MeHg in sediments, and in our more recent work, the potential formation of MeHg in the oxic water column of coastal waters. Sediment measurements (core and grab samples) included both solid phase and porewater MeHg and total mercury (HgT) and important ancillary parameters. Water column parameters included dissolved and particulate MeHg and HgT, TSS, nutrients, and DOC. Stable Hg isotope tracer incubations were used to assess the degree of methylation and demethylation in sediments and surface waters. Average suspended particle MeHg ranged from <5 to 120 pmol/g, and was 1-8% of HgT across sites. Mass balance estimates provide insights into the importance of external MeHg sources to coastal waters. We will use the information to evaluate the following questions: 1) what conditions favor external sources of MeHg over internal production? 2) what conditions enhance net in situ water column formation of MeHg? and 3) what conditions enhance the exchange of MeHg at the sediment/water interface in coastal waters?

Exploring sub-daily to seasonal variations in methane exchange in a single-crop rice paddy in central Japan

NASA Astrophysics Data System (ADS)

Iwata, Hiroki; Mano, Masayoshi; Ono, Keisuke; Tokida, Takeshi; Kawazoe, Takahiro; Kosugi, Yoshiko; Sakabe, Ayaka; Takahashi, Kenshi; Miyata, Akira

2018-04-01

Season-long methane (CH4) exchange was observed in a rice paddy field in central Japan (Kanto Region) using the eddy covariance technique to clarify the variations in environmental controls on CH4 exchange in different stages of cultivation. Before heading of rice plant, the CH4 emission depended on wind speed and soil temperature. The soil temperature dependence can be due to an increase in CH4 production, higher molecular diffusion, and higher conductance within rice plant at higher soil temperature. An occurrence of ebullitive emission was also suggested from the wind speed dependence. After heading was completed, relative humidity and water temperature influenced CH4 emission. The amplitude of the diurnal variation in emission increased from 0.03 μmolm-2s-1 in the late pre-heading stage to 0.13 μmolm-2s-1 in the post-heading stage. Induced convective throughflow within the rice aerenchyma after the change in plant structure was attributable to this variation in environmental controls after the heading. After drainage, CH4 emission was confined to short periods after strong rain events. The water level controlled the timing of emission, most likely by influencing the diffusion efficiency from the anoxic soil to the atmosphere and CH4 oxidation in the surface oxic zone. The variation in the dominant transport pathway needs to be accounted for in terrestrial ecosystem models to accurately predict CH4 emission from rice paddies.

Selenate reduction to elemental selenium by anaerobic bacteria in sediments and culture: biogeochemical significance of a novel, sulfate-independent respiration

USGS Publications Warehouse

Oremland, Ronald S.; Hollibaugh, James T.; Maest, Ann S.; Presser, Theresa S.; Miller, Laurence G.; Culbertson, Charles W.

1989-01-01

Interstitial water profiles of SeO42−, SeO32−, SO42−, and Cl− in anoxic sediments indicated removal of the seleno-oxyanions by a near-surface process unrelated to sulfate reduction. In sediment slurry experiments, a complete reductive removal of SeO42− occurred under anaerobic conditions, was more rapid with H2 or acetate, and was inhibited by O2, NO3−, MnO2, or autoclaving but not by SO42− or FeOOH. Oxidation of acetate in sediments could be coupled to selenate but not to molybdate. Reduction of selenate to elemental selenium was determined to be the mechanism for loss from solution. Selenate reduction was inhibited by tungstate and chromate but not by molybdate. A small quantity of the elemental selenium precipitated into sediments from solution could be resolublized by oxidation with either nitrate or FeOOH, but not with MnO2. A bacterium isolated from estuarine sediments demonstrated selenate-dependent growth on acetate, forming elemental selenium and carbon dioxide as respiratory end products. These results indicate that dissimilatory selenate reduction to elemental selenium is the major sink for selenium oxyanions in anoxic sediments. In addition, they suggest application as a treatment process for removing selenium oxyanions from wastewaters and also offer an explanation for the presence of selenite in oxic waters.

Nitrous oxide and methane dynamics in a coral reef lagoon driven by pore water exchange: Insights from automated high-frequency observations

NASA Astrophysics Data System (ADS)

O'Reilly, Chiara; Santos, Isaac R.; Cyronak, Tyler; McMahon, Ashly; Maher, Damien T.

2015-04-01

Automated cavity ring down spectroscopy was used to make continuous measurements of dissolved methane, nitrous oxide, and carbon dioxide in a coral reef lagoon for 2 weeks (Heron Island, Great Barrier Reef). Radon (222Rn) was used to trace the influence of tidally driven pore water exchange on greenhouse gas dynamics. Clear tidal variation was observed for CH4, which correlated to 222Rn in lagoon waters. N2O correlated to 222Rn during the day only, which appears to be a response to coupled nitrification-denitrification in oxic sediments, fueled by nitrate derived from bird guano. The lagoon was a net source of CH4 and N2O to the atmosphere and a sink for atmospheric CO2. The estimated pore water-derived CH4 and N2O fluxes were 3.2-fold and 24.0-fold greater than the fluxes to the atmosphere. Overall, pore water and/or groundwater exchange were the only important sources of CH4 and major controls of N2O in the coral reef lagoon.

On the influence of carbonate in mineral dissolution: I. The thermodynamics and kinetics of hematite dissolution in bicarbonate solutions at T = 25° C

NASA Astrophysics Data System (ADS)

Bruno, Jordi; Stumm, Werner; Wersin, Paul; Brandberg, Frederick

1992-03-01

We have studied the thermodynamics and kinetics of hematite dissolution in bicarbonate solutions under constant pCO 2. The solubility of hematite is increased in the presence of bicarbonate. We have established that the complexes responsible for this increase are FeOHCO 3 (aq) and Fe(CO 3) 2-. The stability constants of these complexes at the infinite dilution standard state are log β 11 = -3.83 ± 0.21 and log β 2 = 7.40 ± 0.11 , respectively (all errors are given at 2σ confidence level through this work). The rate of dissolution of hematite is enhanced in bicarbonate solutions. This rate of dissolution can be expressed as R diss = k 1[HCO 3-] 0.23 (mol m -2h -1), with k 1 = 1.42 10 -7h -1. The combination of the study of the surface complexation and kinetics of dissolution of hematite in bicarbonate solutions indicate that the dissolution of hematite is surface controlled and bicarbonate promoted. The rate of dissolution follows the expression R diss = k HCO 3-FeOH - HCO 3-}, where k HCO 3- = 1.1 10 -3 h -1. The implications of these findings in the oxic cycle of iron in natural waters are discussed, most importantly in order to explain the high-Fe(III) concentrations measured in groundwaters from the Poços de Caldas complex in Brazil.

Isotope Geochemistry and Chronology of Offshore Ground Water Beneath Indian River Bay, Delaware

USGS Publications Warehouse

Böhlke, John Karl; Krantz, David E.

2003-01-01

Results of geophysical surveys in Indian River Bay, Delaware, indicate a complex pattern of salinity variation in subestuarine ground water. Fresh ground-water plumes up to about 20 meters thick extending hundreds of meters offshore are interspersed with saline ground water, with varying degrees of mixing along the salinity boundaries. It is possible that these features represent pathways for nutrient transport and interaction with estuarine surface water, but the geophysical data do not indicate rates of movement or nutrient sources and reactions. In the current study, samples of subestuarine ground water from temporary wells with short screens placed 3 to 22 meters below the sediment-water interface were analyzed chemically and isotopically to determine the origins, ages, transport pathways, and nutrient contents of the fresh and saline components. Apparent ground-water ages determined from chlorofluorocarbons (CFCs), sulfur hexafluoride (SF6), tritium (3H), and helium isotopes (3He and 4He) commonly were discordant, but nevertheless indicate that both fresh and saline ground waters ranged from a few years to at least 50 years in age. Tritium-helium (3H-3He) ages, tentatively judged to be most reliable, indicate that stratified offshore freshwater plumes originating in distant recharge areas on land were bounded by relatively young saline water that was recharged locally from the overlying estuary. Undenitrified and partially denitrified nitrate of agricultural or mixed origin was transported laterally beneath the estuary in oxic and suboxic fresh ground water. Ammonium produced by anaerobic degradation of organic matter in estuarine sediments was transported downward in suboxic saline ground water around the freshwater plumes. Many of the chemical and isotopic characteristics of the subestuarine ground waters are consistent with conservative mixing of the fresh (terrestrial) and saline (estuarine) endmember water types. These data indicate that freshwater plumes detected by geophysical surveys beneath Indian River Bay represent lateral continuations of the active surficial nitrate-contaminated freshwater flow systems originating on land, but they do not indicate directly the magnitude of fresh ground-water discharge or nutrient exchange with the estuary. There is evidence that some of the terrestrial ground-water nitrate is reduced before discharging directly beneath the estuary. Local estuarine sediment-derived ammonium in saline pore water may be a substantial benthic source of nitrogen in offshore areas of the estuary.

Extraterrestrial demise of banded iron formations 1.85 billion years ago

USGS Publications Warehouse

Slack, J.F.; Cannon, W.F.

2009-01-01

In the Lake Superior region of North America, deposition of most banded iron formations (BIFs) ended abruptly 1.85 Ga ago, coincident with the oceanic impact of the giant Sudbury extraterrestrial bolide. We propose a new model in which this impact produced global mixing of shallow oxic and deep anoxic waters of the Paleoproterozoic ocean, creating a suboxic redox state for deep seawater. This suboxic state, characterized by only small concentrations of dissolved O2 (???1 ??M), prevented transport of hydrothermally derived Fe(II) from the deep ocean to continental-margin settings, ending an ???1.1 billion-year-long period of episodic BIF mineralization. The model is supported by the nature of Precambrian deep-water exhalative chemical sediments, which changed from predominantly sulfide facies prior to ca. 1.85 Ga to mainly oxide facies thereafter. ?? 2009 Geological Society of America.

Microscale geochemical gradients in Hanford 300 Area sediment biofilms and influence of uranium

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nguyen, Hung D.; Cao, Bin; Mishra, Bhoopesh

2012-01-01

The presence and importance of microenvironments in the subsurface at contaminated sites were suggested by previous geochemical studies. However, no direct quantitative characterization of the geochemical microenvironments had been reported. We quantitatively characterized microscale geochemical gradients (dissolved oxygen (DO), H(2), pH, and redox potential) in Hanford 300A subsurface sediment biofilms. Our results revealed significant differences in geochemical parameters across the sediment biofilm/water interface in the presence and absence of U(VI) under oxic and anoxic conditions. While the pH was relatively constant within the sediment biofilm, the redox potential and the DO and H(2) concentrations were heterogeneous at the microscale (<500-1000more » μm). We found microenvironments with high DO levels (DO hotspots) when the sediment biofilm was exposed to U(VI). On the other hand, we found hotspots (high concentrations) of H(2) under anoxic conditions both in the presence and in the absence of U(VI). The presence of anoxic microenvironments inside the sediment biofilms suggests that U(VI) reduction proceeds under bulk oxic conditions. To test this, we operated our biofilm reactor under air-saturated conditions in the presence of U(VI) and characterized U speciation in the sediment biofilm. U L(III)-edge X-ray absorption spectroscopy (XANES and EXAFS) showed that 80-85% of the U was in the U(IV) valence state.« less

Spatial distributions of biogeochemical reactions in freshwater-saltwater mixing zones of sandy beach aquifers

NASA Astrophysics Data System (ADS)

Kim, K. H.; Michael, H. A.; Ullman, W. J.; Cai, W. J.

2017-12-01

Beach aquifers host biogeochemically dynamic mixing zones between fresh and saline groundwaters of contrasting origins, histories, and compositions. Seawater, driven up the beachface by waves and tides, infiltrates into the sand and meets the seaward-discharging fresh groundwater, creating and maintaining a highly reactive intertidal circulation cell well-defined by salinity. Seawater supplies oxygen and reactive carbon to the circulation cell, supporting biogeochemical reactions within the cell that transform and attenuate dissolved nutrient fluxes from terrestrial sources. We investigated the spatial distribution of chemical reaction zones within the intertidal circulation cell at Cape Shores, Lewes, Delaware. Porewater samples were collected from multi-level wells along a beach-perpendicular transect. Samples were analyzed for particulate carbon and reactive solutes, and incubated to obtain rates of oxic respiration and denitrification. High rates of oxic respiration were observed higher on the beach, in the landward freshwater-saline water mixing zone, where dissolved oxygen availability was high. Denitrification was dominant in lower areas of the beach, below the intertidal discharge point. High respiration rates did not correlate with particulate carbon concentrations entrained within porewater, suggesting that dissolved organic carbon or immobile particulate carbon trapped within the sediment can contribute to and alter bulk reactivity. A better understanding of the sources and sinks of carbon within the beach will improve our ability to predict nutrient fluxes to estuaries and oceans, aiding the management of coastal environments and ecosystems.

Microscale geochemical gradients in Hanford 300 Area sediment biofilms and influence of uranium.

PubMed

Nguyen, Hung Duc; Cao, Bin; Mishra, Bhoopesh; Boyanov, Maxim I; Kemner, Kenneth M; Fredrickson, Jim K; Beyenal, Haluk

2012-01-01

The presence and importance of microenvironments in the subsurface at contaminated sites were suggested by previous geochemical studies. However, no direct quantitative characterization of the geochemical microenvironments had been reported. We quantitatively characterized microscale geochemical gradients (dissolved oxygen (DO), H(2), pH, and redox potential) in Hanford 300A subsurface sediment biofilms. Our results revealed significant differences in geochemical parameters across the sediment biofilm/water interface in the presence and absence of U(VI) under oxic and anoxic conditions. While the pH was relatively constant within the sediment biofilm, the redox potential and the DO and H(2) concentrations were heterogeneous at the microscale (<500-1000 μm). We found microenvironments with high DO levels (DO hotspots) when the sediment biofilm was exposed to U(VI). On the other hand, we found hotspots (high concentrations) of H(2) under anoxic conditions both in the presence and in the absence of U(VI). The presence of anoxic microenvironments inside the sediment biofilms suggests that U(VI) reduction proceeds under bulk oxic conditions. To test this, we operated our biofilm reactor under air-saturated conditions in the presence of U(VI) and characterized U speciation in the sediment biofilm. U L(III)-edge X-ray absorption spectroscopy (XANES and EXAFS) showed that 80-85% of the U was in the U(IV) valence state. Copyright © 2011 Elsevier Ltd. All rights reserved.

Membrane fouling and performance evaluation of conventional membrane bioreactor (MBR), moving biofilm MBR and oxic/anoxic MBR.

PubMed

Khan, Sher Jamal; Ahmad, Aman; Nawaz, Muhammad Saqib; Hankins, Nicholas P

2014-01-01

In this study, three laboratory scale submerged membrane bioreactors (MBRs) comprising a conventional MBR (C-MBR), moving bed MBR (MB-MBR) and anoxic-oxic MBR (A/O-MBR) were continuously operated with synthesized domestic wastewater (chemical oxygen demand, COD = 500 mg/L) for 150 days under similar operational and environmental conditions. Kaldnes(®) plastic media with 20% dry volume was used as a biofilm carrier in the MB-MBR and A/O-MBR. The treatment performance and fouling propensity of the MBRs were evaluated. The effect of cake layer formation in all three MBRs was almost the same. However, pore blocking caused a major difference in the resultant water flux. The A/O-MBR showed the highest total nitrogen and phosphorus (PO4-P) removal efficiencies of 83.2 and 69.7%, respectively. Due to the high removal of nitrogen, fewer protein contents were found in the soluble and bound extracellular polymeric substances (EPS) of the A/O-MBR. Fouling trends of the MBRs showed 12, 14 and 20 days filtration cycles for C-MBR, MB-MBR and A/O-MBR, respectively. A 25% reduction of the soluble EPS and a 37% reduction of the bound EPS concentrations in A/O-MBR compared with C-MBR was a major contributing factor for fouling retardation and the enhanced filtration capacity of the A/O-MBR.

Anomalous δ13C in POC at the chemoautotrophy maximum in the Cariaco Basin

NASA Astrophysics Data System (ADS)

Scranton, M. I.; Taylor, G. T.; Thunell, R.; Tappa, E.; benitez-Nelson, C. R.; Muller-Karger, F. E.; Lorenzoni, L.; Astor, Y. M.

2016-02-01

The Cariaco Basin is the world's largest truly marine, permanently anoxic basin and is located on the continental shelf of Venezuela which experiences strong seasonal upwelling. The CARIACO program has been studying the hydrography, biogeochemistry and properties of sinking flux of the Cariaco Basin since 1995. One of the major puzzles of CARIACO has been the nature of the chemoautotrophic maximum which is seen at depths just below the appearance of hydrogen sulfide ( 250-300 m). The identity and sources of oxidants and reductants to this active microbial community, and the identity of the chemoautotrophic organisms themselves, are still only partially known. Below about 50m (the euphotic zone), δ13C values of suspended particulates range from -23 to -26‰, typical of marine phytoplankton. However we have observed both enrichments (values of up to -16‰) and depletions (values of -28‰) near the redox interface. We had expected to see isotopically light POC in the chemoautotrophy maximum, since DIC δ13C should decrease with depth as organic carbon is remineralized. However both positive and negative isotopic excursions in POC occur at depths where dark carbon fixation is at a maximum, and at or near the transition from micro-oxic to sulfidic water. We postulate that this signal may help to define carbon fixation pathways (and dominant chemoautotrophic populations) in the oxic/sulfidic transition region.

Microbiological and Geochemical Characterization of Fluvially Deposited Sulfidic Mine Tailings

PubMed Central

Wielinga, Bruce; Lucy, Juliette K.; Moore, Johnnie N.; Seastone, October F.; Gannon, James E.

1999-01-01

The fluvial deposition of mine tailings generated from historic mining operations near Butte, Montana, has resulted in substantial surface and shallow groundwater contamination along Silver Bow Creek. Biogeochemical processes in the sediment and underlying hyporheic zone were studied in an attempt to characterize interactions consequential to heavy-metal contamination of shallow groundwater. Sediment cores were extracted and fractionated based on sediment stratification. Subsamples of each fraction were assayed for culturable heterotrophic microbiota, specific microbial guilds involved in metal redox transformations, and both aqueous- and solid-phase geochemistry. Populations of cultivable Fe(III)-reducing bacteria were most prominent in the anoxic, circumneutral pH regions associated with a ferricrete layer or in an oxic zone high in organic carbon and soluble iron. Sulfur- and iron-oxidizing bacteria were distributed in discrete zones throughout the tailings and were often recovered from sections at and below the anoxic groundwater interface. Sulfate-reducing bacteria were also widely distributed in the cores and often occurred in zones overlapping iron and sulfur oxidizers. Sulfate-reducing bacteria were consistently recovered from oxic zones that contained high concentrations of metals in the oxidizable fraction. Altogether, these results suggest a highly varied and complex microbial ecology within a very heterogeneous geochemical environment. Such physical and biological heterogeneity has often been overlooked when remediation strategies for metal contaminated environments are formulated. PMID:10103249

Sphaerotilus natans encrusted with nanoball-shaped Fe(III) oxide minerals formed by nitrate-reducing mixotrophic Fe(II) oxidation

PubMed Central

Park, Sunhwa; Kim, Dong-Hun; Lee, Ji-Hoon; Hur, Hor-Gil

2014-01-01

Ferrous iron has been known to function as an electron source for iron-oxidizing microorganisms in both anoxic and oxic environments. A diversity of bacteria has been known to oxidize both soluble and solid-phase Fe(II) forms coupled to the reduction of nitrate. Here, we show for the first time Fe(II) oxidation by Sphaerotilus natans strain DSM 6575T under mixotrophic condition. Sphaerotilus natans has been known to form a sheath structure enclosing long chains of rod-shaped cells, resulting in a thick biofilm formation under oxic conditions. Here, we also demonstrate that strain DSM 6575T grows mixotrophically with pyruvate, Fe(II) as electron donors and nitrate as an electron acceptor and single cells of strain DSM 6575T are dominant under anoxic conditions. Furthermore, strain DSM 6575T forms nanoball-shaped amorphous Fe(III) oxide minerals encrusting on the cell surfaces through the mixotrophic iron oxidation reaction under anoxic conditions. We propose that cell encrustation results from the indirect Fe(II) oxidation by biogenic nitrite during nitrate reduction and that causes the bacterial morphological change to individual rod-shaped single cells from filamentous sheath structures. This study extends the group of existing microorganisms capable of mixotrophic Fe(II) oxidation by a new strain, S. natans strain DSM 6575T, and could contribute to biogeochemical cycles of Fe and N in the environment. PMID:24965827

Novel Pelagic Iron-Oxidizing Zetaproteobacteria from the Chesapeake Bay Oxic-Anoxic Transition Zone.

PubMed

Chiu, Beverly K; Kato, Shingo; McAllister, Sean M; Field, Erin K; Chan, Clara S

2017-01-01

Chemolithotrophic iron-oxidizing bacteria (FeOB) could theoretically inhabit any environment where Fe(II) and O 2 (or nitrate) coexist. Until recently, marine Fe-oxidizing Zetaproteobacteria had primarily been observed in benthic and subsurface settings, but not redox-stratified water columns. This may be due to the challenges that a pelagic lifestyle would pose for Zetaproteobacteria, given low Fe(II) concentrations in modern marine waters and the possibility that Fe oxyhydroxide biominerals could cause cells to sink. However, we recently cultivated Zetaproteobacteria from the Chesapeake Bay oxic-anoxic transition zone, suggesting that they can survive and contribute to biogeochemical cycling in a stratified estuary. Here we describe the isolation, characterization, and genomes of two new species, Mariprofundus aestuarium CP-5 and Mariprofundus ferrinatatus CP-8, which are the first Zetaproteobacteria isolates from a pelagic environment. We looked for adaptations enabling strains CP-5 and CP-8 to overcome the challenges of living in a low Fe redoxcline with frequent O 2 fluctuations due to tidal mixing. We found that the CP strains produce distinctive dreadlock-like Fe oxyhydroxide structures that are easily shed, which would help cells maintain suspension in the water column. These oxides are by-products of Fe(II) oxidation, likely catalyzed by the putative Fe(II) oxidase encoded by the cyc2 gene, present in both CP-5 and CP-8 genomes; the consistent presence of cyc2 in all microaerophilic FeOB and other FeOB genomes supports its putative role in Fe(II) oxidation. The CP strains also have two gene clusters associated with biofilm formation (Wsp system and the Widespread Colonization Island) that are absent or rare in other Zetaproteobacteria. We propose that biofilm formation enables the CP strains to attach to FeS particles and form flocs, an advantageous strategy for scavenging Fe(II) and developing low [O 2 ] microenvironments within more oxygenated waters. However, the CP strains appear to be adapted to somewhat higher concentrations of O 2 , as indicated by the presence of genes encoding aa 3 -type cytochrome c oxidases, but not the cbb 3 -type found in all other Zetaproteobacteria isolate genomes. Overall, our results reveal adaptations for life in a physically dynamic, low Fe(II) water column, suggesting that niche-specific strategies can enable Zetaproteobacteria to live in any environment with Fe(II).

Phosphorus regeneration and burial in near-shore marine sediments (the Gulf of Trieste, northern Adriatic Sea)

NASA Astrophysics Data System (ADS)

Ogrinc, N.; Faganeli, J.

2006-05-01

According to bioassay studies and high dissolved nutrient N/P ratios in the seawater column, phosphorus (P) is thought to control marine productivity in the northern Adriatic Sea. P in near-shore marine sediments of the Gulf of Trieste, the northernmost part of the Adriatic Sea, was investigated using pore water P distributions, and benthic P flux studies under oxic and anoxic conditions. The data show that P regeneration is up to three-fold more extensive in sediments overlain by oxygen-depleted waters and proceeds in parallel with Fe and Mn enhanced benthic fluxes. It appears from the incubation experiments that degradation of sedimentary organic matter is the main contribution to the flux of P at the sediment-water interface, while the release of phosphate adsorbed on the iron oxide surface is of minor importance. It appears that about 50% of P in the Gulf of Trieste is retained within in the sediments, probably bonded to clay minerals and carbonate grains or precipitated as fluoroapatite. In these sediments total P (P tot) is preserved preferentially over organic C (C org). P regenerated from surficial sediments contributes about 1/3 of the P that is assimilated by benthic microalgae. The phytoplankton P requirement should be entirely supplied from fresh-water sources. These results suggest that oxygen depletion in coastal areas caused by eutrophication enhances P regeneration from sediments, providing the additional P necessary for increased biological productivity. The development of anoxic bottom waters in coastal areas enhances the recycling of P, exacerbating the nutrient requirement in the area. A geochemical record of P burial in a longer sedimentary sequence revealed an increasing trend of P tot and organic P (P org) contents occurring approximately 50 years BP (after 1950), probably due to increasing use of inorganic fertilizers and detergents in the area.

Occurrence and fate of benzotriazoles UV filters in a typical residential wastewater treatment plant in Harbin, China.

PubMed

Zhao, Xue; Zhang, Zi-Feng; Xu, Lei; Liu, Li-Yan; Song, Wei-Wei; Zhu, Fu-Jie; Li, Yi-Fan; Ma, Wan-Li

2017-08-01

Benzotriazoles (BTs) UV filters are widely used as ultraviolet absorbents for our daily products, which received increasing attention in the past decades. Residential wastewater treatment plant (WWTP) is both an important sink for wastewater and a key pollution source for receiving water for these chemicals. In this study, pretreatment and gas chromatography-tandem mass spectrometry analysis method were developed to determine the occurrence and fate of 9 BTs UV filters in wastewater and sludge from the WWTP with anaerobic-oxic treatment process (A/O) and biological aerated filter treatment process (BAF). Totally, 81 wastewater samples and 11 sludge samples were collected in four seasons. In wastewater, UV-326 and UV-329 were frequently detected, while the highest mean concentrations were detected for UV-234 and UV-329. The concentrations were in the range of 85% in A/O process and 60-77% in BAF process except for UV-350, which was more difficult to remove with lower removal efficiencies of 33.3% for both A/O and BAF. All the target chemicals except for UV-320 were detected in sludge samples with the mean concentration ranging from 0.90 ng/g to 303.39 ng/g. There was no significant difference with concentrations and removal efficiency among different seasons. Higher detection frequency and concentration of BTs UV filters in downstream of the receiving water system indicated the contribution of effluent of the WWTP. Compared with other rivers, the lower concentrations in surface water in the Songhua River indicated light pollution status with of BTs UV filters. Copyright © 2017 Elsevier Ltd. All rights reserved.

The denitrification paradox: The role of O2 in sediment N2O production

NASA Astrophysics Data System (ADS)

Barnes, Jonathan; Upstill-Goddard, Robert C.

2018-01-01

We designed a novel laboratory sediment flux chamber in which we maintained the headspace O2 partial pressure at preselected values, allowing us to experimentally regulate "in-situ" O2 to evaluate its role in net N2O production by an intertidal estuarine sediment (Tyne, UK). In short-term (30 h) incubations with 10 L of overlying estuarine water (∼3 cm depth) and headspace O2 regulation (headspace: sediment/water ratio ∼9:1), net N2O production was highest at 1.2% O2 (sub-oxic; 32.3 nmol N2O m-2 d-1), an order of magnitude higher than at either 0.0% (anoxic; 2.5 N2O nmol m-2 d-1) or 20.85% (ambient; 2.3 nmol N2O m-2 d-1) O2. In a longer-term sealed incubation (∼490 h) without O2 control, time-dependent behaviour of N2O in the tank headspace was highly non-linear with time, showing distinct phases: (i) an initial period of no or little change in O2 or N2O up to ∼ 100 h; (ii) a quasi-linear, inverse correlation between O2 and N2O to ∼360 h, in which O2 declined to ∼2.1% and N2O rose to ∼7800 natm; (iii) over the following 50 h a slower O2 decline, to ∼1.1%, and a more rapid N2O increase, to ∼12000 natm; (iv) over the next 24 h a slowed O2 decline towards undetectable levels and a sharp fall in N2O to ∼4600 natm; (iv) a continued N2O decrease at zero O2, to ∼3000 natm by ∼ 490 h. These results show clearly that rapid N2O consumption (∼115 nmol m-2 d-1), presumably via heterotrophic denitrification (HD), occurs under fully anoxic conditions and therefore that N2O production, which was optimal for sub-oxic O2, results from other nitrogen transformation processes. In experiments in which we amended sediment overlying water to either 1 mM NH4+ or 1 mM NO3-, N2O production rates were 2-134 nmol N2O m-2 d-1 (NH4+ addition) and 0.4-2.2 nmol N2O m-2 d-1 (NO3- addition). We conclude that processes involving NH4+ oxidation (nitrifier nitrification; nitrifier denitrification; nitrification-coupled denitrification) are principally responsible for N2O production in Tyne sediments. Highest N2O production occurred under sub-oxic headspace (∼1.2 O2%) incubations. Anoxic sediments where HD was isolated acted as periodic N2O sinks or relatively small sources of N2O. Our experimental approach thus gives valuable insight into the O2 effect on N2O fluxes from intertidal sediments.

A dynamic microbial community with high functional redundancy inhabits the cold, oxic subseafloor aquifer.

PubMed

Tully, Benjamin J; Wheat, C Geoff; Glazer, Brain T; Huber, Julie A

2018-01-01

The rock-hosted subseafloor crustal aquifer harbors a reservoir of microbial life that may influence global marine biogeochemical cycles. Here we utilized metagenomic libraries of crustal fluid samples from North Pond, located on the flanks of the Mid-Atlantic Ridge, a site with cold, oxic subseafloor fluid circulation within the upper basement to query microbial diversity. Twenty-one samples were collected during a 2-year period to examine potential microbial metabolism and community dynamics. We observed minor changes in the geochemical signatures over the 2 years, yet the microbial community present in the crustal fluids underwent large shifts in the dominant taxonomic groups. An analysis of 195 metagenome-assembled genomes (MAGs) were generated from the data set and revealed a connection between litho- and autotrophic processes, linking carbon fixation to the oxidation of sulfide, sulfur, thiosulfate, hydrogen, and ferrous iron in members of the Proteobacteria, specifically the Alpha-, Gamma- and Zetaproteobacteria, the Epsilonbacteraeota and the Planctomycetes. Despite oxic conditions, analysis of the MAGs indicated that members of the microbial community were poised to exploit hypoxic or anoxic conditions through the use of microaerobic cytochromes, such as cbb 3 - and bd-type cytochromes, and alternative electron acceptors, like nitrate and sulfate. Temporal and spatial trends from the MAGs revealed a high degree of functional redundancy that did not correlate with the shifting microbial community membership, suggesting functional stability in mediating subseafloor biogeochemical cycles. Collectively, the repeated sampling at multiple sites, together with the successful binning of hundreds of genomes, provides an unprecedented data set for investigation of microbial communities in the cold, oxic crustal aquifer.

Dynamics of bacterial assemblages and removal of polycyclic aromatic hydrocarbons in oil-contaminated coastal marine sediments subjected to contrasted oxygen regimes.

PubMed

Militon, Cécile; Jézéquel, Ronan; Gilbert, Franck; Corsellis, Yannick; Sylvi, Léa; Cravo-Laureau, Cristiana; Duran, Robert; Cuny, Philippe

2015-10-01

To study the impact of oxygen regimes on the removal of polycylic aromatic hydrocarbons (PAHs) in oil-spill-affected coastal marine sediments, we used a thin-layer incubation method to ensure that the incubated sediment was fully oxic, anoxic, or was influenced by oxic-anoxic switches without sediment stirring. Hydrocarbon content and microbial assemblages were followed during 60 days to determine PAH degradation kinetics and microbial community dynamics according to the oxygenation regimes. The highest PAH removal, with 69 % reduction, was obtained at the end of the experiment under oxic conditions, whereas weaker removals were obtained under oscillating and anoxic conditions (18 and 12 %, respectively). Bacterial community structure during the experiment was determined using a dual 16S rRNA genes/16S rRNA transcripts approach, allowing the characterization of metabolically active bacteria responsible for the functioning of the bacterial community in the contaminated sediment. The shift of the metabolically active bacterial communities showed that the selection of first responders belonged to Pseudomonas spp. and Labrenzia sp. and included an unidentified Deltaproteobacteria-irrespective of the oxygen regime-followed by the selection of late responders adapted to the oxygen regime. A novel unaffiliated phylotype (B38) was highly active during the last stage of the experiment, at which time, the low-molecular-weight (LMW) PAH biodegradation rates were significant for permanent oxic- and oxygen-oscillating conditions, suggesting that this novel phylotype plays an active role during the restoration phase of the studied ecosystem.

Effect of Staged Dissolved Oxygen Optimization on In-situ sludge Reduction and Enhanced Nutrient Removal in an A2MMBR-M System

NASA Astrophysics Data System (ADS)

Yang, Shan-Shan; Pang, Ji-Wei; Jin, Xiao-Man; Wu, Zhong-Yang; Yang, Xiao-Yin; Guo, Wan-Qian; Zhao, Zhi-Qing; Ren, Nan-Qi

2018-03-01

Redundant excess sludge production and considerable non-standard wastewater discharge from existing activated sludge processes are facing more and more challenges. The investigations on lower sludge production and higher sewage treatment efficiency are urgently needed. In this study, an anaerobic/anoxic/micro-aerobic/oxic-MBR combining a micro-aerobic starvation sludge holding tank (A2MMBR-M) system is developed. Batch tests on the optimization of the staged dissolved oxygen (DO) in the micro-aerobic, the first oxic, and the second oxic tanks were carried out by a 3-factor and 3-level Box-Behnken design (BBD). The optimal actual values of X1 , X2 , and X3 were DO1 of 0.3-0.5 mg/L, DO2 of 3.5-4.5 mg/L, and DO3 of 3-4 mg/L. After the optimization tests, continuous-flow experiments of anaerobic/anoxic/oxic (AAO) and A2MMBR-M systems were further conducted. Compared to AAO system, a 37.45% reduction in discharged excess sludge in A2MMBR-M system was achieved. The COD, TN, and TP removal efficiencies in A2MMBR-M system were respective 4.06%, 2.68%, and 4.04% higher than AAO system. The A2MMBR-M system is proved a promising wastewater treatment technology possessing enhanced in-situ sludge reduction and improved effluent quality. The staged optimized DO concentrations are the key controlling parameters for the realization of simultaneous in-situ sludge reduction and nutrient removal.

Identification of groundwater nitrate sources in pre-alpine catchments: a multi-tracer approach

NASA Astrophysics Data System (ADS)

Stoewer, Myriam; Stumpp, Christine

2014-05-01

Porous aquifers in pre-alpine areas are often used as drinking water resources due to their good water quality status and water yield. Maintaining these resources requires knowledge about possible sources of pollutants and a sustainable management practice in groundwater catchment areas. Of particular interest in agricultural areas, like in pre-alpine regions, is limiting nitrate input as main groundwater pollutant. Therefore, the objective of the presented study is i) to identify main nitrate sources in a pre-alpine groundwater catchment with current low nitrate concentration using stable isotopes of nitrate (d18O and d15N) and ii) to investigate seasonal dynamics of nitrogen compounds. The groundwater catchment areas of four porous aquifers are located in Southern Germany. Most of the land use is organic grassland farming as well as forestry and residential area. Thus, potential sources of nitrate mainly are mineral fertilizer, manure/slurry, leaking sewage system and atmospheric deposition of nitrogen compounds. Monthly freshwater samples (precipitation, river water and groundwater) are analysed for stable isotope of water (d2H, d18O), the concentration of major anions and cations, electrical conductivity, water temperature, pH and oxygen. In addition, isotopic analysis of d18O-NO3- and d15N-NO3- for selected samples is carried out using the denitrifier method. In general, all groundwater samples were oxic (10.0±2.6mg/L) and nitrate concentrations were low (0.2 - 14.6mg/L). The observed nitrate isotope values in the observation area compared to values from local precipitation, sewage, manure and mineral fertilizer as well as to data from literature shows that the nitrate in freshwater samples is of microbial origin. Nitrate derived from ammonium in fertilizers and precipitation as well as from soil nitrogen. It is suggested that a major potential threat to the groundwater quality is ammonia and ammonium at a constant level mainly from agriculture activities as well as continuously release of nitrogen stored in agricultural soils due to mineralization processes. In all groundwater and river water samples a seasonal variation of nitrate sources and concentration is absent but nitrate in precipitation shows a clear seasonal variation with peaks in spring and fall according to agricultural activity. This points to dilution effects of high nitrate inputs due to the large groundwater volume and mean residence time and highlights the function of soil as initial sink for nitrogen compounds delivered by fertilizer. Even though nitrate contamination was low in the study area, the results emphasize the importance of reducing additional nitrate sources in pre-alpine oxic aquifers. This will maintain the good water quality status of the aquifers and enable its use for drinking water supply.

Variation of Oxygenation Conditions on a Hydrocarbonoclastic Microbial Community Reveals Alcanivorax and Cycloclasticus Ecotypes

PubMed Central

Terrisse, Fanny; Cravo-Laureau, Cristiana; Noël, Cyril; Cagnon, Christine; Dumbrell, Alex J.; McGenity, Terry J.; Duran, Robert

2017-01-01

Deciphering the ecology of marine obligate hydrocarbonoclastic bacteria (MOHCB) is of crucial importance for understanding their success in occupying distinct niches in hydrocarbon-contaminated marine environments after oil spills. In marine coastal sediments, MOHCB are particularly subjected to extreme fluctuating conditions due to redox oscillations several times a day as a result of mechanical (tide, waves and currents) and biological (bioturbation) reworking of the sediment. The adaptation of MOHCB to the redox oscillations was investigated by an experimental ecology approach, subjecting a hydrocarbon-degrading microbial community to contrasting oxygenation regimes including permanent anoxic conditions, anoxic/oxic oscillations and permanent oxic conditions. The most ubiquitous MOHCB, Alcanivorax and Cycloclasticus, showed different behaviors, especially under anoxic/oxic oscillation conditions, which were more favorable for Alcanivorax than for Cycloclasticus. The micro-diversity of 16S rRNA gene transcripts from these genera revealed specific ecotypes for different oxygenation conditions and their dynamics. It is likely that such ecotypes allow the colonization of distinct ecological niches that may explain the success of Alcanivorax and Cycloclasticus in hydrocarbon-contaminated coastal sediments during oil-spills. PMID:28861063

Ubiquitous anaerobic ammonium oxidation in inland waters of China: an overlooked nitrous oxide mitigation process

PubMed Central

Zhu, Guibing; Wang, Shanyun; Zhou, Leiliu; Wang, Yu; Zhao, Siyan; Xia, Chao; Wang, Weidong; Zhou, Rong; Wang, Chaoxu; Jetten, Mike S. M.; Hefting, Mariet M.; Yin, Chengqing; Qu, Jiuhui

2015-01-01

Denitrification has long been regarded as the only pathway for terrestrial nitrogen (N) loss to the atmosphere. Here we demonstrate that large-scale anaerobic ammonium oxidation (anammox), an overlooked N loss process alternative to denitrification which bypasses nitrous oxide (N2O), is ubiquitous in inland waters of China and contributes significantly to N loss. Anammox rates in aquatic systems show different levels (1.0–975.9 μmol N m−2 h−1, n = 256) with hotspots occurring at oxic-anoxic interfaces and harboring distinct biogeochemical and biogeographical features. Extrapolation of these results to the China-national level shows that anammox could contribute about 2.0 Tg N yr−1, which equals averagely 11.4% of the total N loss from China’s inland waters. Our results indicate that a significant amount of the nitrogen lost from inland waters bypasses denitrification, which is important for constructing more accurate climate models and may significantly reduce potential N2O emission risk at a large scale. PMID:26610807

Biomarker Evidence From Demerara Rise for Surface and Deep Water Redox Conditions in the mid Cretaceous Western Equatorial Atlantic

NASA Astrophysics Data System (ADS)

Beckmann, B.; Hofmann, P.; Schouten, S.; Sinninghe Damsté, J. S.; Wagner, T.

2006-12-01

Oceanic Anoxic Events (OAEs) provide deep insights into rapid climate change and atmosphere-land ocean interactions during an extremely warm mode of the Earth system. We present results from ODP Leg 207 at Demerara Rise deposited in the western tropical Atlantic during transition from the Turonian OAE 2 to the Santonian OAE 3. Molecular markers in organic matter-rich black shale identify the composition of primary producers and provide detailed information on the oxygenation state of surface and deep waters. This information is relevant to infer the dynamics and controls of sedimentation leading to black shale in the tropical Atlantic. Bulk organic geochemical data suggest the dominance of lipid-rich marine organic matter throughout the study section. Biomarkers from the aliphatic fraction instead reveal variable contributions of e.g., archaea, diatoms, and dinoflagellates supporting changes in the community of primary producers that thrived in the oxic part of the photic zone in response to changing environmental conditions similar to modern high productive areas along continental margins. Also comparable to modern high productive areas the sea floor remained generally oxygen-depleted throughout the Turonian to Santonian as supported by elevated lycopane contents along with an enrichment of redox-sensitive elements and documented by persistent high TOC concentrations (1 to 14%). Isorenieratane derivates indicative of photic zone euxinia (PZE) were only detected in low abundances in the lowest part of the study section. This observation contrasts biomarker records from the eastern low latitude Atlantic where PZE was a temporal feature determining black shale formation. The new biomarker data from Leg 207 support progressive weakening of upwelling intensity along with oxygenation of surface and possibly mid waters from the upper Coniacian on. Different from black shale sites in many semi-sheltered sub-basins along the Equatorial Atlantic, Demerara Rise was fully exposed to open marine currents throughout the mid-Cretaceous. Increasing ocean circulation along with the widening of the Equatorial Atlantic probably had a significant effect on shallow ocean oxygenation off tropical S-America. Notably deep ocean oxygenation was decoupled from these processes posing the general question what maintained anoxia at the sea floor over millions of years in the aftermath of OAE 2 at Demerara Rise.

The hydrology of northern peatlands as affected by biogenic gas: Current developments and research needs

USGS Publications Warehouse

Rosenberry, D.O.; Glaser, P.H.; Siegel, D.I.

2006-01-01

Recent research indicates that accumulation and release of biogenic gas from northern peatlands may substantially affect future climate. Sudden release of free-phase gas bubbles into the atmosphere may preclude the conversion of methane to carbon dioxide in the uppermost oxic layer of the peat, resulting in greater contribution of methane to the atmosphere than is currently estimated. The hydrology of these peatlands also affects and is affected by this process, especially when gas is released suddenly and episodically. Indirect hydrological evidence indicates that ebullitive gas releases are relatively frequent in some peatlands and time-averaged rates may be significantly greater than diffusive releases. Estimates of free-phase gas contained in peat have ranged from 0 to nearly 20% of the peat volume. Abrupt changes in the volume of gas may alter hydraulic gradients and movement of water and solutes in peat, which in turn could alter composition and fluxes of the gas. Peat surfaces also move vertically and horizontally in response to accumulation and release of free-phase gas. Future research should address the distribution, temporal variability, and relative significance of ebullition in peatlands and the consequent hydrological responses to these gas-emission events. Copyright ?? 2006 John Wiley & Sons, Ltd.

Schwertmannite stability in acidified coastal environments

NASA Astrophysics Data System (ADS)

Collins, Richard N.; Jones, Adele M.; Waite, T. David

2010-01-01

A combination of analytical and field measurements has been used to probe the speciation and cycling of iron in coastal lowland acid sulfate soils. Iron K-edge EXAFS spectroscopy demonstrated that schwertmannite dominated (43-77%) secondary iron mineralization throughout the oxidized and acidified soil profile, while pyrite and illite were the major iron-bearing minerals in the reduced potential acid sulfate soil layers. Analyses of contemporary precipitates from shallow acid sulfate soil groundwaters indicated that 2-line ferrihydrite, in addition to schwertmannite, is presently controlling secondary Fe(III) mineralization. Although aqueous pH values and concentrations of Fe(II) were seasonally high, no evidence was obtained for the Fe(II)-catalyzed crystallization of either mineral to goethite. The results of this study indicate that: (a) schwertmannite is likely to persist in coastal lowland acid sulfate soils on a much longer time-scale than predicted by laboratory experiments; (b) this mineral is less reactive in these types of soils due to surface-site coverage by components such as silicate and possibly, to a lesser extent, natural organic matter and phosphate and; (c) active water table management to promote oxic/anoxic cycles around the Fe(II)-Fe(III) redox couple, or reflooding of these soils, will be ineffective in promoting the Fe(II)-catalyzed transformation of either schwertmannite or 2-line ferrihydrite to crystalline iron oxyhydroxides.

Impact of a wastewater treatment plant on microbial community composition and function in a hyporheic zone of a eutrophic river

NASA Astrophysics Data System (ADS)

Atashgahi, Siavash; Aydin, Rozelin; Dimitrov, Mauricio R.; Sipkema, Detmer; Hamonts, Kelly; Lahti, Leo; Maphosa, Farai; Kruse, Thomas; Saccenti, Edoardo; Springael, Dirk; Dejonghe, Winnie; Smidt, Hauke

2015-11-01

The impact of the installation of a technologically advanced wastewater treatment plant (WWTP) on the benthic microbial community of a vinyl chloride (VC) impacted eutrophic river was examined two years before, and three and four years after installation of the WWTP. Reduced dissolved organic carbon and increased dissolved oxygen concentrations in surface water and reduced total organic carbon and total nitrogen content in the sediment were recorded in the post-WWTP samples. Pyrosequencing of bacterial 16S rRNA gene fragments in sediment cores showed reduced relative abundance of heterotrophs and fermenters such as Chloroflexi and Firmicutes in more oxic and nutrient poor post-WWTP sediments. Similarly, quantitative PCR analysis showed 1-3 orders of magnitude reduction in phylogenetic and functional genes of sulphate reducers, denitrifiers, ammonium oxidizers, methanogens and VC-respiring Dehalococcoides mccartyi. In contrast, members of Proteobacteria adapted to nutrient-poor conditions were enriched in post-WWTP samples. This transition in the trophic state of the hyporheic sediments reduced but did not abolish the VC respiration potential in the post-WWTP sediments as an important hyporheic sediment function. Our results highlight effective nutrient load reduction and parallel microbial ecological state restoration of a human-stressed urban river as a result of installation of a WWTP.

Availability of free oxygen in deep bottom water of some Archean-Early Paleoproterozoic ocean basins as derived from iron formation facies analyses

NASA Astrophysics Data System (ADS)

Beukes, N. J.; Smith, A.

2013-12-01

Archean to Early Paleoproterozoic ocean basins are commonly, although not exclusively, depicted as rather static systems; either permanently stratified with shallow mixed oxygenated water overlying anoxic deep water or with a totally anoxic water column. The anoxic water columns are considered enriched in dissolved ferrous iron derived from hydrothermal plume activity. These sourced deposition of iron formations through precipitation of mainly ferrihydrite via reaction with free oxygen in the stratified model or anaerobic iron oxidizing photoautotrophs in the anoxic model. However, both these models face a simple basic problem if detailed facies reconstructions of deepwater microbanded iron formations (MIFs) are considered. In such MIFs it is common that the deepest water and most distal facies is hematite rich followed shoreward by magnetite, iron silicate and siderite facies iron formation. Examples of such facies relations are known from jaspilitic iron formation of the ~3,2 Ga Fig Tree Group (Barberton Mountainland), ~ 2,95 Ga iron formations of the Witwatersrand-Mozaan basin and the ~2,5 Ga Kuruman Iron Formation, Transvaal Supergroup, South Africa. Facies relations of these MIFs with associated siliciclastics or carbonates also indicate that the upper water columns of the basins, down to below wave base, were depleted in iron favoring anoxic-oxic stratification rather than total anoxia. In the MIFs it can be shown that hematite in the distal facies represents the earliest formed diagenetic mineral; most likely crystallized from primary ferrihydrite. The problem is one of how ferrihydrite could have been preserved on the ocean floor if it was in direct contact with reducing ferrous deep bottom water. Rather dissolved ferrous iron would have reacted with ferrihydrite to form diagenetic magnetite. This dilemma is resolved if in the area of deepwater hematite MIF deposition, the anoxic ferrous iron enriched plume was detached from the basin floor due to buoyancy in slightly oxygenated cold deep ocean water. Ferrihydrite, precipitated along the oxic-anoxic interface along the bottom of the buoyant plume could then settle to the floor of the basin without interference of dissolved ferrous iron. This model requires that oxygen, derived from photosynthesis in shallow water, circulated down to deep water creating a slightly oxygenated ocean basin system invaded by buoyant anoxic ferrous plumes. In areas where these plumes came in contact with the basin floor, magnetite and/or carbonate facies iron formation formed; the latter in areas of highest organic carbon influx. Extensive glacial diamictites in the Witwatersrand-Mozaan basin argues for climatic zonation in the Mesoarchean driving deep ocean currents. This model may explain why the rise of oxygen in the atmosphere was so long delayed after development of oxygenic photosynthesis; simply because in the dynamic ocean system oxygen could come into contact with much larger volumes of reduced species in the water column and along the ocean floor than in a static stratified system. It also impacts on reconstruction of microbial communities in Archean oceans.

Impact of Varying Wave Conditions on the Mobility of Arsenic in a Nearshore Aquifer on the Great Lakes

NASA Astrophysics Data System (ADS)

Rakhimbekova, S.; O'Carroll, D. M.; Robinson, C. E.

2017-12-01

Groundwater-coastal water interactions play an important role in controlling the behavior of inorganic chemicals in nearshore aquifers and the subsequent flux of these chemicals to receiving coastal waters. Previous studies have shown that dynamic groundwater flows and water exchange across the sediment-water interface can set up strong geochemical gradients and an important reaction zone in a nearshore aquifer that affect the fate of reactive chemicals. There is limited understanding of the impact of transient coastal forcing such as wave conditions on groundwater dynamics and geochemistry in a nearshore aquifer. The goal of this study was to assess the impact of intensified wave conditions on the behavior of arsenic in a nearshore aquifer and to determine the hydrological and geochemical factors controlling its fate and ultimate delivery to receiving coastal waters. Field investigations were conducted over the period of intensified wave conditions on a freshwater beach on Lake Erie, Canada. High spatial resolution aqueous and sediment sampling was conducted to characterize the subsurface distribution of inorganic species in the nearshore aquifer. Numerical groundwater flow and transport simulations were conducted to evaluate wave-induced perturbations in the flow dynamics including characterizing changes in the groundwater flow recirculations in the nearshore aquifer. The combination of field data and numerical simulations reveal that varying wave conditions alter groundwater flows and set up geochemical transition zones within the aquifer resulting in the release and sequestration of arsenic. Interactions between oxic surface water, mildly reducing shallow groundwater, and reducing sulfur- and iron-rich deep groundwater promote dynamic iron, sulfur and manganese cycling which control the mobility of arsenic in the aquifer. The findings of this study have potential implications for the fate and transport of other reactive chemicals (e.g. phosphorus, mercury) in nearshore marine and freshwater aquifers exposed to transient coastal forcing. Understanding the fate of chemicals and the dynamics of the reaction zone in nearshore aquifers is critical for evaluating the importance of groundwater as a pathway for delivering pollutants to coastal waters.

Physical Controls on Oxygen Distribution and Denitrification Potential in the North West Arabian Sea

NASA Astrophysics Data System (ADS)

Queste, Bastien Y.; Vic, Clément; Heywood, Karen J.; Piontkovski, Sergey A.

2018-05-01

At suboxic oxygen concentrations, key biogeochemical cycles change and denitrification becomes the dominant remineralization pathway. Earth system models predict oxygen loss across most ocean basins in the next century; oxygen minimum zones near suboxia may become suboxic and therefore denitrifying. Using an ocean glider survey and historical data, we show oxygen loss in the Gulf of Oman (from 6-12 to <2 μmol kg-1) not represented in climatologies. Because of the nonlinearity between denitrification and oxygen concentration, resolutions of current Earth system models are too coarse to accurately estimate denitrification. We develop a novel physical proxy for oxygen from the glider data and use a high-resolution physical model to show eddy stirring of oxygen across the Gulf of Oman. We use the model to investigate spatial and seasonal differences in the ratio of oxic and suboxic water across the Gulf of Oman and waters exported to the wider Arabian Sea.

Geomicrobiology and hopanoid content of sulfidic subsurface vent biofilms, Little Salt Spring, Florida

NASA Astrophysics Data System (ADS)

Yang, E.; Schaperdoth, I.; Albrecht, H.; Freeman, K. H.; Macalady, J. L.

2008-12-01

Sulfide-rich, oxygen-poor environments are widespread in the subsurface and were prevalent at the earth's surface during critical intervals in the geologic past. Modern microbial communities in sulfidic niches have the potential to shed light on the biogeochemistry and biosignatures of anoxia and euxinia in earth history. Caves and sinkholes provide rare windows into microbially-dominated, sulfidic subsurface environments that are otherwise difficult and expensive to access. Little Salt Spring (Sarasota County, Florida) is a cover-collapse sinkhole lake with oxic surface water and anoxic, sulfidic bottom water (Alvarez Zarikian 2005). The site is famous for excellent preservation of human and animal archaeological remains (Clausen 1979), and its microbiology has never been investigated. Abundant white biofilms develop seasonally at a warm vent that feeds into the anoxic bottom water at 73 m depth below the water surface. The biofilms are of interest both as potential sources of biomarker compounds and because of their likely role in sulfuric acid production and limestone dissolution (speleogenesis). Biofilm samples were collected by expert science divers and investigated using microscopy, nucleic acid, and lipid analytical methods. Microscopy of the live biofilm revealed clusters of microbial filaments with holdfasts and dendritic, sulfur-rich colonial structures similar to those described in the 1960s for Thiobacterium, a sulfur-oxidizing genus with undetermined phylogeny. A 16S rDNA library constructed from the biofilm was split into three main phylotypes, with multiple clones representing (1) a Betaproteobacterial clade with no cultivated representatives, (2) filamentous Epsilonproteobacteria, and (3) a major bacterial lineage without named isolates (OP11/OD2). A full cycle rRNA approach is currently underway to link 16S rDNA phylotypes with specific populations in the biofilm. We confirmed using fluorescence in situ hybridization (FISH) that abundant filamentous cells with holdfasts are Epsilonproteobacteria. Additional FISH experiments will target the Betaproteobacterial and OP11/OD2 phylotypes retrieved by cloning. Based on HPLC-MS analyses, the biofilm contains at least 5 membrane hopanoid structures distinct from the suite of hopanoids present in sinking organic particles from the photic zone of the sinkhole. Future efforts will be aimed at linking hopanoid structures to specific sulfur-oxidizing populations and to geochemical parameters such as sulfide and oxygen concentrations. References Alvarez Zarikian,C. A., P. K. Swart, J. A. Gifford, P. L. Blackwelder, Palaeogeography, Palaeoclimatology, Palaeoecology 225, 134 (2005). Clausen, C. J., A. D. Cohen, C. Emiliani, J. A. Holman, J. J. Stipp, Science 203, 609 (1979).

Seasonal Oxygen Dynamics in a Thermokarst Bog in Interior Alaska: Implications for Rates of Methane Oxidation

NASA Astrophysics Data System (ADS)

Neumann, R. B.; Moorberg, C.; Wong, A.; Waldrop, M. P.; Turetsky, M. R.

2015-12-01

Methane is a potent greenhouse gas, and wetlands represent the largest natural source of methane to the atmosphere. However, much of the methane generated in anoxic wetlands never gets emitted to the atmosphere; up to >90% of generated methane can get oxidized to carbon dioxide. Thus, oxidation is an important methane sink and changes in the rate of methane oxidation can affect wetland methane emissions. Most methane is aerobically oxidized at oxic-anoxic interfaces where rates of oxidation strongly depend on methane and oxygen concentrations. In wetlands, oxygen is often the limiting substrate. To improve understanding of belowground oxygen dynamics and its impact on methane oxidation, we deployed two planar optical oxygen sensors in a thermokarst bog in interior Alaska. Previous work at this site indicated that, similar to other sites, rates of methane oxidation decrease over the growing season. We used the sensors to track spatial and temporal patterns of oxygen concentrations over the growing season. We coupled these in-situ oxygen measurements with periodic oxygen injection experiments performed against the sensor to quantify belowground rates of oxygen consumption. We found that over the season, the thickness of the oxygenated water layer at the peatland surface decreased. Previous research has indicated that in sphagnum-dominated peatlands, like the one studied here, rates of methane oxidation are highest at or slightly below the water table. It is in these saturated but oxygenated locations that both methane and oxygen are available. Thus, a seasonal reduction in the thickness of the oxygenated water layer could restrict methane oxidation. The decrease in thickness of the oxygenated layer coincided with an increase in the rate of oxygen consumption during our oxygen injection experiments. The increase in oxygen consumption was not explained by temperature; we infer it was due to an increase in substrate availability for oxygen consuming reactions and/or abundance of key microbial populations. Together, the data provide an explanation for the seasonal decrease in methane oxidation: rates of oxygen consumption increase over the season, which decreases the amount of oxygen dissolved in porewater at the peatland surface and reduces rates of methane oxidation.

Bioadvection of mercury from the Great Salt Lake to surrounding terrestrial ecosystems

NASA Astrophysics Data System (ADS)

Black, F.; Goodman, J.; Collins, J.; Saxton, H.; Mansfield, C.

2015-12-01

The Great Salt Lake (GSL), Utah, USA, is a hypersaline terminal lake that is home to some of the highest concentrations of methylmercury (MeHg) ever measured in natural waters. While terrestrial organisms typically have very low concentrations of MeHg because it is produced almost exclusively in sub-oxic aquatic environments, we documented elevated concentrations of MeHg in brine flies (Ephydra spp.) and spiders along the shores of the GSL. We hypothesized that brine flies, with their larval and pupal stages in the GSL, act as vectors that transfer Hg from the lake to surrounding terrestrial ecosystems as flying adults where they are eaten by spiders and other organisms. The GSL is visited annually by millions of migratory birds, and a major food source for both resident and migratory birds at the GSL are brine flies, so brine flies may represent an important source of Hg to birds here. We conducted a spatial and temporal study of HgT and MeHg in surface waters, brine flies, spiders, and Loggerhead Shrikes (Lanius ludovicianus) a predatory terrestrial songbird of conservation concern, and investigated sublethal effects due to Hg exposure on Antelope Island in the GSL. Samples were also analyzed for their stable carbon and nitrogen isotopic ratios. While HgT and MeHg concentrations in surface waters were elevated, they varied relatively little throughout the year and exhibited no clear seasonal trends. However, seasonal maxima in concentrations of HgT and MeHg in brine flies and spiders occurred in spring and fall, periods of peak migratory bird numbers at the GSL. Approximately 20% of adult/juvenile shrikes had blood HgT concentrations above thresholds previously shown to reduce breeding success in other songbirds, with these concentrations increasing after the annual appearance of orb weaving spiders. HgT concentrations of shrikes decreased with increasing distance from the shoreline and decreasing brine fly abundance, again suggesting the GSL is the ultimate source of Hg in these organisms. Preliminary data from a subset of videos do not show a correlation between nestling Hg levels and nestling feeding rates or growth rate.

Geochemistry of carbon and sulfur in the 2.7 Ga stromatolitic carbonate and shale (ABDP#10 core) from Meentheena, Western Australia

NASA Astrophysics Data System (ADS)

Tomiuka, T.; Yamaguchi, K. E.

2014-12-01

Earth's surface environments about 2.7 Ga ago likely experienced drastic changes such as rapid continental growth, negative excursion of organic carbon isotopes, and positive excursion of mass-independently fractionated sulfur isotopes. Discovery of biomarkers indicating cyanobacteria, although questionable, was also claimed. The coeval shallow ocean could have contained appreciable amount of molecular O2 produced by cyanobacteria, but it has been unknown whether deep sea was oxygenated by ocean circulation. In order to unravel the shallow water environment, we obtained modern-weathering-free 2.7 Ga drilcore samples of stromatolitic carbonate and shale by Archean Biosphere Drilling Project (ABDP#10 core) in Meentheena, NE Western Australia. The purpose of this study is to extract information regarding the surface ocean chemistry by abundance (of various species) and corresponding stable isotope compositions of carbon and sulfur. Based on mass balance calculation, we obtained a much reduced fraction of organic carbon to total carbon (forg) to be 0.11 (c.f., Phanerozoic average is 0.2), suggesting that aerobic and/or anaerobic decomposition of organic matter was vigorous. The very low δ13Corg values suggest carbon recycling involving methanogenesis by methanogen (e.g., 2CH2O → CH4 + CO2) accompanied by large isotope fractionation. Generated CH4 was oxidized by methylotroph to CO2, which was reused to form organic matter by biochemical processes such as photosynthesis. Either O2 or SO42- was required to facilitate CH4 oxidation, suggesting availability of oxidized species in the 2.7 Ga shallow sea environment. Abundance of Spy with near zero δ34Spy values suggest syndepositional and/or diagenetic formation of bacteriogenic pyrite utilizing sulfate formed by oxidation of mantle-derived sulfur (δ34S ≈ 0‰). A plot of Spy vs. Corg abundance shows a trend falling between a Phanerozoic normal marine trend (Spy/Corg = 0.36) and a freshwater trend (Spy << Corg), suggesting formation of Spy in environments fluctuating between near normal marine and fresh water conditions with low SO42- concentration. We suggest that the 2.7 Ga shallow water near Meentheena was slightly oxic in lacustrine setting.

The role of clay minerals in the preservation of organic matter in sediments of Qinghai Lake, NW China

USGS Publications Warehouse

Yu, Bingsong; Dong, Hailiang; Jiang, Hongchen; Lv, Guo; Eberl, Dennis D.; Li, Shanying; Kim, Jinwook

2009-01-01

The role of saline lake sediments in preserving organic matter has long been recognized. In order to further understand the preservation mechanisms, the role of clay minerals was studied. Three sediment cores, 25, 57, and 500 cm long, were collected from Qinghai Lake, NW China, and dissected into multiple subsamples. Multiple techniques were employed, including density fractionation, X-ray diffraction, scanning and transmission electron microscopy (SEM and TEM), total organic carbon (TOC) and carbon compound analyses, and surface area determination. The sediments were oxic near the water-sediment interface, but became anoxic at depth. The clay mineral content was as much as 36.8%, consisting mostly of illite, chlorite, and halloysite. The TEM observations revealed that organic matter occurred primarily as organic matter-clay mineral aggregates. The TOC and clay mineral abundances are greatest in the mid-density fraction, with a positive correlation between the TOC and mineral surface area. The TOC of the bulk sediments ranges from 1 to 3% with the non-hydrocarbon fraction being predominant, followed by bitumen, saturated hydrocarbon, aromatic hydrocarbons, and chloroform-soluble bitumen. The bimodal distribution of carbon compounds of the saturated hydrocarbon fraction suggests that organic matter in the sediments was derived from two sources: terrestrial plants and microorganisms/algae. Depthrelated systematic changes in the distribution patterns of the carbon compounds suggest that the oxidizing conditions and microbial abundance near the water-sediment interface promote degradation of labile organic matter, probably in adsorbed form. The reducing conditions and small microbial biomass deeper in the sediments favor preservation of organic matter, because of the less labile nature of organic matter, probably occurring within clay mineral-organic matter aggregates that are inaccessible to microorganisms. These results have important implications for our understanding of mechanisms of organic matter preservation in saline lake sediments.

Variable Flow Pathways and Geochemical History of Seepage Under Mississippi River Levees: 2011, 2015, and 2016 Floods

NASA Astrophysics Data System (ADS)

Voll, K.; Davidson, G. R.; Borrok, D. M.; Corcoran, M. K.; Kelley, J.; Ma, L.

2017-12-01

Seepage beneath levees during flood stage is a concern when piping occurs, creating channels under the levee and forming sand boils where transported sediments discharge. The flow depth beneath a levee varies with surface geology, following deeper paths where the levee sits on channel fill deposits and shallower paths where it sits on sandbar deposits. Piping along shallow pathways poses an increased risk of levee failure. The Lower Mississippi River Valley alluvial aquifer is geochemically stratified, with reducing waters at greater depth, resulting in unique geochemical signatures for water passing beneath the Mississippi River levee along variable flow paths. Sampling from sand boils and flowing relief wells north of Vicksburg, MS, during the 2011, 2015, and 2016 flood events demonstrates the utility of using the geochemistry of discharge water to identify different flow pathways, and to provide greater insight on the variable water-rock interactions as a function of depth. Relief wells discharge water mainly from deeper zones, reflected by low redox potential, high Fe and As, and low 87Sr/86Sr ratios. High variability in As concentrations may result from varying degrees of reductive dissolution of Fe and Mn and release of co-precipitated As. At shallower depths the aquifer is mostly oxic, lower in Fe, As, and bicarbonate, and higher in sulfate concentrations and 87Sr/86Sr ratios. The geochemical signatures of sand-boil discharge varied between boils that were short distances apart. Water samples plotted on a Piper Diagram fell along two distinct trends starting with river water and diverging along pathways reflecting unique water-rock interaction at different depths. Strontium isotope ratios indicate differences in geochemistry are not just from variable redox reactions, but also reflect dissolution of primary minerals of unique composition or provenance. Oxygen and hydrogen isotopes of all subsurface samples reflect an unexpected level of evaporation of river water prior to recharge to the aquifer, attributed to the presence of numerous water-filled depressions between the river channel and levee system. Tritium levels from wells and boils ranged from 2.3 to 7.4 TU, with some high values coming from deeper zones indicating localized variation in the residence time of water at equal depths beneath levees.

Increased Oxygenation of the Oceans Since the Mid-Cenozoic as Constrained by Cr/Co and Os/Ir Ratios in Oxic Pelagic Sediments

NASA Astrophysics Data System (ADS)

Hu, M.; Lee, C.

2005-12-01

In terms of redox, the marine sediments can be roughly divided into anoxic to suboxic sediments on the margins and oxic sediments in pelagic (open ocean) environments. The relative amounts of anoxic/suboxic sediments being deposited at any given time could be related to biological productivity and/or the efficiency of the ocean circulation system. How the depositional area of anoxic/suboxic deposition has changed through time is thus of concern. One way to track redox conditions is to investigate variations in the concentrations of redox sensitive trace metals. Most studies along these lines have focused on anoxic sediments. However, one problem with using anoxic sediments to study the global oceans is that such sediments are typically deposited in somewhat isolated basins, whose redox conditions may vary from basin to basin. An alternative approach, taken here, is to examine redox-sensitive elemental ratios in oxic pelagic sediments. This is motivated by the fact that pelagic sediments are more likely to reflect average ocean chemistry. In addition, the redox-sensitive metal contents of oxic sediments represent the complement to anoxic sediments. Choosing an appropriate redox-sensitive elemental ratio which eliminates dilution/concentration effects, requires the identification of trace metals that are preferentially precipitated in oxic conditions and those precipitated in more reducing conditions. Overall elemental behaviors were estimated by comparing hydrogenous or authigenic burial fluxes of various trace metals at given pelagic ODP sites to global riverine input fluxes. If the pelagic burial fluxes of a given element are significantly smaller than the riverine input flux, other burial outputs are implied, and it is hypothesized here that this element may precipitate in reducing conditions, such as in oceanic margin. If, on the other hand, the pelagic burial flux is equal to or greater than the riverine input flux, the implication is that oxic pelagic sediments must account for a significant proportion of the burial output of that element. In this case, we assume that this element is oxic-loving. Results of this work reveal that V, Cr, and Co may be particularly redox-sensitive: V and Cr precipitate in reducing environments while Co precipitates in more oxidizing environments. Results of our study, combined with existing data from the literature, show that Cr/Co ratios decrease with depth in DSDP596, 39, 801A, 319, 321, 465A, 577 in the N and S Pacific. After correcting for sedimentation rate, it is shown that the variation of Cr/Co versus time in all of these cores converge, which suggests that the variations in Cr/Co reflect a true variation in seawater composition. This also supported by the lack of sedimentation constrained by Cr/Co and Ce flux. Cr/Co remains low during the Cretaceous but begins to rise at ~25Ma across the entire Pacific. If the Cr/Co and Os/Ir ratio of inputs to the ocean have not changed much, this trend also matches that Os/Ir in the DSDP 596 site in the south Pacific. One interpretation of these results is that there has been a decrease in the area of anoxic/suboxic sedimentation beginning at this time. If correct, the implication is that there was a fundamental change in the redox conditions of the ocean in the mid-Cenozoic. We speculate that this might have been related to mid-Cenozoic global cooling, which may have increased the efficiency of the oceanic circulation system.

Determining Changes in Groundwater Quality during Managed Aquifer Recharge

NASA Astrophysics Data System (ADS)

Gambhir, T.; Houlihan, M.; Fakhreddine, S.; Dadakis, J.; Fendorf, S. E.

2016-12-01

Managed aquifer recharge (MAR) is becoming an increasingly prevalent technology for improving the sustainability of freshwater supply. However, recharge water can alter the geochemical conditions of the aquifer, mobilizing contaminants native to the aquifer sediments. Geochemical alterations on deep (>300 m) injection of highly treated recycled wastewater for MAR has received limited attention. We aim to determine how residual disinfectants used in water treatment processes, specifically the strong oxidants chloramine and hydrogen peroxide, affect metal mobilization within deep injection wells of the Orange County Water District. Furthermore, as the treated recharge water has very low ionic strength (44.6 mg L-1 total dissolved solids), we tested how differing concentrations of magnesium chloride and calcium chloride affected metal mobilization within deep aquifers. Continuous flow experiments were conducted on columns dry packed with sediments from a deep injection MAR site in Orange County, CA. The effluent was analyzed for shifts in water quality, including aqueous concentrations of arsenic, uranium, and chromium. Interaction between the sediment and oxic recharge solution causes naturally-occurring arsenopyrite to repartition onto iron oxides. The stability of arsenic on the newly precipitated iron oxides is dependent on pH changes during recharge.

Survival and Recovery of Methanotrophic Bacteria Starved Under Oxic and Anoxic Conditions

NASA Technical Reports Server (NTRS)

Roslev, Peter; King, Gary M.

1994-01-01

The effects of carbon deprivation on survival of methanotrophic bacteria were compared in cultures incubated in the presence and absence of oxygen in the starvation medium. Survival and recovery of the examined methanotrophs were generally highest for cultures starved under anoxic conditions as indicated by poststarvation measurements of methane oxidation, tetrazolium salt reduction, plate counts, and protein synthesis. Methylosinus trichosporium OB3b survived up to 6 weeks of carbon deprivation under anoxic conditions while maintaining a physiological state that allowed relatively rapid (hours) methane oxidation after substrate addition. A small fraction of cells starved under oxic and anoxic conditions (4 and 10%, respectively) survived more than 10 weeks but required several days for recovery on plates and in liquid medium. A non-spore-forming methanotroph, strain WP 12, displayed 36 to 118% of its initial methane oxidation capacity after 5 days of carbon deprivation. Oxidation rates varied with growth history prior to the experiments as well as with starvation conditions. Strain WP 12 starved under anoxic conditions showed up to 90% higher methane oxidation activity and 46% higher protein production after starvation than did cultures starved under oxic conditions. Only minor changes in biomass and niorpholow were seen for methanotrophic bacteria starved tinder anoxic conditions. In contrast, starvation under oxic conditions resulted in morphology changes and an initial 28 to 35% loss of cell protein. These data suggest that methanotrophic bacteria can survin,e carbon deprivation under anoxic conditions by using maintenance energy derived Solelyr from an anaerobic endogenous metabolism. This capability could partly explain a significant potential for methane oxidation in environments not continuously, supporting aerobic methanotrophic growth.

A dynamic microbial community with high functional redundancy inhabits the cold, oxic subseafloor aquifer

PubMed Central

Tully, Benjamin J; Wheat, C Geoff; Glazer, Brain T; Huber, Julie A

2018-01-01

The rock-hosted subseafloor crustal aquifer harbors a reservoir of microbial life that may influence global marine biogeochemical cycles. Here we utilized metagenomic libraries of crustal fluid samples from North Pond, located on the flanks of the Mid-Atlantic Ridge, a site with cold, oxic subseafloor fluid circulation within the upper basement to query microbial diversity. Twenty-one samples were collected during a 2-year period to examine potential microbial metabolism and community dynamics. We observed minor changes in the geochemical signatures over the 2 years, yet the microbial community present in the crustal fluids underwent large shifts in the dominant taxonomic groups. An analysis of 195 metagenome-assembled genomes (MAGs) were generated from the data set and revealed a connection between litho- and autotrophic processes, linking carbon fixation to the oxidation of sulfide, sulfur, thiosulfate, hydrogen, and ferrous iron in members of the Proteobacteria, specifically the Alpha-, Gamma- and Zetaproteobacteria, the Epsilonbacteraeota and the Planctomycetes. Despite oxic conditions, analysis of the MAGs indicated that members of the microbial community were poised to exploit hypoxic or anoxic conditions through the use of microaerobic cytochromes, such as cbb3- and bd-type cytochromes, and alternative electron acceptors, like nitrate and sulfate. Temporal and spatial trends from the MAGs revealed a high degree of functional redundancy that did not correlate with the shifting microbial community membership, suggesting functional stability in mediating subseafloor biogeochemical cycles. Collectively, the repeated sampling at multiple sites, together with the successful binning of hundreds of genomes, provides an unprecedented data set for investigation of microbial communities in the cold, oxic crustal aquifer. PMID:29099490

Dissipation of hydrological tracers and the herbicide S-metolachlor in batch and continuous-flow wetlands.

PubMed

Maillard, Elodie; Lange, Jens; Schreiber, Steffi; Dollinger, Jeanne; Herbstritt, Barbara; Millet, Maurice; Imfeld, Gwenaël

2016-02-01

Pesticide dissipation in wetland systems with regard to hydrological conditions and operational modes is poorly known. Here, we investigated in artificial wetlands the impact of batch versus continuous-flow modes on the dissipation of the chiral herbicide S-metolachlor (S-MET) and hydrological tracers (bromide, uranine and sulforhodamine B). The wetlands received water contaminated with the commercial formulation Mercantor Gold(®) (960 g L(-1) of S-MET, 87% of the S-enantiomer). The tracer mass budget revealed that plant uptake, sorption, photo- and presumably biodegradation were prominent under batch mode (i.e. characterized by alternating oxic-anoxic conditions), in agreement with large dissipation of S-MET (90%) under batch mode. Degradation was the main dissipation pathway of S-MET in the wetlands. The degradate metolachlor oxanilic acid (MOXA) mainly formed under batch mode, whereas metolachlor ethanesulfonic acid (MESA) prevailed under continuous-flow mode, suggesting distinct degradation pathways in each wetland. R-enantiomer was preferentially degraded under batch mode, which indicated enantioselective biodegradation. The release of MESA and MOXA by the wetlands as well as the potential persistence of S-MET compared to R-MET under both oxic and anoxic conditions may be relevant for groundwater and ecotoxicological risk assessment. This study shows the effect of batch versus continuous modes on pollutant dissipation in wetlands, and that alternate biogeochemical conditions under batch mode enhance S-MET biodegradation. Copyright © 2015 Elsevier Ltd. All rights reserved.

Metal Sulfide Cluster Complexes and their Biogeochemical Importance in the Environment

NASA Astrophysics Data System (ADS)

Luther, George W.; Rickard, David T.

2005-10-01

Aqueous clusters of FeS, ZnS and CuS constitute a major fraction of the dissolved metal load in anoxic oceanic, sedimentary, freshwater and deep ocean vent environments. Their ubiquity explains how metals are transported in anoxic environmental systems. Thermodynamic and kinetic considerations show that they have high stability in oxic aqueous environments, and are also a significant fraction of the total metal load in oxic river waters. Molecular modeling indicates that the clusters are very similar to the basic structural elements of the first condensed phase forming from aqueous solutions in the Fe-S, Zn-S and Cu-S systems. The structure of the first condensed phase is determined by the structure of the cluster in solution. This provides an alternative explanation of Ostwald's Rule, where the most soluble, metastable phases form before the stable phases. For example, in the case of FeS, we showed that the first condensed phase is nanoparticulate, metastable mackinawite with a particle size of 2 nm consisting of about 150 FeS subunits, representing the end of a continuum between aqueous FeS clusters and condensed material. These metal sulfide clusters and nanoparticles are significant in biogeochemistry. Metal sulfide clusters reduce sulfide and metal toxicity and help drive ecology. FeS cluster formation drives vent ecology and AgS cluster formation detoxifies Ag in Daphnia magna neonates. We also note a new reaction between FeS and DNA and discuss the potential role of FeS clusters in denaturing DNA.

Formation of Fe(III) oxyhydroxide colloids in freshwater and brackish seawater, with incorporation of phosphate and calcium

NASA Astrophysics Data System (ADS)

Gunnars, Anneli; Blomqvist, Sven; Johansson, Peter; Andersson, Christian

2002-03-01

The formation of Fe(III) oxyhydroxide colloids by oxidation of Fe(II) and their subsequent aggregation to larger particles were studied in laboratory experiments with natural water from a freshwater lake and a brackish coastal sea. Phosphate was incorporated in the solid phase during the course of hydrolysis of iron. The resulting precipitated amorphous Fe(III) oxyhydroxide phases were of varying composition, depending primarily on the initial dissolved Fe/P molar ratio, but with little influence by salinity or concentration of calcium ions. The lower limiting Fe/P ratio found for the solid phase suggests the formation of a basic Fe(III) phosphate compound with a stoichiometric Fe/P ratio of close to two. This implies that an Fe/P stoichiometry of ≈2 ultimately limits the capacity of precipitating Fe(III) to fix dissolved phosphate at oxic/anoxic boundaries in natural waters. In contrast to phosphorus, the uptake of calcium seemed to be controlled by sorption processes at the surface of the iron-rich particles formed. This uptake was more efficient in freshwater than in brackish water, suggesting that salinity restrains the uptake of calcium by newly formed Fe(III) oxyhydroxides in natural waters. Moreover, salinity enhanced the aggregation rate of the colloids formed. The suspensions were stabilised by the presence of organic matter, although this effect was less pronounced in seawater than in freshwater. Thus, in seawater of 6 to 33 ‰S, the removal of particles was fast (removal half time < 200 h), whereas the colloidal suspensions formed in freshwater were stable (removal half time > 900 h). Overall, oxidation of Fe(II) and removal of Fe(III) oxyhydroxide particles were much faster in seawater than in freshwater. This more rapid turnover results in lower iron availability in coastal seawater than in freshwater, making iron more likely to become a limiting element for chemical scavenging and biologic production.

Disequilibrium biosignatures over Earth history and implications for detecting exoplanet life

PubMed Central

Krissansen-Totton, Joshua; Olson, Stephanie; Catling, David C.

2018-01-01

Chemical disequilibrium in planetary atmospheres has been proposed as a generalized method for detecting life on exoplanets through remote spectroscopy. Among solar system planets with substantial atmospheres, the modern Earth has the largest thermodynamic chemical disequilibrium due to the presence of life. However, how this disequilibrium changed over time and, in particular, the biogenic disequilibria maintained in the anoxic Archean or less oxic Proterozoic eons are unknown. We calculate the atmosphere-ocean disequilibrium in the Precambrian using conservative proxy- and model-based estimates of early atmospheric and oceanic compositions. We omit crustal solids because subsurface composition is not detectable on exoplanets, unlike above-surface volatiles. We find that (i) disequilibrium increased through time in step with the rise of oxygen; (ii) both the Proterozoic and Phanerozoic may have had remotely detectable biogenic disequilibria due to the coexistence of O2, N2, and liquid water; and (iii) the Archean had a biogenic disequilibrium caused by the coexistence of N2, CH4, CO2, and liquid water, which, for an exoplanet twin, may be remotely detectable. On the basis of this disequilibrium, we argue that the simultaneous detection of abundant CH4 and CO2 in a habitable exoplanet’s atmosphere is a potential biosignature. Specifically, we show that methane mixing ratios greater than 10−3 are potentially biogenic, whereas those exceeding 10−2 are likely biogenic due to the difficulty in maintaining large abiotic methane fluxes to support high methane levels in anoxic atmospheres. Biogenicity would be strengthened by the absence of abundant CO, which should not coexist in a biological scenario. PMID:29387792

Disequilibrium biosignatures over Earth history and implications for detecting exoplanet life.

PubMed

Krissansen-Totton, Joshua; Olson, Stephanie; Catling, David C

2018-01-01

Chemical disequilibrium in planetary atmospheres has been proposed as a generalized method for detecting life on exoplanets through remote spectroscopy. Among solar system planets with substantial atmospheres, the modern Earth has the largest thermodynamic chemical disequilibrium due to the presence of life. However, how this disequilibrium changed over time and, in particular, the biogenic disequilibria maintained in the anoxic Archean or less oxic Proterozoic eons are unknown. We calculate the atmosphere-ocean disequilibrium in the Precambrian using conservative proxy- and model-based estimates of early atmospheric and oceanic compositions. We omit crustal solids because subsurface composition is not detectable on exoplanets, unlike above-surface volatiles. We find that (i) disequilibrium increased through time in step with the rise of oxygen; (ii) both the Proterozoic and Phanerozoic may have had remotely detectable biogenic disequilibria due to the coexistence of O 2 , N 2 , and liquid water; and (iii) the Archean had a biogenic disequilibrium caused by the coexistence of N 2 , CH 4 , CO 2 , and liquid water, which, for an exoplanet twin, may be remotely detectable. On the basis of this disequilibrium, we argue that the simultaneous detection of abundant CH 4 and CO 2 in a habitable exoplanet's atmosphere is a potential biosignature. Specifically, we show that methane mixing ratios greater than 10 -3 are potentially biogenic, whereas those exceeding 10 -2 are likely biogenic due to the difficulty in maintaining large abiotic methane fluxes to support high methane levels in anoxic atmospheres. Biogenicity would be strengthened by the absence of abundant CO, which should not coexist in a biological scenario.

Fate of Nutrients in Shallow Groundwater Receiving Treated Septage, Malibu, CA

PubMed Central

Izbicki, John A

2014-01-01

Treated wastewater discharged from more than 400 onsite wastewater treatment systems (OWTS) near the Civic Center area of Malibu, California, 40 km west of downtown Los Angeles, composes 28% of the recharge to a 3.4 km2 alluvial aquifer. On the basis of δ18O and δD data, the fraction of wastewater in some samples was >70%. Ammonium and nitrate concentrations in water from 15 water-table wells sampled in July 2009 and April 2010 ranged from <0.01 to 12 milligrams per liter as nitrogen (mg/L as N), and from <0.01 to 11 mg/L as N, respectively. Chemical and isotopic data (δ15N of ammonium and nitrate, and δ18O of nitrate) show two processes remove nitrogen discharged from OWTS. Where groundwater was reducing, sorption of ammonium resulted in 30 to 50% nitrogen removal. Where groundwater was initially oxic, nitrification with subsequent denitrification as reducing conditions developed, resulted in up to 60% nitrogen removal. Nitrogen removal through sorption dominated during the cooler April sample period, and denitrification dominated during the warmer July sample period. The combination of mixing and nitrogen removal due to denitrification, sorption, and volatilization produces a δ15N apparent fractionation factor (εapp = −5), that can be explained using laboratory-derived fractionation factors (ε) for the individual processes. Phosphate concentrations ranged from < 0.04 to 2 mg/L as phosphorous. Sorption to iron oxides on the surfaces of mineral grains at near-neutral pH's removed some phosphate; however, little removal occurred at more alkaline pH's (>7.3). PMID:24902718

Fate of nutrients in shallow groundwater receiving treated septage, Malibu, CA

USGS Publications Warehouse

Izbicki, John

2014-01-01

Treated wastewater discharged from more than 400 onsite wastewater treatment systems (OWTS) near the Civic Center area of Malibu, California, 40 km west of downtown Los Angeles, composes 28% of the recharge to a 3.4 km2 alluvial aquifer. On the basis of δ18O and δD data, the fraction of wastewater in some samples was >70%. Ammonium and nitrate concentrations in water from 15 water-table wells sampled in July 2009 and April 2010 ranged from <0.01 to 12 milligrams per liter as nitrogen (mg/L as N), and from <0.01 to 11 mg/L as N, respectively. Chemical and isotopic data (δ15N of ammonium and nitrate, and δ18O of nitrate) show two processes remove nitrogen discharged from OWTS. Where groundwater was reducing, sorption of ammonium resulted in 30 to 50% nitrogen removal. Where groundwater was initially oxic, nitrification with subsequent denitrification as reducing conditions developed, resulted in up to 60% nitrogen removal. Nitrogen removal through sorption dominated during the cooler April sample period, and denitrification dominated during the warmer July sample period. The combination of mixing and nitrogen removal due to denitrification, sorption, and volatilization produces a δ15N apparent fractionation factor (εapp= -5), that can be explained using laboratory-derived fractionation factors (ε) for the individual processes. Phosphate concentrations ranged from <0.04 to 2 mg/L as phosphorous. Sorption to iron oxides on the surfaces of mineral grains at near-neutral pH's removed some phosphate; however, little removal occurred at more alkaline pH's (>7.3).

Constraints on global oceanic emissions of N2O from observations and models

NASA Astrophysics Data System (ADS)

Buitenhuis, Erik T.; Suntharalingam, Parvadha; Le Quéré, Corinne

2018-04-01

We estimate the global ocean N2O flux to the atmosphere and its confidence interval using a statistical method based on model perturbation simulations and their fit to a database of ΔpN2O (n = 6136). We evaluate two submodels of N2O production. The first submodel splits N2O production into oxic and hypoxic pathways following previous publications. The second submodel explicitly represents the redox transformations of N that lead to N2O production (nitrification and hypoxic denitrification) and N2O consumption (suboxic denitrification), and is presented here for the first time. We perturb both submodels by modifying the key parameters of the N2O cycling pathways (nitrification rates; NH4+ uptake; N2O yields under oxic, hypoxic and suboxic conditions) and determine a set of optimal model parameters by minimisation of a cost function against four databases of N cycle observations. Our estimate of the global oceanic N2O flux resulting from this cost function minimisation derived from observed and model ΔpN2O concentrations is 2.4 ± 0.8 and 2.5 ± 0.8 Tg N yr-1 for the two N2O submodels. These estimates suggest that the currently available observational data of surface ΔpN2O constrain the global N2O flux to a narrower range relative to the large range of results presented in the latest IPCC report.

Geobiochemistry: Placing Biochemistry in Its Geochemical Context

NASA Astrophysics Data System (ADS)

Shock, E.; Boyer, G. M.; Canovas, P. A., III; Prasad, A.; Dick, J. M.

2014-12-01

Goals of geobiochemistry include simultaneously evaluating the relative stabilities of microbial cells and minerals, and predicting how the composition of biomolecules can change in response to the progress of geochemical reactions. Recent developments in theoretical geochemistry make it possible to predict standard thermodynamic properties of proteins, nucleotides, lipids, and many metabolites including the constituents of the citric acid cycle, at all temperatures and pressures where life is known to occur, and beyond. Combining these predictions with constraints from geochemical data makes it possible to assess the relative stabilities of biomolecules. Resulting independent predictions of the environmental occurrence of homologous proteins and lipid side-chains can be compared with observations from metagenomic and metalipidomic data to quantify geochemical driving forces that shape the composition of biomolecules. In addition, the energetic costs of generating biomolecules from within a diverse range of habitable environments can be evaluated in terms of prevailing geochemical variables. Comparisons of geochemical bioenergetic calculations across habitats leads to the generalization that the availability of H2 determines the cost of autotrophic biosynthesis relative to the aquatic environment external to microbial cells, and that pH, temperature, pressure, and availability of C, N, P, and S are typically secondary. Increasingly reduced conditions, which are determined by reactions of water with mineral surfaces and mineral assemblages, allow many biosynthetic reactions to shift from costing energy to releasing energy. Protein and lipid synthesis, as well as the reverse citric acid cycle, become energy-releasing processes under these conditions. The resulting energy balances that determine habitability contrast dramatically with assumptions derived from oxic surface conditions, such as those where human biochemistry operates.

Temporal Dynamics of Dissolved Oxygen Concentrations in the Hyporheic Zone.

NASA Astrophysics Data System (ADS)

Reeder, W. J.; Quick, A. M.; Farrell, T. B.; Benner, S. G.; Feris, K. P.; Tonina, D.

2016-12-01

Dissolved oxygen (DO) concentration profiles and DO consumption rates are primary indicators of the redox state of porewaters in the hyporheic zone (HZ). Previous studies (mostly numeric) of reactive solute transport, in the HZ, are steady state and give a fixed, in time, view of the biogeochemical activity and redox state of the HZ. Through the use of a novel, multichannel fiber optic DO measurement system and a robotic surface probe system in a large flume experiment, we have been able to track DO concentration, in the HZ, over time and at high spatial and temporal resolutions never achieved before. Our research shows that in carbon-limited systems (i.e., ones in which organic carbon replenishment is largely episodic), DO concentration profiles and consumption rates will vary as a function of time. As the most readily available organic carbon is consumed, (first near the bed surface/water interface) respiration rates, in that area, will drop and DO will be transported deeper into the HZ. Over time, and lacking either an external source of bioavailable carbon or an alternate electron donor substrate, microbial metabolic activity will slow substantially and the majority of the HZ will be rendered oxic. Hyporheic fluxes affect the time scale of biological reactions resulting in faster growth of the aerobic zone in high-flux systems. While this temporal variability can result in a multitude of DO consumption curves (DO vs. residence time), the careful application of dimensional analysis can collapse the consumption curves to a single characteristic curve that accounts for a wide range of morphology and reactivity.

Characterization of contamination, source and degradation of petroleum between upland and paddy fields based on geochemical characteristics and phospholipid fatty acids.

PubMed

Zhang, Juan; Wang, Renqing; Du, Xiaoming; Li, Fasheng; Dai, Jiulan

2012-01-01

To evaluate contamination caused by petroleum, surface soil samples were collected from both upland and paddy fields along the irrigation canals in the Hunpu wastewater irrigation region in northeast China. N-alkanes, terpanes, steranes, and phospholipid fatty acids (PLFA) in the surface soil samples were analyzed. The aliphatic hydrocarbon concentration was highest in the samples obtained from the upland field near an operational oil well; it was lowest at I-3P where wastewater irrigation promoted the downward movement of hydrocarbons. The Hunpu region was found contaminated by heavy petroleum from oxic lacustrine fresh water or marine deltaic source rocks. Geochemical parameters also indicated significantly heavier contamination and degradation in the upland fields compared with the paddy fields. Principal component analysis based on PLFA showed various microbial communities between petroleum contaminated upland and paddy fields. Gram-negative bacteria indicated by 15:0, 3OH 12:0, and 16:1(9) were significantly higher in the paddy fields, whereas Gram-positive bacteria indicated by i16:0 and 18:1(9)c were significantly higher in the upland fields (p < 0.05). These PLFAs were related to petroleum contamination. Poly-unsaturated PLFA (18:2omega6, 9; indicative of hydrocarbon-degrading bacteria and fungi) was also significantly elevated in the upland fields. This paper recommends more sensitive indicators of contamination and degradation of petroleum in soil. The results also provide guidelines on soil pollution control and remediation in the Hunpu region and other similar regions.

Ocean anoxia did not cause the Latest Permian Extinction

NASA Astrophysics Data System (ADS)

Proemse, Bernadette C.; Grasby, Stephen E.; Wieser, Michael E.; Mayer, Bernhard; Beauchamp, Benoit

2014-05-01

The Latest Permian Extinction (LPE, ~252 million years ago) was a turning point in the history of life on Earth with a loss of ~96% of all marine species and ~70% of all terrestrial species. While, the event undoubtedly shaped the evolution of life its cause remains enigmatic. A leading hypothesis is that the global oceans became depleted in oxygen (anoxia). In order to test this hypothesis we investigated a proxy for marine oxygen levels (molybdenum isotopic composition) in shale across the LPE horizon located on the subtropical northwest margin of Pangea at that time. We studied two sedimentary records in the Sverdrup basin, Canadian High Arctic: Buchanan Lake (eastern Axel Heiberg Island; 79° 26.1'N, 87° 12.6'W), representing a distal deep-water slope environment, and West Blind Fiord (southwest Ellesmere Island; 78° 23.9'N, 85° 57.2'W), representing a deep outer shelf environment (below storm wave base). The molybdenum isotopic composition (δ98/95Mo) of sediments has recently become a powerful tool as a paleo-oceanographic proxy of marine oxygen levels. Sample preparation was carried out in a metal-free clean room facility in the isotope laboratory of the Department of Physics and Astronomy, University of Calgary, Canada, that is supplied by HEPA-filtered air. Molybdenum isotope ratios were determined on a Thermo Scientific multi-collector inductively coupled plasma mass spectrometer (MC-ICP-MS) with an uncertainty better than ±0.10o for δ98/95Mo values. Results from the Buchanan Lake section show a large shift in δ98/95Mo values from 2.02o to +2.23o at the extinction horizon, consistent with onset of euxinic conditions. In contrast, West Blind Fiord shales, representing the sub-storm wave base shelf environment, show little change in the molybdenum isotopic composition (1.34o to +0.05), indicating ongoing oxic conditions across the LPE (Proemse et al., 2013). Our results suggest that areas of the Pangea continental shelf (North West Pangea) experienced oxic conditions throughout the LPE event, while anoxic conditions developed in the deep ocean. Hence, anoxic marine waters did not extend globally onto shelf environments and as such ocean anoxia cannot have been the main driver of the extinction event. While global systems were stressed by anoxia, the anoxic conditions may better represent a symptom of Siberian Trap eruptions that had catastrophic impact on the environment, potentially through nutrient loading and deposition of toxic substances into marine and terrestrial systems. Proemse et al., 2013: Molybdenum isotopic evidence for oxic marine conditions during the latest Permian extinction. Geology 41, 967-970.

Effect of bottom water oxygenation on oxygen consumption and benthic biogeochemical processes at the Crimean Shelf (Black Sea)

NASA Astrophysics Data System (ADS)

Lichtschlag, A.; Janssen, F.; Wenzhöfer, F.; Holtappels, M.; Struck, U.; Jessen, G.; Boetius, A.

2012-04-01

Hypoxia occurs where oxygen concentrations fall below a physiological threshold of many animals, usually defined as <63 µmol L-1. Oxygen depletion can be caused by anthropogenic influences, such as global warming and eutrophication, but as well occurs naturally due to restricted water exchange in combination with high nutrient loads (e.g. upwelling). Bottom-water oxygen availability not only influences the composition of faunal communities, but is also one of the main factors controlling sediment-water exchange fluxes and organic carbon degradation in the sediment, usually shifting processes towards anaerobic mineralization pathways mediated by microorganisms. The Black Sea is one of the world's largest meromictic marine basins with an anoxic water column below 180m. The outer shelf edge, where anoxic waters meet the seafloor, is an ideal natural laboratory to study the response of benthic ecosystems to hypoxia, including benthic biogeochemical processes. During the MSM 15/1 expedition with the German research vessel MARIA S. MERIAN, the NW area of the Black Sea (Crimean Shelf) was studied. The study was set up to investigate the influence of bottom water oxygenation on, (1) the respective share of fauna-mediated oxygen uptake, microbial respiration, or re-oxidation of reduced compounds formed in the deeper sediments for the total oxygen flux and (2) on the efficiency of benthic biogeochemical cycles. During our study, oxygen consumption and pathways of organic carbon degradation were estimated from benthic chamber incubations, oxygen microprofiles measured in situ, and pore water and solid phase profiles measured on retrieved cores under oxic, hypoxic, and anoxic water column conditions. Benthic oxygen fluxes measured in Crimean Shelf sediments in this study were comparable to fluxes from previous in situ and laboratory measurements at similar oxygen concentrations (total fluxes -8 to -12 mmol m-2 d-1; diffusive fluxes: -2 to -5 mmol m-2 d-1) with oxygen penetrating less than 5 mm into the seafloor. In total oxygen uptake by the seafloor, the fraction of the diffusive flux, which comprises microbial consumption plus re-oxidation of reduced compounds, increased with declining oxygen concentrations. Measurements and modeling of penetration depths and fluxes of the electron acceptors nitrate, iron- and manganese oxides, sulfate suggest that as long as oxygen is available in the oxic and the hypoxic zones of the Crimean shelf, the largest fraction of oxygen is consumed directly during aerobic mineralization of organic matter and re-oxidation processes play only a minor role. Furthermore, the combination of rapid and strong fluctuation of bottom water oxygen concentration and low sedimentation rates appear to repress anaerobic organic matter degradation. This study was carried out within the framework of the EU-funded project HYPOX (www.hypox.net), which is set up to improve our understanding of hypoxia formation and to develop capacities and know-how for hypoxia monitoring.

Apparent pollution of groundwater caused by natural formation of chloroform in forest soils

NASA Astrophysics Data System (ADS)

Jacobsen, O.; Laier, T.; Albers, C. N.; Hunkeler, D.

2011-12-01

Halogenated compounds are known to be formed in natural environments. Many of these compounds are similar to industrially produced compounds and are toxic or carcinogenic. High concentration of chloroform in groundwater is usually attributed to anthropogenic input, but we have found that the groundwater beneath some pristine areas contained chloroform exceeding 1 μg/L. We investigated four coniferous forests over a period of several years in order to measure the net-formation of chloroform. Field measurements of atmospheric and soil air concentrations of chloroform were monitored. Analyses of soil air at 40 cm depth in different parts of the forests and adjacent areas revealed an extremely large variation in chloroform concentration exceeding two orders of magnitude. Up to 100 ppbv was found in soil air under the spruce forest, to be compared to an ambient atmospheric concentration of 0.02 ppbv. The concentration of chloroform in soil air showed seasonal variation similar to that of CO2. Chloroform formation during incubation of undisturbed top-soil samples was found to be largest in soils from dense conifers stands with well-developed humus layers, while low chloroform formation occurred in soils from beech forest and agricultural grassland. We suggest that the mechanism behind the formation of chloroform is an unspecific chlorination of organic matter, caused by microbial activity in the soil. The aquifers are in fluvio-glacial sands with few layers of silt and a groundwater table from 4 to 7 m below the surface. In the shallowest parts of the aquifer, the groundwater has chloroform concentrations of 0.1 to 5 μg/L, and the groundwater is oxic with an age from 5 to 45 years using CFC-dating. Analyses of oxic groundwater > 40 years showed that it still contained chloroform at concentrations of 1 μg/L. Stable carbon isotopic analyses of chloroform from the uppermost groundwater in different parts of the forests and from soil water showed values from δ13C = -13 % to -27 %, corresponding to the ratio in natural organic materials and quite different from those of industrial products and from contaminated groundwater (δ13C = -46 % to -63 %). The isotopic ratio showed a minor decrease with depth due to a decomposition of chloroform. Measurements in a groundwater transect in one of the forest areas indicated that anoxic conditions in the groundwater depleted chloroform totally.

Downflow limestone beds for treatment of net-acidic, oxic, iron-laden drainage from a flooded anthracite mine, Pennsylvania, USA: 2. Laboratory evaluation

USGS Publications Warehouse

Cravotta, C.A.; Ward, S.J.; Hammarstrom, J.M.

2008-01-01

Acidic mine drainage (AMD) containing elevated concentrations of dissolved iron and other metals can be neutralized to varying degrees by reactions with limestone in passive treatment systems. We evaluated the chemical and mineralogical characteristics and the effectiveness of calcitic and dolomitic limestone for the neutralization of net-acidic, oxic, iron-laden AMD from a flooded anthracite mine. The calcitic limestone, with CaCO3 and MgCO3 contents of 99.8 and <0.1 wt%, respectively, and the dolomitic limestone, with CaCO3 and MgCO3 contents of 60.3 and 40.2 wt%, were used to construct a downflow treatment system in 2003 at the Bell Mine, a large source of AMD and baseflow to the Schuylkill River in the Southern Anthracite Coalfield, in east-central Pennsylvania. In the winter of 2002-2003, laboratory neutralization-rate experiments evaluated the evolution of effluent quality during 2 weeks of continuous contact between AMD from the Bell Mine and the crushed calcitic or dolomitic limestone in closed, collapsible containers (cubitainers). The cubitainer tests showed that: (1) net-alkaline effluent could be achieved with detention times greater than 3 h, (2) effluent alkalinities and associated dissolution rates were equivalent for uncoated and Fe(OH)3-coated calcitic limestone, and (3) effluent alkalinities and associated dissolution rates for dolomitic limestone were about half those for calcitic limestone. The dissolution rate data for the cubitainer tests were used with data on the volume of effuent and surface area of limestone in the treatment system at the Bell Mine to evaluate the water-quality data for the first 1.5 years of operation of the treatment system. These rate models supported the interpretation of field results and indicated that treatment benefits were derived mainly from the dissolution of calcitic limestone, despite a greater quantity of dolomitic limestone within the treatment system. The dissolution-rate models were extrapolated on a decadal scale to indicate the expected decreases in the mass of limestone and associated alkalinities resulting from the long-term reaction of AMD with the treatment substrate. The models indicated the calcitic limestone would need to be replenished approaching the 5-year anniversary of treatment operations to maintain net-alkaline effluent quality. ?? 2008 Springer-Verlag.

Micropollutant removal by attached and suspended growth in a hybrid biofilm-activated sludge process.

PubMed

Falås, P; Longrée, P; la Cour Jansen, J; Siegrist, H; Hollender, J; Joss, A

2013-09-01

Removal of organic micropollutants in a hybrid biofilm-activated sludge process was investigated through batch experiments, modeling, and full-scale measurements. Batch experiments with carriers and activated sludge from the same full-scale reactor were performed to assess the micropollutant removal rates of the carrier biofilm under oxic conditions and the sludge under oxic and anoxic conditions. Clear differences in the micropollutant removal kinetics of the attached and suspended growth were demonstrated, often with considerably higher removal rates for the biofilm compared to the sludge. For several micropollutants, the removal rates were also affected by the redox conditions, i.e. oxic and anoxic. Removal rates obtained from the batch experiments were used to model the micropollutant removal in the full-scale process. The results from the model and plant measurements showed that the removal efficiency of the process can be predicted with acceptable accuracy (± 25%) for most of the modeled micropollutants. Furthermore, the model estimations indicate that the attached growth in hybrid biofilm-activated sludge processes can contribute significantly to the removal of individual compounds, such as diclofenac. Copyright © 2013 Elsevier Ltd. All rights reserved.

Perils of categorical thinking: "Oxic/anoxic" conceptual model in environmental remediation

USGS Publications Warehouse

Bradley, Paul M.

2012-01-01

Given ambient atmospheric oxygen concentrations of about 21 percent (by volume), the lower limit for reliable quantitation of dissolved oxygen concentrations in groundwater samples is in the range of 0.1–0.5 mg/L. Frameworks for assessing in situ redox condition are often applied using a simple two-category (oxic/anoxic) model of oxygen condition. The "oxic" category defines the environmental range in which dissolved oxygen concentrations are clearly expected to impact contaminant biodegradation, either by supporting aerobic biodegradation of electron-donor contaminants like petroleum hydrocarbons or by inhibiting anaerobic biodegradation of electron-acceptor contaminants like chloroethenes. The tendency to label the second category "anoxic" leads to an invalid assumption that oxygen is insignificant when, in fact, the dissolved oxygen concentration is less than detection but otherwise unknown. Expressing dissolved oxygen concentrations as numbers of molecules per volume, dissolved oxygen concentrations that fall below the 0.1 mg/L field detection limit range from 1 to 1017 molecules/L. In light of recent demonstrations of substantial oxygen-linked biodegradation of chloroethene contaminants at dissolved oxygen concentrations well below the 0.1–0.5 mg/L field detection limit, characterizing "less than detection" oxygen concentrations as "insignificant" is invalid.

Intraspecific variation in an Ediacaran skeletal metazoan: Namacalathus from the Nama Group, Namibia.

PubMed

Penny, A M; Wood, R A; Zhuravlev, A Yu; Curtis, A; Bowyer, F; Tostevin, R

2017-01-01

Namacalathus hermanastes is one of the oldest known skeletal metazoans, found in carbonate settings of the terminal Ediacaran (~550-541 million years ago [Ma]). The palaeoecology of this widespread, goblet-shaped, benthic organism is poorly constrained yet critical for understanding the dynamics of the earliest metazoan communities. Analysis of in situ assemblages from the Nama Group, Namibia (~548-541 Ma), shows that Namacalathus exhibited size variation in response to differing water depths, hydrodynamic conditions and substrate types. In low-energy, inner ramp environments, Namacalathus attains the largest average sizes but grew in transient, loosely aggregating, monospecific aggregations attached to microbial mats. In high-energy mid-ramp reefs, Namacalathus spatially segregated into different palaeoecological habitats with distinct size distributions. In outer ramp environments, individuals were small and formed patchy, dense, monospecific aggregations attached to thin microbial mats. Asexual budding is common in all settings. We infer that variations in size distribution in Namacalathus reflect differences in habitat heterogeneity and stability, including the longevity of mechanically stable substrates and oxic conditions. In the Nama Group, long-lived skeletal metazoan communities developed within topographically heterogeneous mid-ramp reefs, which provided diverse mechanically stable microbial substrates in persistently oxic waters, while inner and outer ramp communities were often ephemeral, developing during fleeting episodes of either oxia and/or substrate stability. We conclude that Namacalathus, which forms a component of these communities in the Nama Group, was a generalist that adapted to various palaeoecological habitats within a heterogeneous ecosystem landscape where favourable conditions persisted, and was also able to opportunistically colonise transiently hospitable environments. These early skeletal metazoans colonised previously unoccupied substrates in thrombolitic reefs and other microbial carbonate settings, and while they experienced relatively low levels of interspecific competition, they were nonetheless adapted to the diverse environments and highly dynamic redox conditions present in the terminal Ediacaran. © 2016 John Wiley & Sons Ltd.

The geochemical cycling of trace elements in a biogenic meromictic lake

NASA Astrophysics Data System (ADS)

Balistrieri, Laurie S.; Murray, James W.; Paul, Barbara

1994-10-01

The geochemical processes affecting the behavior and speciation of As, Co, Cr, Cu, Fe, Mn, Mo, Ni, Pb, V, and Zn in Hall Lake, Washington, USA, are assessed by examining dissolved and acid soluble particulate profiles of the elements and utilizing results from thermodynamic calculations. The water column of this meromictic lake is highly stratified and contains distinctive oxic, suboxic, and anoxic layers. Changes in the redox state of the water column with depth affect the distribution of all the elements studied. Most noticeable are increases in dissolved Co, Cr, Fe, Mn, Ni, Pb, and Zn concentrations across the oxic-suboxic boundary, increases in dissolved As, Co, Cr, Fe, Mn, and V concentrations with depth in the anoxic layer, significant decreases in dissolved Cu, Ni, Pb, and Zn concentrations in the anoxic region below the sulfide maximum, and large increases in acid soluble particulate concentrations of As, Cr, Cu, Fe, Mo, Ni, Pb, V, and Zn in the anoxic zone below the sulfide maximum. Thermodynamic calculations for the anoxic region indicate that all redox sensitive elements exist in their reduced forms, the primary dissolved forms of Cu, Ni, Pb, and Zn are metal sulfide solution complexes, and solid sulfide phases of Cu, Fe, Mo, and Pb are supersaturated. Calculations using a vertical diffusion and reaction model indicate that the oxidation rate constant for Mn(II) in Hall Lake is estimated to be 0.006 d -1 and is at the lower end of the range of microbial oxidation rates observed in other natural systems. The main geochemical processes influencing the distribution and speciation of trace elements in Hall Lake appear to be transformations of dissolved elements between their oxidation states (As, Cr, Cu, Fe, Mn, V), cocycling of trace elements with Mn and Fe (As, Co, Cr, Cu, Mo, Ni, Pb, V, Zn), formation of soluble metal sulfide complexes (Co, Cu, Ni, Pb, Zn), sorption (As, Co, Cr, Ni, V), and precipitation (Cu, Fe, Mn, Mo, Pb, Zn).

The geochemical cycling of trace elements in a biogenic meromictic lake

USGS Publications Warehouse

Balistrieri, L.S.; Murray, J.W.; Paul, B.

1994-01-01

The geochemical processes affecting the behavior and speciation of As, Co, Cr, Cu, Fe, Mn, Mo, Ni, Pb, V, and Zn in Hall Lake, Washington, USA, are assessed by examining dissolved and acid soluble particulate profiles of the elements and utilizing results from thermodynamic calculations. The water column of this meromictic lake is highly stratified and contains distinctive oxic, suboxic, and anoxic layers. Changes in the redox state of the water column with depth affect the distribution of all the elements studied. Most noticeable are increases in dissolved Co, Cr, Fe, Mn, Ni, Pb, and Zn concentrations across the oxic-suboxic boundary, increases in dissolved As, Co, Cr, Fe, Mn, and V concentrations with depth in the anoxic layer, significant decreases in dissolved Cu, Ni, Pb, and Zn concentrations in the anoxic region below the sulfide maximum, and large increases in acid soluble particulate concentrations of As, Cr, Cu, Fe, Mo, Ni, Pb, V, and Zn in the anoxic zone below the sulfide maximum. Thermodynamic calculations for the anoxic region indicate that all redox sensitive elements exist in their reduced forms, the primary dissolved forms of Cu, Ni, Pb, and Zn are metal sulfide solution complexes, and solid sulfide phases of Cu, Fe, Mo, and Pb are supersaturated. Calculations using a vertical diffusion and reaction model indicate that the oxidation rate constant for Mn(II) in Hall Lake is estimated to be 0.006 d-1 and is at the lower end of the range of microbial oxidation rates observed in other natural systems. The main geochemical processes influencing the distribution and speciation of trace elements in Hall Lake appear to be transformations of dissolved elements between their oxidation states (As, Cr, Cu, Fe, Mn, V), cocycling of trace elements with Mn and Fe (As, Co, Cr, Cu, Mo, Ni, Pb, V, Zn), formation of soluble metal sulfide complexes (Co, Cu, Ni, Pb, Zn), sorption (As, Co, Cr, Ni, V), and precipitation (Cu, Fe, Mn, Mo, Pb, Zn). ?? 1994.

Plutonium Oxidation State Distribution under Aerobic and Anaerobic Subsurface Conditions for Metal-Reducing Bacteria

NASA Astrophysics Data System (ADS)

Reed, D. T.; Swanson, J.; Khaing, H.; Deo, R.; Rittmann, B.

2009-12-01

The fate and potential mobility of plutonium in the subsurface is receiving increased attention as the DOE looks to cleanup the many legacy nuclear waste sites and associated subsurface contamination. Plutonium is the near-surface contaminant of concern at several DOE sites and continues to be the contaminant of concern for the permanent disposal of nuclear waste. The mobility of plutonium is highly dependent on its redox distribution at its contamination source and along its potential migration pathways. This redox distribution is often controlled, especially in the near-surface where organic/inorganic contaminants often coexist, by the direct and indirect effects of microbial activity. The redox distribution of plutonium in the presence of facultative metal reducing bacteria (specifically Shewanella and Geobacter species) was established in a concurrent experimental and modeling study under aerobic and anaerobic conditions. Pu(VI), although relatively soluble under oxidizing conditions at near-neutral pH, does not persist under a wide range of the oxic and anoxic conditions investigated in microbiologically active systems. Pu(V) complexes, which exhibit high chemical toxicity towards microorganisms, are relatively stable under oxic conditions but are reduced by metal reducing bacteria under anaerobic conditions. These facultative metal-reducing bacteria led to the rapid reduction of higher valent plutonium to form Pu(III/IV) species depending on nature of the starting plutonium species and chelating agents present in solution. Redox cycling of these lower oxidation states is likely a critical step in the formation of pseudo colloids that may lead to long-range subsurface transport. The CCBATCH biogeochemical model is used to explain the redox mechanisms and final speciation of the plutonium oxidation state distributions observed. These results for microbiologically active systems are interpreted in the context of their importance in defining the overall migration of plutonium in the subsurface.

Variation in aluminum, iron, and particle concentrations in oxic ground-water samples collected by use of tangential-flow ultrafiltration with low-flow sampling

USGS Publications Warehouse

Szabo, Z.; Oden, J.H.; Gibs, J.; Rice, D.E.; Ding, Y.; ,

2001-01-01

Particulates that move with ground water and those that are artificially mobilized during well purging could be incorporated into water samples during collection and could cause trace-element concentrations to vary in unfiltered samples, and possibly in filtered samples (typically 0.45-um (micron) pore size) as well, depending on the particle-size fractions present. Therefore, measured concentrations may not be representative of those in the aquifer. Ground water may contain particles of various sizes and shapes that are broadly classified as colloids, which do not settle from water, and particulates, which do. In order to investigate variations in trace-element concentrations in ground-water samples as a function of particle concentrations and particle-size fractions, the U.S. Geological Survey, in cooperation with the U.S. Air Force, collected samples from five wells completed in the unconfined, oxic Kirkwood-Cohansey aquifer system of the New Jersey Coastal Plain. Samples were collected by purging with a portable pump at low flow (0.2-0.5 liters per minute and minimal drawdown, ideally less than 0.5 foot). Unfiltered samples were collected in the following sequence: (1) within the first few minutes of pumping, (2) after initial turbidity declined and about one to two casing volumes of water had been purged, and (3) after turbidity values had stabilized at less than 1 to 5 Nephelometric Turbidity Units. Filtered samples were split concurrently through (1) a 0.45-um pore size capsule filter, (2) a 0.45-um pore size capsule filter and a 0.0029-um pore size tangential-flow filter in sequence, and (3), in selected cases, a 0.45-um and a 0.05-um pore size capsule filter in sequence. Filtered samples were collected concurrently with the unfiltered sample that was collected when turbidity values stabilized. Quality-assurance samples consisted of sequential duplicates (about 25 percent) and equipment blanks. Concentrations of particles were determined by light scattering. Variations in concentrations aluminum and iron (1 -74 and 1-199 ug/L (micrograms per liter), respectively), common indicators of the presence of particulate-borne trace elements, were greatest in sample sets from individual wells with the greatest variations in turbidity and particle concentration. Differences in trace-element concentrations in sequentially collected unfiltered samples with variable turbidity were 5 to 10 times as great as those in concurrently collected samples that were passed through various filters. These results indicate that turbidity must be both reduced and stabilized even when low-flow sample-collection techniques are used in order to obtain water samples that do not contain considerable particulate artifacts. Currently (2001) available techniques need to be refined to ensure that the measured trace-element concentrations are representative of those that are mobile in the aquifer water.

Characterization and Modeling Of Microbial Carbon Metabolism In Thawing Permafrost

NASA Astrophysics Data System (ADS)

Graham, D. E.; Phelps, T. J.; Xu, X.; Carroll, S.; Jagadamma, S.; Shakya, M.; Thornton, P. E.; Elias, D. A.

2012-12-01

Increased annual temperatures in the Arctic are warming the surface and subsurface, resulting in thawing permafrost. Thawing exposes large pools of buried organic carbon to microbial degradation, increasing greenhouse gas generation and emission. Most global-scale land-surface models lack depth-dependent representations of carbon conversion and GHG transport; therefore they do not adequately describe permafrost thawing or microbial mineralization processes. The current work was performed to determine how permafrost thawing at moderately elevated temperatures and anoxic conditions would affect CO2 and CH4 generation, while parameterizing depth-dependent GHG production processes with respect to temperature and pH in biogeochemical models. These enhancements will improve the accuracy of GHG emission predictions and identify key biochemical and geochemical processes for further refinement. Three core samples were obtained from discontinuous permafrost terrain in Fairbanks, AK with a mean annual temperature of -3.3 °C. Each core was sectioned into surface/near surface (0-0.8 m), active layer (0.8-1.6 m), and permafrost (1.6-2.2 m) horizons, which were homogenized for physico-chemical characterization and microcosm construction. Surface samples had low pH values (6.0), low water content (18% by weight), low organic carbon (0.8%), and high C:N ratio (43). Active layer samples had higher pH values (6.4), higher water content (34%), more organic carbon (1.4%) and a lower C:N ratio (24). Permafrost samples had the highest pH (6.5), highest water content (46%), high organic carbon (2.5%) and the lowest C:N ratio (19). Most organic carbon was quantified as labile or intermediate pool versus stable pool in each sample, and all samples had low amounts of carbonate. Surface layer microcosms, containing 20 g sediment in septum-sealed vials, were incubated under oxic conditions, while similar active and permafrost layer samples were anoxic. These microcosms were incubated at -2, +3, or +5 °C for 6 months. The pH decreased in all samples (5.5 to 5.9). The proportions of carbon in labile and intermediate turnover pools from permafrost samples decreased during incubation, while microbial biomass carbon increased in all cases. Microcosm samples and original core material were analyzed by 16S rDNA pyrosequencing and showed increased populations of bacteria that ferment simple and complex carbohydrates, as well as acidophilic bacteria. Microbial diversity declined in permafrost samples. Concentrations of CO2 and CH4 were measured monthly by gas chromatography. CO2 production was highest in the surface/near surface incubations (4-14%) while CH4 was undetectable. Active layer sediments produced considerably less CO2 (0.2-0.7%) but CH4 was detected up to 0.25%. Concentrations of CO2 found in the deep permafrost incubations were comparable to those in the active layer, while CH4 was considerably higher ranging from 0.2-0.6%. Overall, the CO2 generation rate (0.02-0.12 μmol/g/month) was roughly 50 times that of methanogenesis (0.002-0.007 μmol/g/month). GHG levels peaked after 4 months, and the decreasing pH suggested that organic acid accumulation could control GHG biogenesis. Surprisingly, increasing temperature and water content did not necessarily increase GHG emission rates or proportions of CO2 and CH4.

Physical versus chemical effects on bacterial and bromide transport as determined from on site sediment column pulse experiments

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hall, James A.; Mailloux, Brian J.; Onstott, Tullis C.

2005-02-01

Twenty eight bacterial and Br transport experiments were performed in the field to determine the effects of physical and chemical heterogeneity of the aquifer sediment. The experiments were performed using groundwater from two field locations to examine the effects of groundwater chemistry on transport. Groundwater was extracted from multilevel samplers and pumped through 7 cm long columns of intact sediment or re-packed sieved and coated or uncoated sediment from the underlying aquifer. Two bacterial strains, Comamonas sp. DA001 and Paenibacillus polymyxa FER-02, were injected along with Br into the influent end of the columns to examine the effect of cellmore » morphology and surface properties on bacterial transport. The effect of column sediment grain size and mineral coatings coupled with groundwater geochemistry were also delineated. Significant irreversible attachment of DA001 was observed in the Fe oxyhydroxide coated columns, but only in the sub-oxic groundwater where the concentrations of dissolved organic carbon (DOC) were ca. 1 ppm. In the oxic groundwater where DOC was ca. 8 ppm, little attachment of DA001 to the Fe oxyhydroxide coated columns was observed. This indicates that DOC can significantly reduce bacterial attachment due electrostatic interactions. The larger and more negatively charged FER-02 displayed increasing attachment with decreasing grain size regardless of DOC concentration, and modeling of FER-02 attachment revealed that the presence of Fe and Al coatings on the sediment also promoted attachment. Finally, the presence of Al coatings and Al containing minerals appeared to significantly retard the Br tracer regardless of the concentration of DOC. These findings suggest that DOC in shallow oxic groundwater aquifers can significantly enhance the transport of bacteria by reducing attachment to Fe, Mn and Al oxyhydroxides. This effect is profound for weakly charged, hydrophilic bacteria and may contribute to differences in observations between laboratory experiments verses field-scale investigations particularly if the groundwater pH remains circum-neutral and Fe oxyhydroxide phases exist. These observations validate the novel approach taken in the experiments outlined here of performing laboratory-scale experiments on site to facilitate the use of fresh groundwater and thus be more representative of in situ groundwater conditions.« less

Hydrogeologic and geochemical characterization and evaluation of two arroyos for managed aquifer recharge by surface infiltration in the Pojoaque River Basin, Santa Fe County, New Mexico, 2014–15

USGS Publications Warehouse

Robertson, Andrew J.; Cordova, Jeffrey; Teeple, Andrew; Payne, Jason; Carruth, Rob

2017-02-22

In order to provide long-term storage of diverted surface water from the Rio Grande as part of the Aamodt water rights settlement, managed aquifer recharge by surface infiltration in Pojoaque River Basin arroyos was proposed as an option. The initial hydrogeologic and geochemical characterization of two arroyos located within the Pojoaque River Basin was performed in 2014 and 2015 in cooperation with the Bureau of Reclamation to evaluate the potential suitability of these two arroyos as sites for managed aquifer recharge through surface infiltration.The selected reaches were high-gradient (average 3.0–3.5 percent) braided channels filled with unconsolidated sand and gravel-sized deposits that were generally 30–50 feet thick. Saturation was not observed in the unconsolidated channel sands in four subsurface borings but was found at 7–60 feet below the contact between the unconsolidated channel sands and the bedrock. The poorly to well-cemented alluvial deposits that make up the bedrock underlying the unconsolidated channel material is the Tesuque Formation. The individual beds of the Tesuque Formation are reported to be highly heterogeneous and anisotropic, and the bedrock at the site was observed to have variable moisture and large changes in lithology. Surface electrical-resistivity geophysical survey methods showed a sharp contrast between the electrically resistive unconsolidated channel sands and the highly conductive bedrock; however, because of the high conductivity, the resistivity methods were not able to image the water table or preferential flow paths (if they existed) in the bedrock.Infiltration rates measured by double-ring and bulk infiltration tests on a variety of channel morphologies in the study reaches were extremely large (9.7–94.5 feet per day), indicating that the channels could potentially accommodate as much as 6.6 cubic feet per second of applied water without generating surface runoff out of the reach; however, the small volume available for storage in the unconsolidated channel sands (about 410 acre-feet in the east arroyo and about 190 acre-feet in the west arroyo) and the potential for the infiltrating water to preferentially flow over the bedrock contact and out of the reach present a challenge for storing water. Although a detailed assessment of the infiltration rate of the Tesuque Formation is beyond the scope of this investigation, one double-ring infiltrometer test was conducted on an outcrop, resulting in an estimated infiltration rate of about 4 feet per day.The shallow groundwater observed in this investigation was determined to be recharged locally on the basis of groundwater elevations and geochemical and isotopic signatures. The channel sands and shallow bedrock were observed to be weathered, indicating contact with oxic groundwater following deposition. This observation was supported by whole-rock elemental analysis and mineralogy of several core samples. The downward groundwater gradient between the shallow wells and those wells screened at greater depths suggests that the shallow groundwater is recharged by local precipitation and has the potential to migrate to the deeper aquifer units. The two age-dating tracers measured in this investigation, however, demonstrate that the shallow groundwater flow paths are very slow and that the deeper flow paths are likely part of a larger regional system.The composition of the shallow, native groundwater suggests that storing water diverted from the Rio Grande is not likely to leach constituents of concern that would cause the stored water to exceed health-based U.S. Environmental Protection Agency Maximum Contaminant Levels.

Methanotrophy within the water column of a large meromictic tropical lake (Lake Kivu, East Africa)

NASA Astrophysics Data System (ADS)

Morana, C.; Borges, A. V.; Roland, F. A. E.; Darchambeau, F.; Descy, J.-P.; Bouillon, S.

2015-04-01

The permanently stratified Lake Kivu is one of the largest freshwater reservoirs of dissolved methane (CH4) on Earth. Yet CH4 emissions from its surface to the atmosphere have been estimated to be 2 orders of magnitude lower than the CH4 upward flux to the mixed layer, suggesting that microbial CH4 oxidation is an important process within the water column. A combination of natural abundance stable carbon isotope analysis (δ13C) of several carbon pools and 13CH4-labelling experiments was carried out during the rainy and dry season to quantify (i) the contribution of CH4-derived carbon to the biomass, (ii) methanotrophic bacterial production (MBP), and (iii) methanotrophic bacterial growth efficiency (MBGE), defined as the ratio between MBP and gross CH4 oxidation. We also investigated the distribution and the δ13C of specific phospholipid fatty acids (PLFAs), used as biomarkers for aerobic methanotrophs. Maximal MBP rates were measured in the oxycline, suggesting that CH4 oxidation was mainly driven by oxic processes. Moreover, our data revealed that methanotrophic organisms in the water column oxidized most of the upward flux of CH4, and that a significant amount of CH4-derived carbon was incorporated into the microbial biomass in the oxycline. The MBGE was variable (2-50%) and negatively related to CH4 : O2 molar ratios. Thus, a comparatively smaller fraction of CH4-derived carbon was incorporated into the cellular biomass in deeper waters, at the bottom of the oxycline where oxygen was scarce. The aerobic methanotrophic community was clearly dominated by type I methanotrophs and no evidence was found for an active involvement of type II methanotrophs in CH4 oxidation in Lake Kivu, based on fatty acids analyses. Vertically integrated over the water column, the MBP was equivalent to 16-60% of the average phytoplankton particulate primary production. This relatively high magnitude of MBP, and the substantial contribution of CH4-derived carbon to the overall biomass in the oxycline, suggest that methanotrophic bacteria could potentially sustain a significant fraction of the pelagic food web in the deep, meromictic Lake Kivu.

Dominance of 'Gallionella capsiferriformans' and heavy metal association with Gallionella-like stalks in metal-rich pH 6 mine water discharge

USGS Publications Warehouse

Fabisch, Maria; Freyer, Gina; Johnson, Carol A.; Buchel, Georg; Akob, Denise M.; Neu, Thomas R.; Kusel, Kirsten

2016-01-01

Heavy metal-contaminated, pH 6 mine water discharge created new streams and iron-rich terraces at a creek bank in a former uranium-mining area near Ronneburg, Germany. The transition from microoxic groundwater with ~5 mm Fe(II) to oxic surface water may provide a suitable habitat for microaerobic iron-oxidizing bacteria (FeOB). In this study, we investigated the potential contribution of these FeOB to iron oxidation and metal retention in this high-metal environment. We (i) identified and quantified FeOB in water and sediment at the outflow, terraces, and creek, (ii) studied the composition of biogenic iron oxides (Gallionella-like twisted stalks) with scanning and transmission electron microscopy (SEM, TEM) as well as confocal laser scanning microscopy (CLSM), and (iii) examined the metal distribution in sediments. Using quantitative PCR, a very high abundance of FeOB was demonstrated at all sites over a 6-month study period. Gallionella spp. clearly dominated the communities, accounting for up to 88% ofBacteria, with a minor contribution of other FeOB such as Sideroxydans spp. and ‘Ferrovum myxofaciens’. Classical 16S rRNA gene cloning showed that 96% of the Gallionella-related sequences had ≥97% identity to the putatively metal-tolerant ‘Gallionella capsiferriformans ES-2’, in addition to known stalk formers such as Gallionella ferruginea and Gallionellaceae strain R-1. Twisted stalks from glass slides incubated in water and sediment were composed of the Fe(III) oxyhydroxide ferrihydrite, as well as polysaccharides. SEM and scanning TEM-energy-dispersive X-ray spectroscopy revealed that stalk material contained Cu and Sn, demonstrating the association of heavy metals with biogenic iron oxides and the potential for metal retention by these stalks. Sequential extraction of sediments suggested that Cu (52–61% of total sediment Cu) and other heavy metals were primarily bound to the iron oxide fractions. These results show the importance of ‘G. capsiferriformans’ and biogenic iron oxides in slightly acidic but highly metal-contaminated freshwater environments.

Mercury cycling in agricultural and managed wetlands of California: experimental evidence of vegetation-driven changes in sediment biogeochemistry and methylmercury production

USGS Publications Warehouse

Windham-Myers, Lisamarie; Marvin-DiPasquale, Mark; Stricker, Craig A.; Agee, Jennifer L.; Kieu, Le H.; Kakouros, Evangelos

2014-01-01

The role of live vegetation in sediment methylmercury (MeHg) production and associated biogeochemistry was examined in three types of agricultural wetlands (domesticated or white rice, wild rice, and fallow fields) and adjacent managed natural wetlands (cattail- and bulrush or tule-dominated) in the Yolo Bypass region of California's Central Valley, USA. During the active growing season for each wetland, a vegetated:de-vegetated paired plot experiment demonstrated that the presence of live plants enhanced microbial rates of mercury methylation by 20 to 669% (median = 280%) compared to de-vegetated plots. Labile carbon exudation by roots appeared to be the primary mechanism by which microbial methylation was enhanced in the presence of vegetation. Pore-water acetate (pw[Ac]) decreased significantly with de-vegetation (63 to 99%) among all wetland types, and within cropped fields, pw[Ac] was correlated with both root density (r = 0.92) and microbial Hg(II) methylation (kmeth. r = 0.65). Sediment biogeochemical responses to de-vegetation were inconsistent between treatments for “reactive Hg” (Hg(II)R), as were reduced sulfur and sulfate reduction rates. Sediment MeHg concentrations in vegetated plots were double those of de-vegetated plots (median = 205%), due in part to enhanced microbial MeHg production in the rhizosphere, and in part to rhizoconcentration via transpiration-driven pore-water transport. Pore-water concentrations of chloride, a conservative tracer, were elevated (median = 22%) in vegetated plots, suggesting that the higher concentrations of other constituents around roots may also be a function of rhizoconcentration rather than microbial activity alone. Elevated pools of amorphous iron (Fe) in vegetated plots indicate that downward redistribution of oxic surface waters through transpiration acts as a stimulant to Fe(III)-reduction through oxidation of Fe(II)pools. These data suggest that vegetation significantly affected rhizosphere biogeochemistry through organic exudation and transpiration-driven concentration of pore-water constituents and oxidation of reduced compounds. While the relative role of vegetation varied among wetland types, macrophyte activity enhanced MeHg production.

Investigating the Role of Hydrologic Residence Time in Nitrogen Transformations at the Sediment-Water Interface using Controlled Variable Head Experiments

NASA Astrophysics Data System (ADS)

Hampton, T. B.; Zarnetske, J. P.; Briggs, M. A.; Singha, K.; Day-Lewis, F. D.

2017-12-01

Many important biogeochemical processes governing both carbon and nitrogen dynamics in streams take place at the sediment-water interface (SWI). This interface is highly variable in biogeochemical function, with stream stage often influencing the magnitude and direction of water and solute exchange through the SWI. It is well known that the SWI can be an important location for carbon and nitrogen transformations, including denitrification and greenhouse gas production. The degree of mixing of carbon and nitrate, along with oxygen from surface waters, is strongly influenced by hydrologic exchange at the SWI. We hypothesize that hydrologic residence time, which is also determined by the magnitude of exchange, is a key control on the fate of nitrate at the SWI and on the end products of denitrification. Previous studies in the headwaters of the Ipswich River in MA as part of the Lotic Intersite Nitrogen Experiments (LINX II) and other long-term monitoring suggest that the Ipswich River SWI represents an important source of nitrous oxide, a potent greenhouse gas. Using a novel constant-head infiltrometer ring embedded in the stream sediments, we created four unique controlled down-welling (i.e., recharge) conditions, and tested how varying this hydrologic flux and thus the residence time distribution influenced biogeochemical function of the Ipswich River SWI. Specifically, we added isotopically-labelled 15N-nitrate to stream water during each controlled hydrologic flux experiment to quantify nitrate transformation rates, including denitrification end products, under the different hydrologic conditions. We also measured a suite of carbon and nitrogen solutes, along with dissolved oxygen conditions throughout each experiment to characterize the broader residence timescale and biogeochemical responses to the hydrologic manipulations. Initial results show that the oxic conditions of the SWI were strongly responsive to changes in hydrologic flux rates, thereby changing the redox conditions and likely the fate of the nitrate through the infiltrometer. The forthcoming 15N data will quantify the nitrate response. Overall, this study will help demonstrate how the SWI of this historically important research river transforms nitrate under variable hydrologic conditions.

Metabolic Potential of Microbial Genomes Reconstructed from a Deep-Sea Oligotrophic Sediment Metagenome

NASA Astrophysics Data System (ADS)

Tully, B. J.; Huber, J. A.; Heidelberg, J. F.

2016-02-01

The South Pacific Gyre (SPG) possesses the lowest rates of sedimentation, surface chlorophyll concentration and primary productivity in the global oceans, making it one of the most oligotrophic environments on earth. As a direct result of the low-standing biomass in surface waters, deep-sea sediments are thin and contain small amount of labile organic carbon. It was recently shown that the sediment column within the SPG is fully oxic through to the underlying basalt basement and may be representative of 9-37% of the global marine environment. In addition, it appears that approximately 50% of the total organic carbon is removed from the oligotrophic sediments within the first 20 centimeters beneath the sea floor (cmbsf). To understand the microbial processes that contribute to the removal of the labile organic matter, metagenomic sequencing and analysis was carried out on a sample of sediment collected from 0-5 cmbsf from SPG site 10 (U1369). Analysis of 9 partially reconstructed environmental genomes revealed that the members of the SPG surface sediment microbial community are phylogenetically distinct from surface/upper ocean organisms, with deep branches within the Alpha- and Gammaproteobacteria, Nitrospirae, Nitrospina, the phylum NC10, and several unique phylogenetic groups. Within these partially complete genomes there is evidence for microbially mediated metal (iron/manganese) oxidation and carbon fixation linked to the nitrification. Additionally, despite low sedimentation and hypothesized energy-limitation, members of the SPG microbial community had motility and chemotactic genes and possessed mechanisms for the utilization of high molecular weight organic matter, including exoproteases and peptide specific membrane transporters. Simultaneously, the SPG genomes showed a limited potential for the degradation of recalcitrant carbon compounds. Finally, the presence of putative genes with functions involved with denitrification and the consumption of C1 compounds suggest that there may be microenvironments in the surface sediments were microbes can deplete oxygen concentrations to hypoxic/anoxic levels. This study represents an important first analysis in understanding how microorganisms in oligotrophic sediments impact deep-sea carbon transformations.

Nitrogen cycling in 2.7 Ga oceans

NASA Astrophysics Data System (ADS)

Yang, J.; Zerkle, A.; Grassineau, N.; Nisbet, E.; Mettam, C.; Izon, G. J.; Morag, H.; Anthony, M.; Newton, J.; Boyce, A.

2016-12-01

A growing body of geochemical evidence suggests that localized oxygenation of the surface earth must have begun much earlier than the GOE ( 2.4 Ga). This could have triggered the emergence of the aerobic biogeochemical cycle of nitrogen (N), an essential nutrient for all organisms. However, the timing of this revolutionary transition is poorly known. Some sediments from 2.7 Ga possess exceptionally high enrichment of 15N. Whether these values are linked to the onset of the aerobic N cycle[1], or reflective of alkaline lakes on land[2], has been in dispute. To explore this, we are investigating one of the best-preserved unambiguously marine Achaean successions from the Belingwe Greenstone Belt, in Zimbabwe. We are focusing on nearly pristine sediments from the 2.7 Ga Manjeri Formation, which span both shallow and deep-water environments, preserving organic-rich shales and some of the oldest and most well-preserved stromatolites. The depositional conditions for this succession are further constrained by iron speciation data and sulfur isotopes, which show a redox transition from ferruginous to oxic environments from older to younger sediments. Nitrogen isotopes in these sediments will constrain the global nature of the extremely 15N-enriched values, and test hypotheses for the Neoarchean nitrogen cycle in a non-disputed marine setting. [1] Thomazo et al. (2011) Geobiology; [2] Stüeken et al. (2015) EPSL.

Metagenomic Assessment of a Dynamic Microbial Population from Subseafloor Aquifer Fluids in the Cold, Oxygenated Crust

NASA Astrophysics Data System (ADS)

Tully, B. J.; Heidelberg, J. F.; Kraft, B.; Girguis, P. R.; Huber, J. A.

2016-12-01

The oceanic crust contains the largest aquifer on Earth with a volume approximately 2% of the global ocean. Ongoing research at the North Pond (NP) site, west of the Mid-Atlantic Ridge, provides an environment representative of oxygenated crustal aquifers beneath oligotrophic surface waters. Using subseafloor CORK observatories for multiple sampling depths beneath the seafloor, crustal fluids were sampled along the predicted aquifer fluid flow path over a two-year period. DNA was extracted and sequenced for metagenomic analysis from 22 crustal fluid samples, along with the overlying bottom. At broad taxonomic groupings, the aquifer system is highly dynamic over time and space, with shifts in dominant taxa and "blooms" of transient groups that appear at discreet time points and sample depths. We were able to reconstruct 194 high-quality, low-contamination bacterial and archaeal metagenomic-assembled genomes (MAGs) with estimated completeness >50% (429 MAGs >20% complete). Environmental genomes were assigned to phylogenies from the major bacterial phyla, putative novel groups, and poorly sampled phylogenetic groups, including the Marinimicrobia, Candidate Phyla Radiation, and Planctomycetes. Biogeochemically relevant processes were assigned to MAGs, including denitrification, dissimilatory sulfur and hydrogen cycling, and carbon fixation. Collectively, the oxic NP aquifer system represents a diverse, dynamic microbial habitat with the metabolic potential to impact multiple globally relevant biogeochemical cycles, including nitrogen, sulfur, and carbon.

Fate of phthalate esters in municipal wastewater treatment plant and their environmental impact.

PubMed

Kong, Minghao; Song, Yonghui; Zhang, Yizhang; Liu, Ruixia; Wei, Jian; Zheng, Lei

2016-01-01

The fate and distribution of six phthalate esters (PAEs) in a municipal wastewater treatment plant (WWTP) employing an anaerobic/anoxic/oxic (A(2)/O) process were investigated. The process achieved relatively high removal efficiencies of PAEs in the range 55-97%. It illustrated that biotransformation and sludge-adsorption were major elimination pathways by analyzing the mass balance and flux of PAEs. About 83% of ∑PAEs was entirely removed by A(2)/O bioreactors indicating biotransformation is the dominant removal mechanism. PAEs with shorter alkyl chain length and higher water solubility were more biodegradable. Less than 6% of ∑PAEs were removed by excess sludge adsorption. The sludge-adsorption capacity of PAE depends on its hydrophobicity. The levels and fluxes of PAEs were analyzed by monitoring different sites of the receiving river of the WWTP effluent to clarify the potential impact of discharge. Daily flux of PAEs upstream and downstream of the discharging point were 113 kg·d(-1) and 205 kg·d(-1), respectively, which were higher than the effluent devotion value of 6.67 kg·d(-1). It suggested that the emissions from the WWTP appeared to be less than those from the other possible sources, such as potential untreated discharge and surface runoff. Improvement of wastewater collection efficiencies is necessary to eliminate the PAE load in the urban river.

Contrasting nitrogen fate in watersheds using agricultural and water quality information

USGS Publications Warehouse

Essaid, Hedeff I.; Baker, Nancy T.; McCarthy, Kathleen A.

2016-01-01

Surplus nitrogen (N) estimates, principal component analysis (PCA), and end-member mixing analysis (EMMA) were used in a multisite comparison contrasting the fate of N in diverse agricultural watersheds. We applied PCA-EMMA in 10 watersheds located in Indiana, Iowa, Maryland, Nebraska, Mississippi, and Washington ranging in size from 5 to 1254 km2 with four nested watersheds. Watershed Surplus N was determined by subtracting estimates of crop uptake and volatilization from estimates of N input from atmospheric deposition, plant fixation, fertilizer, and manure for the period from 1987 to 2004. Watershed average Surplus N ranged from 11 to 52 kg N ha−1 and from 9 to 32% of N input. Solute concentrations in streams, overland runoff, tile drainage, groundwater (GW), streambeds, and the unsaturated zone were used in the PCA-EMMA procedure to identify independent components contributing to observed stream concentration variability and the end-members contributing to streamflow and NO3 load. End-members included dilute runoff, agricultural runoff, benthic-processing, tile drainage, and oxic and anoxic GW. Surplus N was larger in watersheds with more permeable soils (Washington, Nebraska, and Maryland) that allowed greater infiltration, and oxic GW was the primary source of NO3 load. Subsurface transport of NO3 in these watersheds resulted in some removal of Surplus N by denitrification. In less permeable watersheds (Iowa, Indiana, and Mississippi), NO3 was rapidly transported to the stream by tile drainage and runoff with little removal. Evidence of streambed removal of NO3 by benthic diatoms was observed in the larger watersheds.

Variations in toxicity of semi-coking wastewater treatment processes and their toxicity prediction.

PubMed

Ma, Xiaoyan; Wang, Xiaochang; Liu, Yongjun; Gao, Jian; Wang, Yongkun

2017-04-01

Chemical analyses and bioassays using Vibrio fischeri and Daphnia magna were conducted to evaluate comprehensively the variation of biotoxicity caused by contaminants in wastewater from a semi-coking wastewater treatment plant (WWTP). Pretreatment units (including an oil-water separator, a phenols extraction tower, an ammonia stripping tower, and a regulation tank) followed by treatment units (including anaerobic-oxic treatment units, coagulation-sedimentation treatment units, and an active carbon adsorption column) were employed in the semi-coking WWTP. Five benzenes, 11 phenols, and five polycyclic aromatic hydrocarbons (PAHs) were investigated as the dominant contaminants in semi-coking wastewater. Because of residual extractant, the phenols extraction process increased acute toxicity to V. fischeri and immobilization and lethal toxicity to D. magna. The acute toxicity of pretreated wastewater to V. fischeri was still higher than that of raw semi-coking wastewater, even though 90.0% of benzenes, 94.8% of phenols, and 81.0% of PAHs were removed. After wastewater pretreatment, phenols and PAHs were mainly removed by anaerobic-oxic and coagulation-sedimentation treatment processes respectively, and a subsequent active carbon adsorption process further reduced the concentrations of all target chemicals to below detection limits. An effective biotoxicity reduction was found during the coagulation-sedimentation and active carbon adsorption treatment processes. The concentration addition model can be applied for toxicity prediction of wastewater from the semi-coking WWTP. The deviation between the measured and predicted toxicity results may result from the effects of compounds not detectable by instrumental analyses, the synergistic effect of detected contaminants, or possible transformation products. Copyright © 2016. Published by Elsevier Inc.

Bioturbation and the role of microniches for sulfate reduction in coastal marine sediments.

PubMed

Bertics, Victoria J; Ziebis, Wiebke

2010-11-01

The effects of bioturbation in marine sediments are mainly associated with an increase in oxic and oxidized zones through an influx of oxygen-rich water deeper into the sediment and the rapid transport of particles between oxic and anoxic conditions. However, macrofaunal activity also can increase the occurrence of reduced microniches and anaerobic processes, such as sulfate reduction. Our goal was to determine the two-dimensional distribution of microniches associated with burrows of a ghost shrimp (Neotrypaea californiensis) and to determine microbial activities. In laboratory experiments, detailed measurements of sulfate reduction rates (SRR) were measured by injecting, in a 1 cm grid, radiolabelled sulfate directly into a narrow aquarium (40 cm × 30 cm × 3 cm) containing the complex burrow of an actively burrowing shrimp. Light-coloured oxidized burrow walls, along with black reduced microniches, were clearly visible through the aquarium walls. Direct injection of radiotracers allowed for whole-aquarium incubation to obtain two-dimensional documentation of sulfate reduction. Results indicated SRR were up to three orders of magnitude higher (140-790 nmol SO(4) (2-) cm(-3) day(-1) ) in reduced microniches associated with burrows when compared with the surrounding sediment. Additionally, some of the subsurface sulfate-reducing microniches associated with the burrow system appeared to be zones of dinitrogen fixation. Bioturbation may also lead to decreased sulfate reduction in other microniches and the sum of the activity in all microniches might not result in a total increase of sulfate reduction compared with non-bioturbated control sediments. © 2010 Society for Applied Microbiology and Blackwell Publishing Ltd.

Exploring the uncultured microeukaryote majority in the oceans: reevaluation of ribogroups within stramenopiles.

PubMed

Massana, Ramon; del Campo, Javier; Sieracki, Michael E; Audic, Stéphane; Logares, Ramiro

2014-04-01

Molecular surveys in planktonic marine systems have unveiled a large novel diversity of small protists. A large part of this diversity belongs to basal heterotrophic stramenopiles and is distributed in a set of polyphyletic ribogroups (described from rDNA sequences) collectively named as MAST (MArine STramenopiles). In the few groups investigated, MAST cells are globally distributed and abundant bacterial grazers, therefore having a putatively large impact on marine ecosystem functioning. The main aim of this study is to reevaluate the MAST ribogroups described so far and to determine whether additional groups can be found. For this purpose, we used traditional and state-of-the-art molecular tools, combining 18S rDNA sequences from publicly available clone libraries, single amplified genomes (SAGs) of planktonic protists, and a pyrosequencing survey from coastal waters and sediments. Our analysis indicated a final set of 18 MAST groups plus 5 new ribogroups within Ochrophyta (named as MOCH). The MAST ribogroups were then analyzed in more detail. Seven were typical of anoxic systems and one of oxic sediments. The rest were clearly members of oxic marine picoplankton. We characterized the genetic diversity within each MAST group and defined subclades for the more diverse (46 subclades in 8 groups). The analyses of sequences within subclades revealed further ecological specializations. Our data provide a renovated framework for phylogenetic classification of the numerous MAST ribogroups and support the notion of a tight link between phylogeny and ecological distribution. These diverse and largely uncultured protists are widespread and ecologically relevant members of marine microbial assemblages.

Effect of Free Ammonia, Free Nitrous Acid, and Alkalinity on the Partial Nitrification of Pretreated Pig Slurry, Using an Alternating Oxic/Anoxic SBR

PubMed Central

Hsieh, Chia-Fang; Guerrero, Lorna; Méndez, Ramón; Mosquera-Corral, Anuska; Vidal, Gladys

2017-01-01

The effect of free ammonia (NH3 or FA), free nitrous acid (HNO2 or FNA), and total alkalinity (TA) on the performance of a partial nitrification (PN) sequencing batch reactor (SBR) treating anaerobically pretreated pig slurry was studied. The SBR was operated under alternating oxic/anoxic (O/A) conditions and was fed during anoxic phases. This strategy allowed using organic matter to partially remove nitrite (NO2−) and nitrate (NO3−) generated during oxic phases. The desired NH4+ to NO2− ratio of 1.3 g N/g N was obtained when an Ammonium Loading Rate (ALR) of 0.09 g NH4+-N/L·d was applied. The system was operated at a solid retention time (SRT) of 15–20 d and dissolved oxygen (DO) levels higher than 3 mg O2/L during the whole operational period. PN mainly occurred caused by the inhibitory effect of FNA on nitrite oxidizing bacteria (NOB). Once HNO2 concentration was negligible, NH4+ was fully oxidized to NO3− in spite of the presence of FA. The use of biomass acclimated to ammonium as inoculum avoided a possible effect of FA on NOB activity. PMID:29018815

Nitrification denitrification enhanced biological phosphorous removal (NDEBPR) occurs in a lab-scale alternating hypoxic/oxic membrane bioreactor.

PubMed

Sibag, Mark; Kim, Han-Seung

2012-01-01

Strict anaerobic or anoxic maintenance of the system and process susceptibility to low organic loading are major concerns in nitrification denitrification enhanced biological phosphorous removal (NDEBPR). The study has initiated NDEBPR in a lab-scale alternating hypoxic/oxic membrane bioreactor by developing an enhanced mixed microbial culture capable of removing 97±2% COD, 99±0.84% NH(3)-N, 90±3% TN, and 96±1% TP-PO(4)(3-) with 20-day SRT. The viable cells ranging from 1.6×10(8) to 2.0×10(8)cells/ml estimated from the total bacterial genomic DNA (6.43-7.83 μg DNA/ml) represented only 5% of the MLVSS indicating low microbial biomass concentration. Reducing the organic load from 1250 to 750 mg COD/ml as glucose did not deteriorate the effluent quality (3.77±1.0 mg N-TN/l; 0.08±0.24 mg NH(3)-N/l; and 0.32±0.10 mg PO(4)(3-)-P/l). These observations are characteristics of activated sludge that harbors denitrifying polyphosphate accumulating organisms (DPAOs). The results showed that NDEBPR can be achieved under alternating hypoxic/oxic conditions. Copyright © 2011 Elsevier Ltd. All rights reserved.

Sphaerotilus natans encrusted with nanoball-shaped Fe(III) oxide minerals formed by nitrate-reducing mixotrophic Fe(II) oxidation.

PubMed

Park, Sunhwa; Kim, Dong-Hun; Lee, Ji-Hoon; Hur, Hor-Gil

2014-10-01

Ferrous iron has been known to function as an electron source for iron-oxidizing microorganisms in both anoxic and oxic environments. A diversity of bacteria has been known to oxidize both soluble and solid-phase Fe(II) forms coupled to the reduction of nitrate. Here, we show for the first time Fe(II) oxidation by Sphaerotilus natans strain DSM 6575(T) under mixotrophic condition. Sphaerotilus natans has been known to form a sheath structure enclosing long chains of rod-shaped cells, resulting in a thick biofilm formation under oxic conditions. Here, we also demonstrate that strain DSM 6575(T) grows mixotrophically with pyruvate, Fe(II) as electron donors and nitrate as an electron acceptor and single cells of strain DSM 6575(T) are dominant under anoxic conditions. Furthermore, strain DSM 6575(T) forms nanoball-shaped amorphous Fe(III) oxide minerals encrusting on the cell surfaces through the mixotrophic iron oxidation reaction under anoxic conditions. We propose that cell encrustation results from the indirect Fe(II) oxidation by biogenic nitrite during nitrate reduction and that causes the bacterial morphological change to individual rod-shaped single cells from filamentous sheath structures. This study extends the group of existing microorganisms capable of mixotrophic Fe(II) oxidation by a new strain, S. natans strain DSM 6575(T) , and could contribute to biogeochemical cycles of Fe and N in the environment. © 2014 The Authors. FEMS Microbiology Ecology published by John Wiley & Sons Ltd on behalf of Federation of European Microbiological Societies.

The microbial plankton of Lake Fryxell, southern Victoria Land, Antarctica during the summers of 1992 and 1994

USGS Publications Warehouse

Laybourn-Parry, J.; James, M.R.; McKnight, Diane M.; Priscu, J.; Spaulding, S.A.; Shiel, R.

1997-01-01

Samples collected from Lake Fryxell, southern Victoria Land, Antarctica in January 1992 and 1994 were analysed for the abundance of bacterioplankton and the diversity and abundance of protistan plankton. At the times of sampling, 14 ciliate species and 10 species of autotrophic flagellate were recorded. The samples contained two species of rotifer (Philodina spp.), which formed the first record of planktonic metazoans in the Dry Valley lakes of this region of Antarctica. Bacterial concentrations ranged between 1.0 and 3.8 x 108 l-1 in the upper oxic waters increasing to 20 x 08 l-1 in the anoxic waters. Heterotrophic flagellates decreased in abundance down the oxygenated water column, disappearing completely at 9 m, and ranged between 0.28 and 7.39 x 105 l-1 in abundance. Autotrophic flagellates were much more abundant exhibiting a number of distinct peaks down the water column (1.89 25.3 x 108 l-1). The ciliated protozoa were very abundant (up to 7720 l-1) in relation to flagellate and bacterial numbers, typical of oligotrophic lakes world-wide. The distribution of the protistan plankton showed marked zonation, probably in response to the differing salinity and temperature gradients in the water column. Possible trophic interactions are discussed and comparisons with other continental Antarctic lakes made.

Sugar beet factory lime affects the mobilization of Cd, Co, Cr, Cu, Mo, Ni, Pb, and Zn under dynamic redox conditions in a contaminated floodplain soil.

PubMed

Shaheen, Sabry M; Rinklebe, Jörg

2017-01-15

The impact of sugar beet factory lime (SBFL) on the release dynamics and mobilization of toxic metals (TMs) under dynamic redox conditions in floodplain soils has not been studied up to date. Therefore, the aim of this study was to verify the scientific hypothesis that SBFL is able to immobilize Cd, Co, Cr, Cu, Fe, Mn, Mo, Ni, Pb, and Zn under different redox potentials (E H ) in a contaminated floodplain soil. For this purpose, the non-treated contaminated soil (CS) and the same soil treated with SBFL (CS+SBFL) were flooded in the laboratory using a highly sophisticated automated biogeochemical microcosm apparatus. The experiment was conducted stepwise from reducing (-13 mV) to oxidizing (+519 mV) soil conditions. Soil pH decreased under oxic conditions in CS (from 6.9 to 4.0) and in CS+SBFL (from 7.5 to 4.4). The mobilization of Cu, Cr, Pb, and Fe were lower in CS+SBFL than in CS under both reducing/neutral and oxic/acidic conditions. Those results demonstrate that SBFL is able to decrease concentrations of these elements under a wide range of redox and pH conditions. The mobilization of Cd, Co, Mn, Mo, Ni, and Zn were higher in CS+SBFL than in CS under reducing/neutral conditions; however, these concentrations showed an opposite behavior under oxic/acidic conditions and were lower in CS+SBFL than in CS. We conclude that SBFL immobilized Cu, Cr, Pb, and Fe under dynamic redox conditions and immobilized Cd, Co, Mn, Mo, Ni, and Zn under oxic acidic conditions; however, the latter elements were mobilized under reducing neutral conditions in the studied soil. Therefore, the addition of SBFL to acid floodplain soils contaminated with TMs might be an important alternative for ameliorating these soils with view to a sustainable management of these soils. Copyright © 2016 Elsevier Ltd. All rights reserved.

Sulfide-driven arsenic mobilization from arsenopyrite and black shale pyrite

USGS Publications Warehouse

Zhu, W.; Young, L.Y.; Yee, N.; Serfes, M.; Rhine, E.D.; Reinfelder, J.R.

2008-01-01

We examined the hypothesis that sulfide drives arsenic mobilization from pyritic black shale by a sulfide-arsenide exchange and oxidation reaction in which sulfide replaces arsenic in arsenopyrite forming pyrite, and arsenide (As-1) is concurrently oxidized to soluble arsenite (As+3). This hypothesis was tested in a series of sulfide-arsenide exchange experiments with arsenopyrite (FeAsS), homogenized black shale from the Newark Basin (Lockatong formation), and pyrite isolated from Newark Basin black shale incubated under oxic (21% O2), hypoxic (2% O2, 98% N2), and anoxic (5% H2, 95% N2) conditions. The oxidation state of arsenic in Newark Basin black shale pyrite was determined using X-ray absorption-near edge structure spectroscopy (XANES). Incubation results show that sulfide (1 mM initial concentration) increases arsenic mobilization to the dissolved phase from all three solids under oxic and hypoxic, but not anoxic conditions. Indeed under oxic and hypoxic conditions, the presence of sulfide resulted in the mobilization in 48 h of 13-16 times more arsenic from arsenopyrite and 6-11 times more arsenic from isolated black shale pyrite than in sulfide-free controls. XANES results show that arsenic in Newark Basin black shale pyrite has the same oxidation state as that in FeAsS (-1) and thus extend the sulfide-arsenide exchange mechanism of arsenic mobilization to sedimentary rock, black shale pyrite. Biologically active incubations of whole black shale and its resident microorganisms under sulfate reducing conditions resulted in sevenfold higher mobilization of soluble arsenic than sterile controls. Taken together, our results indicate that sulfide-driven arsenic mobilization would be most important under conditions of redox disequilibrium, such as when sulfate-reducing bacteria release sulfide into oxic groundwater, and that microbial sulfide production is expected to enhance arsenic mobilization in sedimentary rock aquifers with major pyrite-bearing, black shale formations. ?? 2008 Elsevier Ltd. All rights reserved.

Iron speciation in peats: Chemical and spectroscopic evidence for the co-occurrence of ferric and ferrous iron in organic complexes and mineral precipitates

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bhattacharyya, Amrita; Schmidt, Michael P.; Stavitski, Eli

The speciation of iron (Fe) in organic matter (OM)-rich environments under in situ variable redox conditions is largely unresolved. Peatlands provide a natural setting to study Fe–OM interactions. Utilizing chemical, spectroscopic and theoretical modeling approaches, we report the chemical forms, oxidation states and local coordination environment of naturally occurring Fe in the vertically redox-stratified Manning peatlands of western New York. In addition, we report dominant carbon, sulfur and nitrogen species that can potentially stabilize the various Fe species present in these peatlands. Our results provide clear direct and indirect evidence for the co-occurrence of ferrous (Fe 2+) and ferric (Femore » 3+) iron species in peats under both oxic and anoxic conditions. Iron is mostly present within the operationally defined organic and amorphous (i.e., short range ordered, SRO) fractions; ferric iron primarily as magnetically isolated paramagnetic Fe 3+ in Fe(III)-organic complexes, but also in mineral forms such as ferrihydrite; ferrous iron in tetrahedral coordination in Fe(II)-organic complexes with minor contribution from pyrite. All of the Fe species identified stabilize Fe(III) and/or Fe(II) in anoxic and oxic peats. Fundamental differences are also observed in the relative proportion of C, S and N functionalities of OM in oxic and anoxic peats. Aromatic C=C, ester, phenol and anomeric C (R-O-C-O-R), as well as thiol, sulfide and heterocyclic N functionalities are more prevalent in anoxic peats. Collectively, our experimental evidence suggests iron forms coordination complexes with O-, S- and N-containing functional groups of OM. We posit the co-occurrence of organic and mineral forms of Fe(II) and Fe(III) in both oxic and anoxic peat layers results from dynamic complexation and hydrolysis-precipitation reactions that occur under variable redox conditions. In conclusion, our findings aid in understanding the crucial role OM plays in determining Fe species in soils and sediments.« less

Anoxic conditions drive phosphorus limitation in humid tropical forest soil microorganisms

NASA Astrophysics Data System (ADS)

Gross, A.; Pett-Ridge, J.; Weber, P. K.; Blazewicz, S.; Silver, W. L.

2017-12-01

The elemental stoichiometry of carbon (C), nitrogen (N) and phosphorus (P) of soil microorganisms (C:N:P ratios) regulates transfers of energy and nutrients to higher trophic levels. In humid tropical forests that grow on P-depleted soils, the ability of microbes to concentrate P from their surroundings likely plays a critical role in P-retention and ultimately in forest productivity. Models predict that climate change will cause dramatic changes in rainfall patterns in the humid tropics and field studies have shown these changes can affect the redox state of tropical forest soils, influencing soil respiration and biogeochemical cycling. However, the responses of soil microorganisms to changing environmental conditions are not well known. Here, we incubated humid tropical soils under oxic or anoxic conditions with substrates differing in both C:P stoichiometry and lability, to assess how soil microorganisms respond to different redox regimes. We found that under oxic conditions, microbial C:P ratios were similar to the global optimal ratio (55:1), indicating most microbial cells can adapt to persistent aerated conditions in these soils. However, under anoxic conditions, the ability of soil microbes to acquire soil P declined and their C:P ratios shifted away from the optimal ratio. NanoSIMS elemental imaging of single cells extracted from soil revealed that under anoxic conditions, C:P ratios were above the microbial optimal value in 83% of the cells, in comparison to 41% under oxic conditions. These data suggest microbial growth efficiency switched from being energy limited under oxic conditions to P-limited under anoxic conditions, indicating that, microbial growth in low P humid tropical forests soils may be most constrained by P-limitation when conditions are oxygen-limited. We suggest that differential microbial responses to soil redox states could have important implications for productivity of humid tropical forests under future climate scenarios.

Iron speciation in peats: Chemical and spectroscopic evidence for the co-occurrence of ferric and ferrous iron in organic complexes and mineral precipitates

DOE PAGES

Bhattacharyya, Amrita; Schmidt, Michael P.; Stavitski, Eli; ...

2017-10-31

The speciation of iron (Fe) in organic matter (OM)-rich environments under in situ variable redox conditions is largely unresolved. Peatlands provide a natural setting to study Fe–OM interactions. Utilizing chemical, spectroscopic and theoretical modeling approaches, we report the chemical forms, oxidation states and local coordination environment of naturally occurring Fe in the vertically redox-stratified Manning peatlands of western New York. In addition, we report dominant carbon, sulfur and nitrogen species that can potentially stabilize the various Fe species present in these peatlands. Our results provide clear direct and indirect evidence for the co-occurrence of ferrous (Fe 2+) and ferric (Femore » 3+) iron species in peats under both oxic and anoxic conditions. Iron is mostly present within the operationally defined organic and amorphous (i.e., short range ordered, SRO) fractions; ferric iron primarily as magnetically isolated paramagnetic Fe 3+ in Fe(III)-organic complexes, but also in mineral forms such as ferrihydrite; ferrous iron in tetrahedral coordination in Fe(II)-organic complexes with minor contribution from pyrite. All of the Fe species identified stabilize Fe(III) and/or Fe(II) in anoxic and oxic peats. Fundamental differences are also observed in the relative proportion of C, S and N functionalities of OM in oxic and anoxic peats. Aromatic C=C, ester, phenol and anomeric C (R-O-C-O-R), as well as thiol, sulfide and heterocyclic N functionalities are more prevalent in anoxic peats. Collectively, our experimental evidence suggests iron forms coordination complexes with O-, S- and N-containing functional groups of OM. We posit the co-occurrence of organic and mineral forms of Fe(II) and Fe(III) in both oxic and anoxic peat layers results from dynamic complexation and hydrolysis-precipitation reactions that occur under variable redox conditions. In conclusion, our findings aid in understanding the crucial role OM plays in determining Fe species in soils and sediments.« less

The ecology of fiddler crab Uca forcipata in mangrove forest

NASA Astrophysics Data System (ADS)

Mokhtari, Mohammad; Ghaffar, Mazlan Abd; Usup, Gires; Cob, Zaidi Che

2013-11-01

Fiddler crab burrows increase oxygen dispersion in anoxic mangrove sediment and promote iron reduction and nitrification process over sulfate reduction in subsurface sediment. Therefore it is expected to accelerate decomposition rate under oxic and suboxic conditions. In this study the effect of environmental parameters on the local distribution of U. forcipata and subsequently the effect of crab burrows on sediment characteristics were investigated. Our result indicated that U. forcipata prefers to live in the open mudflats under the shade of mangrove trees. The most important factors determining their presence were sediment texture, porosity, organic content, water content, carbon content and temperature. Measurement of redox potential and iron pools clearly indicated a distinct oxidized layer around burrows although sediment porosity, organic and water content did not differ significantly between burrowed and non-burrowed mudflats and even among the burrow profiles. This result implies the oxidation created by burrowing activity of U .forcipata was not efficient to change physical properties of mangrove sediments.

Nitrogen isotope and trace metal analyses from the Mingolsheim core (Germany): Evidence for redox variations across the Triassic-Jurassic boundary

NASA Astrophysics Data System (ADS)

Quan, Tracy M.; van de Schootbrugge, Bas; Field, M. Paul; Rosenthal, Yair; Falkowski, Paul G.

2008-06-01

The Triassic-Jurassic (T-J) boundary was one of the largest but least understood mass extinction events in the Phanerozoic. We measured bulk organic nitrogen and carbon isotopes and trace metal concentrations from a core near Mingolsheim (Germany) to infer paleoenvironmental conditions associated with this event. Poorly fossiliferous claystones across the boundary have relatively low δ15N values and low concentrations of redox-sensitive elements, characteristic of an oxic environment with significant terrestrial input. The Early Jurassic features enrichment in δ15N coincident with high redox-sensitive element concentrations, indicating an increase in water column denitrification and decreased oxygen concentrations. These redox state variations are concordant with shifts in abundance and species composition in terrestrial and marine microflora. We propose that the mass extinction at the T-J boundary was caused by a series of events resulting in a long period of stratification, deep-water hypoxia, and denitrification in this region of the Tethys Ocean basin.

Redox potential - field measurements - meassured vs. expected values

NASA Astrophysics Data System (ADS)

Stavělová, Monika; Kovář, Martin

2016-04-01

Oxidation and reduction (redox) potential is an important and theoretically very well defined parameter and can be calculated accurately. Its value is determinative for management of many electrochemical processes, chemical redox technologies as well as biotechnologies. To measure the redox value that would correspond with the accuracy level of theoretical calculations in field or operational conditions is however nearly impossible. Redox is in practice measured using combined argentochloride electrode with subsequent value conversion to standard hydrogen electrode (EH). Argentochloride electrode does not allow for precise calibration. Prior to the measurement the accuracy of measurement of particular electrode can only be verified in comparative/control solution with value corresponding with oxic conditions (25°C: +220 mV argentochloride electrode, i.e.. +427 mV after conversion to EH). A commercial product of stabile comparative solution for anoxic conditions is not available and therefore not used in every day practice - accuracy of negative redox is not verified. In this presentation results of two tests will be presented: a) monitoring during dynamic groundwater sampling from eight monitoring wells at a site contaminated by chlorinated ethenes (i.e. post-oxic to anoxic conditions) and b) laboratory test of groundwater contaminated by arsenic from two sites during reaction with highly oxidized compounds of iron (ferrates) - i.e. strongly oxic conditions. In both tests a simultaneous measurement by four argentochloride electrodes was implemented - all four electrodes were prior to the test maintained expertly. The redox values of testing electrodes in a comparative solution varied by max. 6 mV. The redox values measured by four electrodes in both anoxic and oxic variant varied by tens to a hundred mV, while with growing time of test the variance of measured redox values increased in both oxic and anoxic variant. Therefore the interpretation of measured redox data must be approached keeping in mind that their accuracy does not correspond with theoretical calculations and their values must be assessed in combination with other parameters - e.g. in case of interpretations of measured redox during remediation of contaminated sites it is appropriate to assess these values together with determined concentrations of significant terminal electron acceptors (TEA) whose laboratory determination is more accurate (NO3-, NO2-, Fe2+,Mn2+ , SO42-, H2S+S2-,CH4….). Acknowledgement: This study has been funded by the Technology Agency of the Czech Republic within the research project Nanobiowat (No. TE01010218), and by AECOM CZ, s.r.o.

Potential for Microbial Degradation of cis-Dichloroethene and Vinyl Chloride in Streambed Sediment at the U.S. Department of Energy, Kansas City Plant, Missouri, 2008

USGS Publications Warehouse

Bradley, Paul M.

2009-01-01

A series of carbon-14 (14C) radiotracer-based microcosm experiments was conducted to assess the mechanisms and products of degradation of cis-dichloroethene (cis-DCE) and vinyl chloride (VC) in streambed sediments at the U.S. Department of Energy, Kansas City Plant in Kansas City, Missouri. The focus of the investigation was the potential for biotic and abiotic cis-DCE and VC degradation in surficial and underlying hyporheic sediment from the Blue River and its tributaries, Indian Creek and Boone Creek. Substantial degradation of [1,2-14C] cis-DCE and [1,2-14C] VC to 14C-carbon dioxide (14CO2) was observed in all viable surficial sediment microcosms prepared under oxic conditions. No significant accumulation of reductive dechlorination products was observed under these oxic incubation conditions. The results indicate that microbial mineralization processes involving direct oxidation or co-metabolic oxidation are the primary mechanisms of cis-DCE and VC biodegradation in oxic stream sediment at the Kansas City Plant. Substantial mineralization of [1,2-14C] VC also was observed in all viable surficial sediment microcosms incubated in the absence of detectable oxygen (dissolved oxygen concentrations less than 25 micrograms per liter). In general, the accumulation of mineralization products (14CO2 and 14C-methane [14CH4]) predominated with only trace-level detection of the reductive dechlorination product, 14C-ethene. In contrast, microbial degradation of [1,2-14C] cis-DCE by reductive dechlorination or mineralization was not significant in the absence of detectable oxygen. The potential for [1,2-14C] VC biodegradation also was significant in sediments from the deeper hyporheic zones under oxic conditions and in the absence of detectable oxygen. In this study, microbial degradation of [1,2-14C] cis-DCE was not significant in hyporheic sediment treatments under either oxygen condition. Taken together, the results indicate that microbial mineralization processes in streambed sediments at the Kansas City Plant can be an important component of cis-DCE and VC degradation under oxic conditions and of VC degradation even in the absence of detectable oxygen. These results demonstrate that an evaluation of the efficiency of in situ cis-DCE and VC biodegradation in streambed sediments, based solely on observed accumulations of reduced daughter products, may underestimate substantially the total extent of contaminant biodegradation and, thus, the potential importance of the hyporheic zone and streambed sediments as barriers to the discharge of contaminated groundwater.

Spatiotemporal analysis of microbial community dynamics during seasonal stratification events in a freshwater lake (Grand Lake, OK, USA)

PubMed Central

Morrison, Jessica M.; Baker, Kristina D.; Zamor, Richard M.; Nikolai, Steve; Elshahed, Mostafa S.

2017-01-01

Many freshwater lakes undergo seasonal stratification, where the formation of phototrophic blooms in the epilimnion and subsequent sedimentation induces hypoxia/anoxia in the thermocline and hypolimnion. This autochthonously produced biomass represents a major seasonal organic input that impacts the entire ecosystem. While the limnological aspects of this process are fairly well documented, relatively little is known regarding the microbial community response to such events, especially in the deeper anoxic layers of the water column. Here, we conducted a spatiotemporal survey of the particle-associated and free-living microbial communities in a warm monomictic freshwater reservoir (Grand Lake O’ the Cherokees) in northeastern Oklahoma, USA. Pre-stratification samples (March) harbored a homogeneous community throughout the oxygenated water column dominated by typical oligotrophic aquatic lineages (acl clade within Actinobacteria, and Flavobacterium within the Bacteroidetes). The onset of phototrophic blooming in June induced the progression of this baseline community into two distinct trajectories. Within the oxic epilimnion, samples were characterized by the propagation of phototrophic (Prochlorococcus), and heterotrophic (Planctomycetes, Verrucomicrobia, and Beta-Proteobacteria) lineages. Within the oxygen-deficient thermocline and hypolimnion, the sedimentation of surface biomass induced the development of a highly diverse community, with the enrichment of Chloroflexi, “Latescibacteria”, Armatimonadetes, and Delta-Proteobacteria in the particle-associated fraction, and Gemmatimonadetes and “Omnitrophica” in the free-living fraction. Our work documents the development of multiple spatially and temporally distinct niches during lake stratification, and supports the enrichment of multiple yet-uncultured and poorly characterized lineages in the lake’s deeper oxygen-deficient layers, an ecologically relevant microbial niche that is often overlooked in lakes diversity surveys. PMID:28493994

The effect of widespread early aerobic marine ecosystems on methane cycling and the Great Oxidation

NASA Astrophysics Data System (ADS)

Daines, Stuart J.; Lenton, Timothy M.

2016-01-01

The balance of evidence suggests that oxygenic photosynthesis had evolved by 3.0-2.7 Ga, several hundred million years prior to the Great Oxidation ≈2.4 Ga. Previous work has shown that if oxygenic photosynthesis spread globally prior to the Great Oxidation, this could have supported widespread aerobic ecosystems in the surface ocean, without oxidising the atmosphere. Here we use a suite of models to explore the implications for carbon cycling and the Great Oxidation. We find that recycling of oxygen and carbon within early aerobic marine ecosystems would have restricted the balanced fluxes of methane and oxygen escaping from the ocean, lowering the atmospheric concentration of methane in the Great Oxidation transition and its aftermath. This in turn would have minimised any bi-stability of atmospheric oxygen, by weakening a stabilising feedback on oxygen from hydrogen escape to space. The result would have been a more reversible and probably episodic rise of oxygen at the Great Oxidation transition, consistent with existing geochemical evidence. The resulting drop in methane levels to ≈10 ppm is consistent with climate cooling at the time but adds to the puzzle of what kept the rest of the Proterozoic warm. A key test of the scenario of abundant methanotrophy in oxygen oases before the Great Oxidation is its predicted effects on the organic carbon isotope (δ13Corg) record. Our open ocean general circulation model predicts δC13org ≈ - 30 to -45‰ consistent with most data from 2.65 to 2.45 Ga. However, values of δC13org ≈ - 50 ‰ require an extreme scenario such as concentrated methanotroph production where shelf-slope upwelling of methane-rich water met oxic shelf water.

Linking Belowground Plant Traits With Ecosystem Processes: A Multi-Biome Perspective

NASA Astrophysics Data System (ADS)

Iversen, C. M.; Norby, R. J.; Childs, J.; McCormack, M. L.; Walker, A. P.; Hanson, P. J.; Warren, J.; Sloan, V. L.; Sullivan, P. F.; Wullschleger, S.; Powell, A. S.

2015-12-01

Fine plant roots are short-lived, narrow-diameter roots that play an important role in ecosystem carbon, water, and nutrient cycling in biomes ranging from the tundra to the tropics. Root ecologists make measurements at a millimeter scale to answer a question with global implications: In response to a changing climate, how do fine roots modulate the exchange of carbon between soils and the atmosphere and how will this response affect our future climate? In a Free-Air CO2 Enrichment experiment in Oak Ridge, TN, elevated [CO2] caused fine roots to dive deeper into the soil profile in search of limiting nitrogen, which led to increased soil C storage in deep soils. In contrast, the fine roots of trees and shrubs in an ombrotrophic bog are constrained to nutrient-poor, oxic soils above the average summer water table depth, though this may change with warmer, drier conditions. Tundra plant species are similarly constrained to surface organic soils by permafrost or waterlogged soils, but have many adaptations that alter ecosystem C fluxes, including aerenchyma that oxygenate the rhizosphere but also allow direct methane flux to the atmosphere. FRED, a global root trait database, will allow terrestrial biosphere models to represent the complexity of root traits across the globe, informing both model representation of ecosystem C and nutrient fluxes, but also the gaps where measurements are needed on plant-soil interactions (for example, in the tropical biome). While the complexity of mm-scale measurements may never have a place in large-scale global models, close collaboration between empiricists and modelers can help to guide the scaling of important, yet small-scale, processes to quantify their important roles in larger-scale ecosystem fluxes.

Laboratory Investigation of Complex Conductivity and Magnetic Susceptibility on Natural Iron Oxide Coated Sand

NASA Astrophysics Data System (ADS)

Wang, C.; Slater, L. D.; Day-Lewis, F. D.; Briggs, M. A.

2017-12-01

Redox reactions occurring at the oxic/anoxic interface where groundwater discharges to surface water commonly result in iron oxide deposition that coats sediment grains. With relatively large total surface area, these iron oxide coated sediments serve as a sink for sorption of dissolved contaminants, although this sink may be temporary if redox conditions fluctuate with varied flow conditions. Characterization of the distribution of iron oxides in streambed sediments could provide valuable understanding of biogeochemical reactions and the ability of a natural system to sorb contaminants. Towards developing a field methodology, we conducted laboratory spectral induced polarization (SIP) and magnetic susceptibility (MS) measurements on natural iron oxide coated sand (Fe-sand) with grain sizes ranging from 0.3 to 2.0 mm in order to assess the sensitivity of these measurements to iron oxides in sediments. The Fe-sand was also sorted by sieving into various grain sizes to study the impact of grain size on the polarization mechanisms. The unsorted Fe-sand saturated with 0.01 S/m NaCl solution exhibited a distinct phase response ( > 4 mrad) in the frequency range from 0.001 to 100 Hz whereas regular silica sand was characterized by a phase response less than 1 mrad under the same conditions. The presence of iron oxide substantially increased MS (3.08×10-3 SI) over that of regular sand ( < 10-5 SI). An increase of both phase peak and relaxation time was found with increasing grain size of the sorted Fe-sand. Laboratory results demonstrated that SIP and MS may be well suited to mapping the distribution of iron oxides in streambed sediments associated with anoxic groundwater discharge.

A high-resolution Late Quaternary upwelling record from the anoxic Cariaco Basin, Venezuela

NASA Astrophysics Data System (ADS)

Peterson, L. C.; Overpeck, J. T.; Kipp, N. G.; Imbrie, J.

1991-02-01

Results are presented of a high-resolution study of the planktonic foraminiferal faunas from two piston cores recovered from the Cariaco Basin in the southern Caribbean Sea. The Cariaco Basin is a small anoxic marine basin on the northern continental margin of Venezuela in an area today characterized by both seasonal trade wind-induced upwelling and pronounced dry and wet seasons. Our data indicate that large changes in the intensity of upwelling, and hence trade wind strength, occurred in this region during the last glacial-interglacial transition and throughout the Holocene. During the last glacial lowstand of sea level, the Cariaco Basin was effectively isolated from the open Caribbean along its northern margin by the then largely emergent Tortuga Bank. Oxic conditions existed in the deep Cariaco Basin at this time, and surface productivity was low. About 12,600 years ago, the abrupt initiation of strong upwelling over the basin and the onset of permanent anoxia in the deep waters are coincident with the rapid rise of sea level that accompanied the peak interval of meltwater discharge from the Laurentide Ice Sheet into the Gulf of Mexico. Strong upwelling between 12,600 and about 10,000 years ago may be related to intensified trade winds resulting, in part, from cooler sea surface temperatures in the Caribbean and Gulf of Mexico. After about 10,000 years ago, upwelling intensity was reduced, though highly variable. A preliminary frequency domain analysis of the Holocene portion of the Cariaco Basin time series suggests that solar forcing may explain a significant component of the century-scale variability observed in the record of upwelling and trade wind strength.

Rare earth elements (REE) as natural and applied tracers in the catchment area of Gessental valley, former uranium mining area of Eastern Thuringia, Germany

NASA Astrophysics Data System (ADS)

Buechel, G.; Merten, D.; Geletneky, J. W.; Kothe, E.

2003-04-01

Between 1947 and 1990 about 113.000 t of uranium were excavated at the former uranium mining site of Ronneburg (Eastern Thuringia, Germany). The legacy consists of more than 200 million m^3 of metasedimentary rocks rich in organic matter, sulfides and heavy metals originally deposited in mining heaps at the surface. The metasedimentary rocks formed under anoxic conditions about a 400 Mio. years ago are now exposed to oxic conditions. The oxidation of markasite and pyrite results in the formation of H_2SO_4. The formation of acid mine drainage (AMD) leads to high concentrations of uranium, rare earth elements (REE) and other heavy metals in surface water, seepage water and groundwater. This mobilization is due to alteration enhanced by high microbial activity and low pH. The tolerance mechanisms towards heavy metal pollution of soil substrate and surface/groundwater has allowed the selection of microbes which have, e.g. specific transporter genes and which are associated to plants in symbiotic interactions like mycorrhiza. In order to follow the processes linking alteration of metasedimentary rocks to biological systems the use of tracers is needed. One group of such tracers occuring in high concentrations in the water phase at the Ronneburg mining site are the REE (La-Lu) which are featured by very similar chemical behaviour. They show smooth but continuous variations of their chemical behaviour as a function of atomic number. For seepage water of the waste rock dump Nordhalde - sampled over a period of two years - the shale normalized REE patterns show enrichment of heavy REE and only minor variations, although the concentration differs. At sampling points in the surface water and in groundwater rather similar REE patterns were observed. Thus, REE can be used as tracers to identify diffuse inflow of REE-rich acid mine drainage of the dumps into the creek and the sediments. The absolute concentrations of REE in the creek and in ground water are up to 1000 times less than in seepage water due to mixing and (co)precipitation of REE. Lu/La and Sm/La relations show a significant decrease with increasing distance from the dump caused by preferential (co)precipitation of heavy REE with amorphous Fe-hydroxides along the Gessenbach. Thus, REE patterns can not only be used as tracers but also to study processes. In contrast to the patterns of the seepage, the REE patterns of the Silurian rocks as determined by LA-ICP-MS feature rather flat patterns with enrichment of middle REE (Sm - Dy). Results from batch experiments show preferentially leaching of heavy REE for all investigated source rocks. The highest absolute concentrations of REE appear in the eluates of the Silurian 'Ockerkalk'. Since the REE pattern closely reflects the pattern found in the seepage water it is assumed to be the most important source for the occurence of the REE pattern observed in seepage water. Studies of microbial heavy metal retention were performed by direct incubation of seepage water using well characterized fungal and bacterial strains. Using the bacterium Escherichia coli for incubation of seepage water sorption of heavy metals to biomass was observed. Use of the fungus Schizophyllum commune for incubation, however, has a much more pronounced effect including significant fractionation of REE pointing to the possibility of a specific active uptake mechanism. Bioextraction with bacteria and fungal mycelia might be an alternative to plant growth and phytoextraction and might be preferable for AMD water treatment since no soil substrate is necessary. Future research must be directed towards genes for active transport, intra- or extracellular storage proteins and their application. Biotechnological use of such genes in, e.g., strains of E. coli, might yield highly useful bioremediation strains that can help to reduce the ecological effects of pollution resulting from former mining activities.

Tracking photosynthetic sulfide oxidation in a meromictic lake using sulfate δ34S and δ18O

NASA Astrophysics Data System (ADS)

Gilhooly, W. P.; Reinhard, C.; Lyons, T. W.; Glass, J. B.

2012-12-01

Phototrophic sulfur bacteria oxidize sulfide and fix carbon dioxide in the presence of sunlight without producing oxygen. Environmental conditions in the Paleo- and Mesoproterozoic, when atmospheric oxygen concentrations were at low levels and portions of the oceans were anoxic and sulfidic (euxinic), were conducive to widespread carbon fixation by anoxygenic photosynthesis. This pathway may have helped sustain euxinic conditions in the Proterozoic water column. With limited organic biomarker and geochemical evidence for widespread production of anoxygenic phototrophs, however, additional proxies are needed to fingerprint paleoecological and biogeochemical signals associated with photic zone euxinia. Paired δ34S and δ18O from ancient sulfates (gypsum, barite, or CAS) may offer an added constraint on the history and ecological dominance of photosynthetic S-oxidation. Sulfate-oxygen can fractionate during sulfate reduction, but the extent of isotopic enrichment is controlled either by kinetic isotope effects imparted during intracellular enzymatic steps or equilibrium oxygen exchange with ambient water. An improved understanding of these processes can be gained from modern natural environments. Mahoney Lake is a density-stratified lake located within the White Lake Basin of British Columbia. The euxinic water column supports a dense plate of purple sulfur bacteria (Amoebobacter purpureus) that thrives where free sulfide intercepts the photic zone at ~7 m water depth. We analyzed the isotopic composition of sulfate (δ34SSO4 and δ18OSO4), sulfide (δ34SH2S), and water (δ18OH2O) to track the potentially coupled processes of dissimilatory sulfate reduction and phototrophic sulfide oxidation within this meromictic lake. Large isotopic offsets observed between sulfate and sulfide within the monimolimnion (δ34SSO4-H2S = 51‰) and within pore waters along the oxic margin (δ34SSO4-H2S >50‰) are consistent with sulfate reduction in both the sediments and the anoxic water column. Given the high sulfide concentrations of the lake ([H2S] = 30 mM), sulfur disproportionation is likely inoperable, and so the large instantaneous fractionations are best explained by single-step sulfate reduction. The offset between sulfate and sulfide decreases at the chemocline (δ34SSO4-H2S = 37‰), a trend possibly explained by sulfide oxidation or decreasing sulfate reduction rates. Sulfate exhibits a curvilinear response in δ18OSO4/δ34SSO4 that approaches δ18OSO4 values (~24-33‰) in equilibrium with ambient water (δ18OH2O = -2.2‰). Although an inverse relationship between δ18OSO4/δ18OH2O is inconsistent with chemical sulfide oxidation (typically a positive relationship), fine-scale variations in δ34SSO4 and δ18OSO4 at the chemocline imply sulfate reduction coupled with near quantitative reoxidation by A. purpureus. Although observed within the microbial plate, this photosynthetic S-bacteria biosignature is restricted to the oxic/anoxic transition zone and is apparently swamped by the more prevalent process of sulfate reduction operative throughout the anoxic water column and sediment pore waters.

The biogeochemical iron cycle and astrobiology

NASA Astrophysics Data System (ADS)

Schröder, Christian; Köhler, Inga; Muller, Francois L. L.; Chumakov, Aleksandr I.; Kupenko, Ilya; Rüffer, Rudolf; Kappler, Andreas

2016-12-01

Biogeochemistry investigates chemical cycles which influence or are influenced by biological activity. Astrobiology studies the origin, evolution and distribution of life in the universe. The biogeochemical Fe cycle has controlled major nutrient cycles such as the C cycle throughout geological time. Iron sulfide minerals may have provided energy and surfaces for the first pioneer organisms on Earth. Banded iron formations document the evolution of oxygenic photosynthesis. To assess the potential habitability of planets other than Earth one looks for water, an energy source and a C source. On Mars, for example, Fe minerals have provided evidence for the past presence of liquid water on its surface and would provide a viable energy source. Here we present Mössbauer spectroscopy investigations of Fe and C cycle interactions in both ancient and modern environments. Experiments to simulate the diagenesis of banded iron formations indicate that the formation of ferrous minerals depends on the amount of biomass buried with ferric precursors rather than on the atmospheric composition at the time of deposition. Mössbauer spectra further reveal the mutual stabilisation of Fe-organic matter complexes against mineral transformation and decay of organic matter into CO2. This corresponds to observations of a `rusty carbon sink' in modern sediments. The stabilisation of Fe-organic matter complexes may also aid transport of particulate Fe in the water column while having an adverse effect on the bioavailability of Fe. In the modern oxic ocean, Fe is insoluble and particulate Fe represents an important source. Collecting that particulate Fe yields small sample sizes that would pose a challenge for conventional Mössbauer experiments. We demonstrate that the unique properties of the beam used in synchrotron-based Mössbauer applications can be utilized for studying such samples effectively. Reactive Fe species often occur in amorphous or nanoparticulate form in the environment and are therefore difficult to study with standard mineralogical tools. Sequential extraction techniques are commonly used as proxies. We provide an example where Mössbauer spectroscopy can replace sequential extraction techniques where mineralogical information is sought. Where mineral separation is needed, for example in the investigation of Fe or S isotope fractionation, Mössbauer spectroscopy can help to optimize sequential extraction procedures. This can be employed in a large number of investigations of soils and sediments, potentially even for mineral separation to study Fe and S isotope fractionation in samples returned from Mars, which might reveal signatures of biological activity. When looking for the possibility of life outside Earth, Jupiter's icy moon Europa is one of the most exciting places. It may be just in reach for a Mössbauer spectrometer deployed by a future lander to study the red streak mineral deposits on its surface to look for clues about the composition of the ocean hidden under the moon's icy surface.

Flow and sorption controls of groundwater arsenic in individual boreholes from bedrock aquifers in central Maine, USA

USGS Publications Warehouse

Yang, Qiang; Culbertson, Charles W.; Nielsen, Martha G.; Schalk, Charles W.; Johnson, Carole D.; Marvinney, Robert G.; Stute, Martin; Zheng, Yan

2014-01-01

To understand the hydrogeochemical processes regulating well water arsenic (As) evolution in fractured bedrock aquifers, three domestic wells with [As] up to 478 μg/L are investigated in central Maine. Geophysical logging reveals that fractures near the borehole bottom contribute 70-100% of flow. Borehole and fracture water samples from various depths show significant proportions of As (up to 69%) and Fe (93-99%) in particulates (>0.45 μm). These particulates and those settled after a 16-day batch experiment contain 560-13,000 g/kg of As and 14-35% weight/weight of Fe. As/Fe ratios (2.5-20 mmol/mol) and As partitioning ratios (adsorbed/dissolved [As], 20,000-100,000 L/kg) suggest that As is sorbed onto amorphous hydrous ferric oxides. Newly drilled cores also show enrichment of As (up to 1300 mg/kg) sorbed onto secondary iron minerals on the fracture surfaces. Pumping at high flow rates induces large decreases in particulate As and Fe, a moderate increase in dissolved [As] and As(III)/As ratio, while little change in major ion chemistry. The δD and δ18O are similar for the borehole and fracture waters, suggesting a same source of recharge from atmospheric precipitation. Results support a conceptual model invoking flow and sorption controls on groundwater [As] in fractured bedrock aquifers whereby oxygen infiltration promotes the oxidation of As-bearing sulfides at shallower depths in the oxic portion of the flow path releasing As and Fe; followed by Fe oxidation to form Fe oxyhydroxide particulates, which are transported in fractures and sorb As along the flow path until intercepted by boreholes. In the anoxic portions of the flow path, reductive dissolution of As-sorbed iron particulates could re-mobilize As. For exposure assessment, we recommend sampling of groundwater without filtration to obtain total As concentration in groundwater.

Flow and sorption controls of groundwater arsenic in individual boreholes from bedrock aquifers in central Maine, USA.

PubMed

Yang, Qiang; Culbertson, Charles W; Nielsen, Martha G; Schalk, Charles W; Johnson, Carole D; Marvinney, Robert G; Stute, Martin; Zheng, Yan

2015-02-01

To understand the hydrogeochemical processes regulating well water arsenic (As) evolution in fractured bedrock aquifers, three domestic wells with [As] up to 478 μg/L are investigated in central Maine. Geophysical logging reveals that fractures near the borehole bottom contribute 70-100% of flow. Borehole and fracture water samples from various depths show significant proportions of As (up to 69%) and Fe (93-99%) in particulates (>0.45 μm). These particulates and those settled after a 16-day batch experiment contain 560-13,000 mg/kg of As and 14-35% weight/weight of Fe. As/Fe ratios (2.5-20 mmol/mol) and As partitioning ratios (adsorbed/dissolved [As], 20,000-100,000 L/kg) suggest that As is sorbed onto amorphous hydrous ferric oxides. Newly drilled cores also show enrichment of As (up to 1300 mg/kg) sorbed onto secondary iron minerals on the fracture surfaces. Pumping at high flow rates induces large decreases in particulate As and Fe, a moderate increase in dissolved [As] and As(III)/As ratio, while little change in major ion chemistry. The δD and δ(18)O are similar for the borehole and fracture waters, suggesting a same source of recharge from atmospheric precipitation. Results support a conceptual model invoking flow and sorption controls on groundwater [As] in fractured bedrock aquifers whereby oxygen infiltration promotes the oxidation of As-bearing sulfides at shallower depths in the oxic portion of the flow path releasing As and Fe; followed by Fe oxidation to form Fe oxyhydroxide particulates, which are transported in fractures and sorb As along the flow path until intercepted by boreholes. In the anoxic portions of the flow path, reductive dissolution of As-sorbed iron particulates could re-mobilize As. For exposure assessment, we recommend sampling of groundwater without filtration to obtain total As concentration in groundwater. Copyright © 2014 Elsevier B.V. All rights reserved.

Flow and sorption controls of groundwater arsenic in individual boreholes from bedrock aquifers in central Maine, USA

PubMed Central

Yang, Qiang; Culbertson, Charles W.; Nielsen, Martha G.; Schalk, Charles W.; Johnson, Carole D.; Marvinney, Robert G.; Stute, Martin; Zheng, Yan

2014-01-01

To understand the hydrogeochemical processes regulating well water arsenic (As) evolution in fractured bedrock aquifers, three domestic wells with [As] up to 478 µg/L are investigated in central Maine. Geophysical logging reveals that fractures near the borehole bottom contribute 70–100% of flow. Borehole and fracture water samples from various depths show significant proportions of As (up to 69%) and Fe (93–99%) in particulates (>0.45 µm). These particulates and those settled after a 16-day batch experiment contain 560–13,000 mg/kg of As and 14–35% weight/weight of Fe. As/Fe ratios (2.5–20 mmole/mole) and As partitioning ratios (adsorbed/dissolved [As], 20,000–100,000 L/kg) suggest that As is sorbed onto amorphous hydrous ferric oxides. Newly drilled cores also show enrichment of As (up to 1,300 mg/kg) sorbed onto secondary iron minerals on the fracture surfaces. Pumping at high flow rates induces large decreases in particulate As and Fe, a moderate increase in dissolved [As] and As(III)/As ratio, while little change in major ion chemistry. The δD and δ18O are similar for the borehole and fracture waters, suggesting a same source of recharge from atmospheric precipitation. Results support a conceptual model invoking flow and sorption controls on groundwater [As] in fractured bedrock aquifers whereby oxygen infiltration promotes oxidation of As-bearing sulfides at shallower depths in the oxic portion of the flow path releasing As and Fe; followed by Fe oxidation to form Fe oxyhydroxide particulates, which are transported in fractures and sorb As along the flow path until intercepted by boreholes. In the anoxic portions of the flow path, reductive dissolution of As-sorbed iron particulates could re-mobilize As. For exposure assessment, we recommend sampling of groundwater without filtration to obtain total As concentration in groundwater. PMID:24842411

Regional patterns of labile organic carbon flux in North American Arctic Margin (NAAM) as reflected by redox sensitive-elements distributions in sediments

NASA Astrophysics Data System (ADS)

Gobeil, C.; Kuzyk, Z. Z. A.; Goni, M. A.; Macdonald, R. W.

2016-02-01

Concentrations of elements (S, Mn, Mo, U, Cd, Re) providing insights on organic C metabolized through oxidative processes at the sea floor were measured in 27 sediment cores collected along a section extending from the North Bering Sea to Davis Strait via the Canadian Archipelago. Sedimentary distributions and accumulation rates of these elements were used to i) document the relative importance of aerobic versus anaerobic degradation of organic C in NAAM sediments, ii) infer variations in water column carbon flux and iii) estimate the importance of this margin as a sink for key elements in the Arctic and global ocean. Distributions of Mn, total S and reduced inorganic S demonstrated that most sediments along the NAAM had relatively thick (>1 cm) surface oxic layers, underlain by sediments with weakly reducing conditions and limited sulphate reduction. Strongly reducing conditions accompanied by substantial sedimentary pyrite burial occurred only in certain subregions, including the Bering-Chukchi Shelves, shallow portions of Barrow Canyon. Estimated accumulation rates of authigenic S, Mo, Cd and U, and total Re displayed marked spatial variability that was related to sedimentary redox conditions induced by the supply of labile C to the seabed, as shown by significant relationships between the accumulation rates and vertical C flux, estimated from regional primary production values and water depth at the coring sites. High primary production combined with shallow water columns drive elevated rates of authigenic trace element accumulation in sediments from the Bering-Chukchi Shelves whereas low production combined with moderately deep conditions drive low rates of accumulation in sediments in the Beaufort Shelf, Davis Strait and Canadian Archipelago. Using the average authigenic trace element accumulation rates in sediments from the various regions, we submit that the shelves along the NAAM margin are important sinks in global marine biogeochemical budgets.

Reoxidation of estuarine sediments during simulated resuspension events: Effects on nutrient and trace metal mobilisation

NASA Astrophysics Data System (ADS)

Vidal-Durà, Andrea; Burke, Ian T.; Stewart, Douglas I.; Mortimer, Robert J. G.

2018-07-01

Estuarine environments are considered to be nutrient buffer systems as they regulate the delivery of nutrients from rivers to the ocean. In the Humber Estuary (UK) seawater and freshwater mixing during tidal cycles leads to the mobilisation of oxic surface sediments (0-1 cm). However, less frequent seasonal events can also mobilise anoxic subsurface (5-10 cm) sediments, which may have further implications for the estuarine geochemistry. A series of batch experiments were carried out on surface and subsurface sediments taken from along the salinity gradient of the Humber Estuary. The aim was to investigate the geochemical processes driving major element (N, Fe, S, and Mn) redox cycling and trace metal behaviour during simulated resuspension events. The magnitude of major nutrient and metal release was significantly greater during the resuspension of outer estuarine sediments rather than from inner estuarine sediments. When comparing resuspension of surface versus subsurface sediment, only the outer estuary experiments showed significant differences in major nutrient behaviour with sediment depth. In general, any ammonium, manganese and trace metals (Cu and Zn) released during the resuspension experiments were rapidly removed from solution as new sorption sites (i.e. Fe/Mn oxyhydroxides) formed. Therefore Humber estuary sediments showed a scavenging capacity for these dissolved species and hence may act as an ultimate sink for these elements. Due to the larger aerial extent of the outer estuary intertidal mudflats in comparison with the inner estuary area, the mobilisation of the outer estuary sediments (more reducing and richer in sulphides and iron) may have a greater impact on the transport and cycling of nutrients and trace metals. Climate change-associated sea level rise combined with an increasing frequency of major storm events in temperate zones, which are more likely to mobilise deeper sediment regions, will impact the nutrient and metal inputs to the coastal waters, and therefore enhance the likelihood of eutrophication in this environment.

History of water-column anoxia in the Black Sea indicated by pyrite framboid size distributions

USGS Publications Warehouse

Wilkin, R.T.; Arthur, M.A.; Dean, W.E.

1997-01-01

A detailed study of size distributions of framboidal pyrite in Holocene Black Sea sediments establishes the timing of a change from deposition under an oxic water column to deposition under an anoxic and sulfidic water column. In the most recent carbonate-rich sediments (Unit I) and in the organic carbon-rich sapropel (Unit II), framboid size distributions are remarkably uniform (mean diameter= 5 ??m); over 95% of the framboids in Unit I and Unit II are < 7 ??m in diameter. These properties of framboidal pyrite are consistent with framboid nucleation and growth within an anoxic and sulfidic water column, followed by transport to the sediment-water interface, cessation of pyrite growth due to the exhaustion of reactive iron, and subsequent burial. In contrast, the organic carbon-poor sediments of lacustrine Unit III contain pyrite framboids that are generally much larger in size (mean diameter = 10 ??m). In Unit III, over 95% of the framboids are < 25 ??m in diameter, 40% of framboids are between 7 ??m and 25 ??m, and framboids up to 50 ??m in diameter are present. This distribution of sizes suggests framboid nucleation and growth within anoxic sediment porewaters. These new data on size distributions of framboidal pyrite confirm that the development of water-column anoxia in the Black Sea coincided with the initiation of deposition of laminated Unit II sapropels.

Sulfur and oxygen isotope insights into sulfur cycling in shallow-sea hydrothermal vents, Milos, Greece

PubMed Central

2014-01-01

Shallow-sea (5 m depth) hydrothermal venting off Milos Island provides an ideal opportunity to target transitions between igneous abiogenic sulfide inputs and biogenic sulfide production during microbial sulfate reduction. Seafloor vent features include large (>1 m2) white patches containing hydrothermal minerals (elemental sulfur and orange/yellow patches of arsenic-sulfides) and cells of sulfur oxidizing and reducing microorganisms. Sulfide-sensitive film deployed in the vent and non-vent sediments captured strong geochemical spatial patterns that varied from advective to diffusive sulfide transport from the subsurface. Despite clear visual evidence for the close association of vent organisms and hydrothermalism, the sulfur and oxygen isotope composition of pore fluids did not permit delineation of a biotic signal separate from an abiotic signal. Hydrogen sulfide (H2S) in the free gas had uniform δ34S values (2.5 ± 0.28‰, n = 4) that were nearly identical to pore water H2S (2.7 ± 0.36‰, n = 21). In pore water sulfate, there were no paired increases in δ34SSO4 and δ18OSO4 as expected of microbial sulfate reduction. Instead, pore water δ34SSO4 values decreased (from approximately 21‰ to 17‰) as temperature increased (up to 97.4°C) across each hydrothermal feature. We interpret the inverse relationship between temperature and δ34SSO4 as a mixing process between oxic seawater and 34S-depleted hydrothermal inputs that are oxidized during seawater entrainment. An isotope mass balance model suggests secondary sulfate from sulfide oxidation provides at least 15% of the bulk sulfate pool. Coincident with this trend in δ34SSO4, the oxygen isotope composition of sulfate tended to be 18O-enriched in low pH (<5), high temperature (>75°C) pore waters. The shift toward high δ18OSO4 is consistent with equilibrium isotope exchange under acidic and high temperature conditions. The source of H2S contained in hydrothermal fluids could not be determined with the present dataset; however, the end-member δ34S value of H2S discharged to the seafloor is consistent with equilibrium isotope exchange with subsurface anhydrite veins at a temperature of ~300°C. Any biological sulfur cycling within these hydrothermal systems is masked by abiotic chemical reactions driven by mixing between low-sulfate, H2S-rich hydrothermal fluids and oxic, sulfate-rich seawater. PMID:25183951

Effects of bottom water dissolved oxygen variability on copper and lead fractionation in the sediments across the oxygen minimum zone, western continental margin of India.

PubMed

Chakraborty, Parthasarathi; Chakraborty, Sucharita; Jayachandran, Saranya; Madan, Ritu; Sarkar, Arindam; Linsy, P; Nath, B Nagender

2016-10-01

This study describes the effect of varying bottom-water oxygen concentration on geochemical fractionation (operational speciation) of Cu and Pb in the underneath sediments across the oxygen minimum zone (Arabian Sea) in the west coast of India. Both, Cu and Pb were redistributed among the different binding phases of the sediments with changing dissolved oxygen level (from oxic to hypoxic and close to suboxic) in the bottom water. The average lability of Cu-sediment complexes gradually decreased (i.e., stability increased) with the decreasing dissolved oxygen concentrations of the bottom water. Decreasing bottom-water oxygen concentration increased Cu association with sedimentary organic matter. However, Pb association with Fe/Mn-oxyhydroxide phases in the sediments gradually decreased with the decreasing dissolved oxygen concentration of the overlying bottom water (due to dissolution of Fe/Mn oxyhydroxide phase). The lability of Pb-sediment complexes increased with the decreasing bottom-water oxygen concentration. This study suggests that bottom-water oxygen concentration is one of the key factors governing stability and lability of Cu and Pb complexes in the underneath sediment. Sedimentary organic matter and Fe/Mn oxyhydroxide binding phases were the major hosting phases for Cu and Pb respectively in the study area. Increasing lability of Pb-complexes in bottom sediments may lead to positive benthic fluxes of Pb at low oxygen environment. Copyright © 2016 Elsevier B.V. All rights reserved.

Sources and flux of natural gases from Mono Lake, California

USGS Publications Warehouse

Oremland, R.S.; Miller, L.G.; Whiticar, Michael J.

1987-01-01

The ability to identify a formation mechanism for natural gas in a particular environment requires consideration of several geochemical factors when there are multiple sources present. Four primary sources of methane have been identified in Mono Lake. Two of these sources were associated with numerous natural gas seeps which occur at various locations in the lake and extend beyond its present boundary; the two other gas sources result from current microbiological processes. In the natural gas seeps, we observed flow rates as high as 160 moles CH4 day-1, and estimate total lakewide annual seep flux to be 2.1 ?? 106 moles CH4. Geochemical parameters (??13CH4,??DCH4,CH4/[C2H6+ C3H8]) and ??14CH4measurements revealed that most of the seeps originate from a paleo-biogenic (??13CH4 = about -70%.). natural gas deposit of Pleistocene age which underlies the current and former lakebed. Gas seeps in the vicinity of hot springs had, in combination with the biogenic gas, a prominent thermogenic gas component resulting from hydrothermal alteration of buried organic matter. Current microbiological processes responsible for sources of natural gas in the lake included pelagic meth- anogenesis and decomposition of terrestrial grasses in the littoral zone. Methanogenesis in the pelagic sediments resulted in methane saturation (2-3 mM at 50 cm; ??13CH4 = about -85%.). Interstitial sulfate decreased from 133 mM at the surface to 35 mM by 110 cm depth, indicating that sulfate-reduction and methanogenesis operated concurrently. Methane diffused out of the sediments resulting in concentrations of about 50 ??M in the anoxic bottom waters. Methane oxidation in the oxic/anoxic boundry lowered the concentration by >98%, but values in surface waters (0.1-1.3??M) were supersaturated with respect to the atmosphere. The ??13CH4 (range = -21.8 to -71.8%.) of this unoxidized residual methane was enriched in 13C relative to methane in the bottom water and sediments. Average outward flux of this methane was 2.77 ?? 107 moles yr-1. A fourth, but minor source of methane (??13CH4 = -55.2%.) was associated with the decomposition of terrestrial grasses taking place in the lake's recently expanded littoral zone. ?? 1987.

Marine Biogeochemistry of Particulate Trace Elements in the Exclusive Economic Zone (eez) of the State of Qatar

NASA Astrophysics Data System (ADS)

Yigiterhan, O.; Al-Ansari, I. S.; Abdel-Moati, M.; Murray, J. W.; Al-Ansi, M.

2016-02-01

We focus on the trace element geochemistry of particulate matter in the Exclusive Economic Zone (EEZ) of Qatar. A main goal of this research was to analyze a complete suite of trace elements on particulate matter samples from the water column from different oceanographic biogeochemical zones of the EEZ around Qatar. The sample set also includes plankton samples which are the main source of biogenic particles, dust samples which are a source of abiological particles to surface seawater and surface sediments which can be a source of resuspended particles and a sink for settling particles. The 15 metals and 2 non-metals analyzed in this study will be Al, Ti, V, Cd, Co, Cu, Fe, Mn, Ni, Pb, Zn, Mo, Ag, Ba, U and P, N. Many factors control the composition of trace elements in marine particles. Most of these are important in the EEZ of Qatar, including:1. Natural sources: These are rivers, atmospheric dust, sediment resuspension and leaks from oil beds. However, due to very limited rainfall rivers play no major role in Qatar but resuspension of shallow carbonate rich sediments and input of atmospheric dust are important due to strong currents and surrounding deserts.2. Adsorption/desorption: These chemical processes occur everywhere in the ocean and transfer metals between particles and the solution phase.3. Biological uptake: This process is likewise a universal ocean process and results in transport of metals from the solution phase to biological particles.4. Redox conditions: These are important chemical reactions in the oxic, suboxic and anoxic zones. This can be the dominant controlling mechanism in the northeastern hypoxic deeper waters of the Qatar EEZ.5. Anthropogenic sources: The eastern part of the Qatar contains numerous industrial sites, petroleum/gas platforms and refineries. There are numerous industrial sources but the main hot spots are the port of Doha and the industrial cities of Mesaieed, Khor Al-Odaid, and Ras Laffan. We aimed to determine the influence of the different current systems, water masses, and terrestrial inputs on the distribution, fractionation, and fate of trace metal contaminants and elemental pollutants. We have also observed the level of anthropogenic enrichments for some of the elements which have not been previously documented. This research should be viewed as the first stage of a complete study.

Are the Element Budget and the Occurrence of Polymetallic Nodules influenced by Fluids Circulating through the Oceanic Crust or/and Sediments?

NASA Astrophysics Data System (ADS)

Heller, C.; Kuhn, T.

2016-12-01

Hydrothermal fluids can extract significant amounts of heat from oceanic lithosphere by lateral fluid flow through permeable basaltic crust of an age of up to 65 Ma. Fluid recharge and discharge occur at basement outcrops in between impermeable pelagic sediments. Recharge of oxic seawater causes upward oxygen diffusion into sediments overlying the permeable basalt in areas proximal to recharge sites. It is suggested that this oxygen have a strong impact on sediments and Mn nodules during fluid exposure time. The aim of this study is to investigate if and how fluid flow through oceanic crust influence the distribution and element budget of the Mn nodules. For that purpose, Mn nodules were examined which were collected during the research cruise SO240 in the equatorial NE Pacific at sites with and without faults in the upper basement and overlying sediments. Faults are thought to be preferred fluid pathways. Nodules were found on the sediment surface as well as in the sediment and consist of different nm- to µm-thick, dense and porous layers. The geochemical composition of bulk nodules and single nodule layers were determined by XRF, ICP-MS/OES and by high resolution analyses with EMPA and LA-ICP-MS. Dense layers have low Mn/Fe ratios (<4) and high concentrations of Co, Zr and REY, while porous layers are characterized by high Mn/Fe ratios (> 10) and high Ni+Cu and Li concentrations (Koschinsky et al., 2010; Kuhn et al., 2010). The different compositions depends on different formation processes of the layers. Dense layers are formed by element precipitation from oxygen rich seawater and/or pore water and are called hydrogenetic, while porous layers were formed by precipitation from almost oxygen-free (suboxic) pore water (Burns & Burns, 1978; Glasby, 2006) and are called diagenetic (Halbach et al., 1988). Preliminary results show that there are significant differences between the geochemical composition of nodules grown at sediment surface and those found within sediments. Compared to surface nodules, buried nodules are enriched in Co and W, but has lower concentration of Mo, Ba, Zn, Li. Distribution of Rare Earth Elements (REY) are also different. Especially, the element distribution in the bulk samples and the single layers of the buried nodules could be used to find a possible influence of circulating fluids on nodule formation.

Post examination of copper ER sensors exposed to bentonite

NASA Astrophysics Data System (ADS)

Kosec, Tadeja; Kranjc, Andrej; Rosborg, Bo; Legat, Andraž

2015-04-01

Copper corrosion in saline solutions under oxic conditions is one of concerns for the early periods of disposal of spent nuclear fuel in deep geological repositories. The main aim of the study was to investigate the corrosion behaviour of copper during this oxic period. The corrosion rate of pure copper was measured by means of thin electrical resistance (ER) sensors that were placed in a test package containing an oxic bentonite/saline groundwater environment at room temperature for a period of four years. Additionally, the corrosion rate was monitored by electrochemical impedance spectroscopy (EIS) measurements that were performed on the same ER sensors. By the end of the exposure period the corrosion rate, as estimated by both methods, had dropped to approximately 1.0 μm/year. The corrosion rate was also estimated by the examination of metallographic cross sections. The post examination tests which were used to determine the type and extent of corrosion products included different spectroscopic techniques (XRD and Raman analysis). It was confirmed that the corrosion rate obtained by means of physical (ER) and electrochemical techniques (EIS) was consistent with that estimated from the metallographic cross section analysis. The corrosion products consisted of cuprous oxide and paratacamite, which was very abundant. From the types of attack it can be concluded that the investigated samples of copper in bentonite underwent uneven general corrosion.

Sequential biofiltration - A novel approach for enhanced biological removal of trace organic chemicals from wastewater treatment plant effluent.

PubMed

Müller, Johann; Drewes, Jörg E; Hübner, Uwe

2017-12-15

Recent studies revealed the benefits of oligotrophic and oxic conditions for the biological removal of many trace organic chemicals (TOrCs) during soil-aquifer treatment. These findings indicate an unused tuning potential that might also be applicable in engineered biofiltration systems with drastically reduced hydraulic retention times for an enhanced mitigation of TOrCs during wastewater treatment. This study introduces the novel approach of sequential biofiltration (SBF) for the advanced treatment of secondary effluent using two granular media filters operated in series with an intermediate aeration step aiming for oxic and oligotrophic conditions in the second filter stage. Results from the experiments conducted at pilot-scale confirm a reduced substrate availability and predominantly oxic conditions in the second filter stage of the SBF setup. An increased removal of several TOrCs was observed in an SBF system as compared to a conventional single-stage biofiltration unit operated at the same overall empty bed contact time (EBCT). Short-term tests with varying EBCTs in the first filter stage revealed a high degree of system robustness of TOrC mitigation when confronted with sudden hydraulic load variations. Higher removal of several TOrCs at increased EBCTs in the second filter stage indicates that EBCT might play a crucial role for the degradation of certain compounds. Copyright © 2017 Elsevier Ltd. All rights reserved.

A dynamic microbial community with high functional redundancy inhabits the cold, oxic subseafloor aquifer

NASA Astrophysics Data System (ADS)

Tully, B. J.; Wheat, C. G.; Glazer, B. T.; Huber, J. A.

2017-12-01

The rock-hosted subseafloor crustal aquifer harbors a reservoir of microbial life that may influence global marine biogeochemical cycles. Here we utilized genomic reconstruction of crustal fluid samples from North Pond, located on the flanks of the Mid-Atlantic Ridge, a site with cold, oxic subseafloor fluid circulation within the upper basement. Twenty-one samples were collected during a two-year period at three different depths and two locations with the basaltic aquifer to examine potential microbial metabolism and community dynamics. We observed minor changes in the geochemical signatures over the two years, yet a dynamic microbial community was present in the crustal fluids that underwent large shifts in the dominant taxonomic groups. An analysis of 195 metagenome-assembled genomes (MAGs) were generated from the dataset and revealed a connection between litho- and autotrophic processes, linking carbon fixation to the oxidation of sulfide, sulfur, thiosulfate, hydrogen, and ferrous iron in a diverse group of microorganisms. Despite oxic conditions, analysis of the MAGs indicated that members of the microbial community were poised to exploit hypoxic or anoxic conditions through the use of microaerobic cytochromes and alternative electron acceptors. Temporal and spatial trends from the MAGs revealed a high degree of functional redundancy that did not correlate with the shifting microbial community membership, suggesting functional stability in mediating subseafloor biogeochemical cycles.

Distribution, production, and ecophysiology of Picocystis strain ML in Mono Lake, California

USGS Publications Warehouse

Roesler, Collin S.; Culbertson, Charles W.; Etheridge, Stacey M.; Goericke, Ralf; Kiene, Ronald P.; Miller, Laurence G.; Oremland, Ronald S.

2002-01-01

A recently described unicellular chlorophytic alga isolated from meromictic Mono Lake, California, occupies a niche that spans two environments: the upper oxic mixolimnion and the deeper anoxic and highly reducing monimolimnion. This organism, Picocystis sp. strain ML, accounts for nearly 25% of the primary production during the winter bloom and more than 50% at other times of the year. In incubations, it is heavily grazed by the brine shrimp, Artemia monica. We assessed growth and photosynthetic parameters over broad ranges of irradiance, salinity, and pH and under oxic and anoxic conditions. Picocystis appears to be particularly adapted to low irradiance; we observed an order of magnitude increase in the cellular pigment concentrations, as well as marked increases in cellspecific photosynthetic parameters for cells acclimated to low-growth irradiance. Growth rates of 0.3–1.5 d21 were observed over a salinity range of 0–260‰ and a pH range of 4–12, with maximal growth at ;50 mmol photons m22 s21 , 40‰, and pH 6–10. Growth and oxygenic photosynthesis were observed under anoxic conditions at rates comparable to those measured under oxic conditions. The ability of the organism to acclimate and grow under such a broad range of environmental conditions makes it an important component of the Mono Lake ecosystem and likely contributes to its dominance of the monimolimnion/mixolimnion interface.

Decomposition of algal lipids in clay-enriched marine sediment under oxic and anoxic conditions

NASA Astrophysics Data System (ADS)

Lü, Dongwei; Song, Qian; Wang, Xuchen

2010-01-01

A series of laboratory incubation experiments were conducted to examine the decomposition of algal organic matter in clay-enriched marine sediment under oxic and anoxic conditions. During the 245-day incubation period, changes in the concentrations of TOC, major algal fatty acid components (14:0, 16:0, 16:1, 18:1 and 20:5), and n-alkanes (C16-C23) were quantified in the samples. Our results indicate that the organic matters were degraded more rapidly in oxic than anoxic conditions. Adsorption of fatty acids onto clay minerals was a rapid and reversible process. Using a simple G model, we calculated the decomposition rate constants for TOC, n-alkanes and fatty acids which ranged from 0.017-0.024 d-1, 0.049-0.103 d-1 and 0.011 to 0.069 d-1, respectively. Algal organic matter degraded in two stages characterized by a fast and a slow degradation processes. The addition of clay minerals montmorillonite and kaolinite to the sediments showed significant influence affecting the decomposition processes of algal TOC and fatty acids by adsorption and incorporation of the compounds with clay particles. Adsorption/association of fatty acids by clay minerals was rapid but appeared to be a slow reversible process. In addition to the sediment redox and clay influence, the structure of the compounds also played important roles in affecting their degradation dynamic in sediments.

Composition and aggregation of extracellular polymeric substances (EPS) in hyperhaline and municipal wastewater treatment plants

PubMed Central

Zeng, Jie; Gao, Jun-Min; Chen, You-Peng; Yan, Peng; Dong, Yang; Shen, Yu; Guo, Jin-Song; Zeng, Ni; Zhang, Peng

2016-01-01

As important constituents of activated sludge flocs, extracellular polymeric substances (EPS) play significant roles in pollutants adsorption, the formation and maintenance of microbial aggregates, and the protection of microbes from external environmental stresses. In this work, EPS in activated sludge from a municipal wastewater treatment plant (M-WWTP) with anaerobic/anoxic/oxic (A2/O) process and a hyperhaline wastewater treatment plant (H-WWTP) with anaerobic/oxic (A/O) process were extracted by ultrasound method. The proteins and polysaccharides contents in EPS were determined by using a modified Lowry method and anthrone colorimetry respectively to analyze the detail differences in two types of WWTPs. Fourier transform-infrared spectroscopy and three-dimensional excitation-emission matrix fluorescence spectroscopy demonstrated proteins and polysaccharides were the dominant components of the two types of EPS, and the aromatic protein-like substances accounted for a larger proportion in EPS proteins. The results of the aggregation test indicated that EPS were good for the sludge aggregation, and the EPS in oxic sludge were more beneficial to sludge aggregation than that in anoxic sludge. Anoxic sludge EPS in H-WWTP showed a negligible effect on sludge aggregation. Comparative study on EPS of different tanks in the M-WWTP and H-WWTP was valuable for understanding the characteristics of EPS isolated from two typical wastewater treatment processes. PMID:27220287

Insights into the ecology, evolution, and metabolism of the widespread Woesearchaeotal lineages.

PubMed

Liu, Xiaobo; Li, Meng; Castelle, Cindy J; Probst, Alexander J; Zhou, Zhichao; Pan, Jie; Liu, Yang; Banfield, Jillian F; Gu, Ji-Dong

2018-06-08

As a recently discovered member of the DPANN superphylum, Woesearchaeota account for a wide diversity of 16S rRNA gene sequences, but their ecology, evolution, and metabolism remain largely unknown. Here, we assembled 133 global clone libraries/studies and 19 publicly available genomes to profile these patterns for Woesearchaeota. Phylogenetic analysis shows a high diversity with 26 proposed subgroups for this recently discovered archaeal phylum, which are widely distributed in different biotopes but primarily in inland anoxic environments. Ecological patterns analysis and ancestor state reconstruction for specific subgroups reveal that oxic status of the environments is the key factor driving the distribution and evolutionary diversity of Woesearchaeota. A selective distribution to different biotopes and an adaptive colonization from anoxic to oxic environments can be proposed and supported by evidence of the presence of ferredoxin-dependent pathways in the genomes only from anoxic biotopes but not from oxic biotopes. Metabolic reconstructions support an anaerobic heterotrophic lifestyle with conspicuous metabolic deficiencies, suggesting the requirement for metabolic complementarity with other microbes. Both lineage abundance distribution and co-occurrence network analyses across diverse biotopes confirmed metabolic complementation and revealed a potential syntrophic relationship between Woesearchaeota and methanogens, which is supported by metabolic modeling. If correct, Woesearchaeota may impact methanogenesis in inland ecosystems. The findings provide an ecological and evolutionary framework for Woesearchaeota at a global scale and indicate their potential ecological roles, especially in methanogenesis.

Hydrologic and chemical data from an experiment to examine temporal variability in water samples from screened wells on Cape Cod, Massachusetts

USGS Publications Warehouse

Reilly, Thomas E.

1994-01-01

An experiment was designed to evaluate the changing chemical composition of the water pumped from a well screened in a physically and chemically heterogenous aquifer. Well F453-63, at the U.S. Geological Survey Toxic-Substances Hydrology research site located on Cape Cod, Massachusetts, was selected because it was known that the screen penetrated both the oxic and anoxic zones of the sewage plume from the Otis Air Base sewage-disposal sand beds. The experiment was conducted on August 12, 1992. Well F453-63 was sampled over time as it was pumped continuously, and three multilevel samplers were used to document the vertical distribution of selected chemicals in the ground water in the immediate vicinity of the well. All water samples obtained during the experiment were analyzed in the field for specific conductance and pH. The samples were subsequently analyzed for concentrations of ferrous iron (Fe+2), boron, calcium, chloride, iron (Fe total), phosphorus, potassium, magnesium, manganese, sodium, zinc, and nitrogen species, including nitrous oxide, ammonium, nitrite and nitrate. The results of these chemical analyses along with appropriate physical measurements of the site and aquifer material are documented in this data report.

The effect of aeration on the removal of wastewater-derived pharmaceutical residues from groundwater - a laboratory study.

PubMed

Burke, Victoria; Duennbier, Uwe; Massmann, Gudrun

2013-01-01

Several studies on waste- or drinking water treatment processes as well as on groundwater have recently shown that some pharmaceutical residues (PRs) are redox-sensitive. Hence, their (bio)degradation depends on the redox conditions prevalent in the aquifer. Groundwater, providing raw water for drinking water production, is often anoxic and aeration is a widespread treatment method applied mainly to eliminate unwanted iron and manganese from the water. As a side-effect, aeration may trigger the elimination of PRs. Within the present study the influence of aeration on the fate of a number of wastewater derived analgesics and their residues as well as several antimicrobial compounds was investigated. For this purpose, anoxic groundwater was transferred into stainless steel tanks, some of which were aerated while others were continuously kept anoxic. Results prove that the degradation of six phenazone type compounds is dependent on oxygen availability and compounds are efficiently removed under oxic conditions only. Concerning the antimicrobials, doxycycline and trimethoprim were better removed during aeration, whereas a slightly improved removal under anoxic conditions was observed for clindamycin, roxithromycin and clarithromycin. The study provides first laboratory proof of the redox-sensitivity of several organic trace pollutants. In addition, results demonstrate that aeration is an effective treatment for the elimination of a number of wastewater derived PRs.

Dissolved sulfides in the oxic water column of San Francisco Bay, California

USGS Publications Warehouse

Kuwabara, J.S.; Luther, G.W.

1993-01-01

Trace contaminants enter major estuaries such as San Francisco Bay from a variety of point and nonpoint sources and may then be repartitioned between solid and aqueous phases or altered in chemical speciation. Chemical speciation affects the bioavailability of metals as well as organic ligands to planktonic and benthic organisms, and the partitioning of these solutes between phases. Our previous, work in south San Francisco Bay indicated that sulfide complexation with metals may be of particular importance because of the thermodynamic stability of these complexes. Although the water column of the bay is consistently well-oxygenated and typically unstratified with respect to dissolved oxygen, the kinetics of sulfide oxidation could exert at least transient controls on metal speciation. Our initial data on dissolved sulfides in the main channel of both the northern and southern components of the bay consistently indicate submicromolar concenrations (from <1 nM to 162 nM), as one would expect in an oxidizing environment. However, chemical speciation calculations over the range of observed sulfide concentrations indicate that these trace concentrations in the bay water column can markedly affect chemical speciation of ecologically significant trace metals such as cadmium, copper, and zinc.

Impact of redox and transport processes in a riparian wetland on stream water quality in the Fichtelgebirge region, southern Germany

NASA Astrophysics Data System (ADS)

Lischeid, G.; Kolb, A.; Alewell, C.; Paul, S.

2007-01-01

Biologically mediated redox processes in the riparian zone, like denitrification, can have substantially beneficial impacts on stream water quality. The extent of these effects, however, depends greatly on the hydrological boundary conditions. The impact of hydrological processes on a wetland's nitrogen sink capacity was investigated in a forested riparian fen which is drained by a first-order perennial stream. Here, we analysed the frequency distributions and time-series of pH and nitrogen, silica, organic carbon and oxygen concentrations in throughfall, soil solution, groundwater and stream water, and the groundwater levels and stream discharges from a 3-year period. During baseflow conditions, the stream was fed by discharging shallow, anoxic groundwater and by deep, oxic groundwater. Whereas the latter delivered considerable amounts of nitrogen (0.37 mg l-1) to the stream, the former was almost entirely depleted of nitrogen. During stormflow, near-surface runoff in the upper 30 cm soil layer bypassed the denitrifying zone and added significant amounts to the nitrogen load of the stream. Nitrate-nitrogen was close to 100% of deep groundwater and stream-water nitrogen concentration. Stream-water baseflow concentrations of nitrate, dissolved carbon and silica were about 1.6 mg l-1, 4 mg l-1 and 7.5 mg l-1 respectively, and >3 mg l-1, >10 mg l-1 and <4 mg l-1 respectively during discharge peaks. In addition to that macroscale bypassing effect, there was evidence for a corresponding microscale effect: Shallow groundwater sampled by soil suction cups indicated complete denitrification and lacked any seasonal signal of solute concentration, which was in contrast to piezometer samples from the same depth. Moreover, mean solute concentration in the piezometer samples resembled more that of suction-cup samples from shallower depth than that of the same depth. We conclude that the soil solution cups sampled to a large extent the immobile soil-water fraction. In contrast, the mobile fraction that was sampled by the piezometers exhibited substantially shorter residence time, thus being less exposed to denitrification, but predominating discharge of that layer to the stream. Consequently, assessing the nitrogen budget based on suction-cup data tended to overestimate the nitrogen consumption in the riparian wetland. These effects are likely to become more important with the increased frequency and intensity of rainstorms that are expected due to climate change. Copyright

Groundwater – The disregarded component in lake water and nutrient budgets. Part 2: effects of groundwater on nutrients

USGS Publications Warehouse

Lewandowski, Jörg; Meinikmann, Karin; Nützmann, Gunnar; Rosenberry, Donald O.

2015-01-01

Lacustrine groundwater discharge (LGD) transports nutrients from a catchment to a lake, which may fuel eutrophication, one of the major threats to our fresh waters. Unfortunately, LGD has often been disregarded in lake nutrient studies. Most measurement techniques are based on separate determinations of volume and nutrient concentration of LGD: Loads are calculated by multiplying seepage volumes by concentrations of exfiltrating water. Typically low phosphorus (P) concentrations of pristine groundwater often are increased due to anthropogenic sources such as fertilizer, manure or sewage. Mineralization of naturally present organic matter might also increase groundwater P. Reducing redox conditions favour P transport through the aquifer to the reactive aquifer-lake interface. In some cases, large decreases of P concentrations may occur at the interface, for example, due to increased oxygen availability, while in other cases, there is nearly no decrease in P. The high reactivity of the interface complicates quantification of groundwater-borne P loads to the lake, making difficult clear differentiation of internal and external P loads to surface water. Anthropogenic sources of nitrogen (N) in groundwater are similar to those of phosphate. However, the environmental fate of N differs fundamentally from P because N occurs in several different redox states, each with different mobility. While nitrate behaves essentially conservatively in most oxic aquifers, ammonium's mobility is similar to that of phosphate. Nitrate may be transformed to gaseous N2 in reducing conditions and permanently removed from the system. Biogeochemical turnover of N is common at the reactive aquifer-lake interface. Nutrient loads from LGD were compiled from the literature. Groundwater-borne P loads vary from 0.74 to 2900 mg PO4-P m−2 year−1; for N, these loads vary from 0.001 to 640 g m−2 year−1. Even small amounts of seepage can carry large nutrient loads due to often high nutrient concentrations in groundwater. Large spatial heterogeneity, uncertain areal extent of the interface and difficult accessibility make every determination of LGD a challenge. However, determinations of LGD are essential to effective lake management.

Lake on life support: Evaluating urban lake management measures by using a coupled 1D-modelling approach

NASA Astrophysics Data System (ADS)

Ladwig, Robert; Kirillin, Georgiy; Hinkelmann, Reinhard; Hupfer, Michael

2017-04-01

Urban surface water systems and especially lakes are heavily stressed and modified systems to comply with water management goals and expectations. In this study we focus on Lake Tegel in Berlin, Germany, as a representative of heavily modified urban lakes. In the 20th century, Lake Tegel received increased loadings of nutrients and leached heavy metals from an upstream sewage farm resulting in severe eutrophication problems. The construction of two upstream treatment plants caused a lowering of nutrient concentrations and a re-oligotrophication of the lake. Additionally, artificial aerators, to keep the hypolimnion oxic, and a lake pipeline, to bypass water for maintaining a minimum discharge, went into operation. Lake Tegel is still heavily used for drinking water extraction by bank filtration. These interacting management measures make the system vulnerable to changing climate conditions and pollutant loads. Past modelling studies have shown the complex hydrodynamics of the lake. Here, we are following a simplified approach by using a less computational time consuming vertical 1D-model to simulate the hydrodynamics and the ecological interactions of the system by coupling the General Lake Model to the Aquatic Ecodynamics Model Library 2. For calibration of the multidimensional parameter space we applied the Covariance Matrix Adaption-Evolution Strategy algorithm. The model is able to sufficiently replicate the vertical field temperature profiles of Lake Tegel as well as to simulate similar concentration ranges of phosphate, dissolved oxygen and nitrate. The calibrated model is used to run an uncertainty analysis by sampling the simulated data within the meaning of the Metropolis-Hastings algorithm. Finally, we are evaluating different scenarios: (1) changing air temperatures, precipitation and wind speed due to effects of climate change, (2) decreased discharges into the lake due to bypassing treated effluents into a near stream instead of Lake Tegel, and (3) increased nutrient elimination at the upstream treatment plants. We are focusing on quantifying the impact of these scenarios on lake stability as well as the abundance and distribution of nutrients.

Intensification and deepening of the Arabian Sea oxygen minimum zone in response to increase in Indian monsoon wind intensity

NASA Astrophysics Data System (ADS)

Lachkar, Zouhair; Lévy, Marina; Smith, Shafer

2018-01-01

The decline in oxygen supply to the ocean associated with global warming is expected to expand oxygen minimum zones (OMZs). This global trend can be attenuated or amplified by regional processes. In the Arabian Sea, the world's thickest OMZ is highly vulnerable to changes in the Indian monsoon wind. Evidence from paleo-records and future climate projections indicates strong variations of the Indian monsoon wind intensity over climatic timescales. Yet, the response of the OMZ to these wind changes remains poorly understood and its amplitude and timescale unexplored. Here, we investigate the impacts of perturbations in Indian monsoon wind intensity (from -50 to +50 %) on the size and intensity of the Arabian Sea OMZ, and examine the biogeochemical and ecological implications of these changes. To this end, we conducted a series of eddy-resolving simulations of the Arabian Sea using the Regional Ocean Modeling System (ROMS) coupled to a nitrogen-based nutrient-phytoplankton-zooplankton-detritus (NPZD) ecosystem model that includes a representation of the O2 cycle. We show that the Arabian Sea productivity increases and its OMZ expands and deepens in response to monsoon wind intensification. These responses are dominated by the perturbation of the summer monsoon wind, whereas the changes in the winter monsoon wind play a secondary role. While the productivity responds quickly and nearly linearly to wind increase (i.e., on a timescale of years), the OMZ response is much slower (i.e., a timescale of decades). Our analysis reveals that the OMZ expansion at depth is driven by increased oxygen biological consumption, whereas its surface weakening is induced by increased ventilation. The enhanced ventilation favors episodic intrusions of oxic waters in the lower epipelagic zone (100-200 m) of the western and central Arabian Sea, leading to intermittent expansions of marine habitats and a more frequent alternation of hypoxic and oxic conditions there. The increased productivity and deepening of the OMZ also lead to a strong intensification of denitrification at depth, resulting in a substantial amplification of fixed nitrogen depletion in the Arabian Sea. We conclude that changes in the Indian monsoon can affect, on longer timescales, the large-scale biogeochemical cycles of nitrogen and carbon, with a positive feedback on climate change in the case of stronger winds. Additional potential changes in large-scale ocean ventilation and stratification may affect the sensitivity of the Arabian Sea OMZ to monsoon intensification.

Effects of Offshore Oil Exploration and Development in the Alaskan Beaufort Sea: A Three-Decade Record for Sediment Metals.

PubMed

Trefry, John H; Neff, Jerry M

2018-06-19

Impacts from oil exploration, development and production in the Beaufort Sea, Alaska, are assessed using concentrations of metals in sediments collected during 2014-15, combined with a large dataset for 1985-2006. Concentrations of 7 (1980 s) or 17 (1999-2015) metals in 423 surface sediments from 134 stations, plus 563 samples from 30 cores were highly variable, primarily as a function of sediment granulometry with naturally greater metal concentrations in fine-grained, Al-rich sediment. Metals versus Al correlation plots were used to normalize metal concentrations and identify values significantly above background. Barium, Cr, Cu, Hg and Pb concentrations were above background, but variable, within 250 m of some offshore sites where drilling occurred between 1981-2001; these areas totaled <6 km 2 of 11,000 km 2 in the total lease area. Random and fixed sampling along the coastal Beaufort Sea from 1985-2015 yielded 40 positive anomalies for metals in surface sediments (∼0.8% of 5,082 data points). About 85% of the anomalies were from developed areas. Half the anomalies were for the five metals found enhanced near drilling sites. No metals concentrations, except As, exceeded accepted sediment quality criteria. Interannual shifts in metals values for surface sediments at inner shelf sites were common and linked to storm-induced transitions in granulometry; however, metal/Al ratios were uniform during these shifts. Sediment cores generally recorded centuries of background values, except for As, Fe and Mn. These three metals were naturally enriched in sediments from deeper water (>100 m) via diagenetic remobilization at sediment depths of 5-15 cm, upward diffusion, and precipitation in surface oxic layers. Minimal evidence for anthropogenic inputs of metals, except near some exploratory drilling sites, is consistent with extraction of most oil from land or barrier islands in the Alaskan Arctic and restricted offshore activity to date. This article is protected by copyright. All rights reserved. This article is protected by copyright. All rights reserved.

Pyrosequencing-based assessment of the bacteria diversity in surface and subsurface peat layers of a northern wetland, with focus on poorly studied phyla and candidate divisions.

PubMed

Serkebaeva, Yulia M; Kim, Yongkyu; Liesack, Werner; Dedysh, Svetlana N

2013-01-01

Northern peatlands play a key role in the global carbon and water budget, but the bacterial diversity in these ecosystems remains poorly described. Here, we compared the bacterial community composition in the surface (0-5 cm depth) and subsurface (45-50 cm) peat layers of an acidic (pH 4.0) Sphagnum-dominated wetland, using pyrosequencing of 16S rRNA genes. The denoised sequences (37,229 reads, average length ∼430 bp) were affiliated with 27 bacterial phyla and corresponded to 1,269 operational taxonomic units (OTUs) determined at 97% sequence identity. Abundant OTUs were affiliated with the Acidobacteria (35.5±2.4% and 39.2±1.2% of all classified sequences in surface and subsurface peat, respectively), Alphaproteobacteria (15.9±1.7% and 25.8±1.4%), Actinobacteria (9.5±2.0% and 10.7±0.5%), Verrucomicrobia (8.5±1.4% and 0.6±0.2%), Planctomycetes (5.8±0.4% and 9.7±0.6%), Deltaproteobacteria (7.1±0.4% and 4.4%±0.3%), and Gammaproteobacteria (6.6±0.4% and 2.1±0.1%). The taxonomic patterns of the abundant OTUs were uniform across all the subsamples taken from each peat layer. In contrast, the taxonomic patterns of rare OTUs were different from those of the abundant OTUs and varied greatly among subsamples, in both surface and subsurface peat. In addition to the bacterial taxa listed above, rare OTUs represented the following groups: Armatimonadetes, Bacteroidetes, Chlamydia, Chloroflexi, Cyanobacteria, Elusimicrobia, Fibrobacteres, Firmicutes, Gemmatimonadetes, Spirochaetes, AD3, WS1, WS4, WS5, WYO, OD1, OP3, BRC1, TM6, TM7, WPS-2, and FCPU426. OTU richness was notably higher in the surface layer (882 OTUs) than in the anoxic subsurface peat (483 OTUs), with only 96 OTUs common to both data sets. Most members of poorly studied phyla, such as the Acidobacteria, Verrucomicrobia, Planctomycetes and the candidate division TM6, showed a clear preference for growth in either oxic or anoxic conditions. Apparently, the bacterial communities in surface and subsurface layers of northern peatlands are highly diverse and taxonomically distinct, reflecting the different abiotic conditions in microhabitats within the peat profile.

Attenuation and colloidal mobilization of bacteriophages in natural sediments under anoxic as compared to oxic conditions.

PubMed

Klitzke, Sondra; Schroeder, Jendrik; Selinka, Hans-Christoph; Szewzyk, Regine; Chorus, Ingrid

2015-06-15

Redox conditions are known to affect the fate of viruses in porous media. Several studies report the relevance of colloid-facilitated virus transport in the subsurface, but detailed studies on the effect of anoxic conditions on virus retention in natural sediments are still missing. Therefore, we investigated the fate of viruses in natural flood plain sediments with different sesquioxide contents under anoxic conditions by considering sorption to the solid phase, sorption to mobilized colloids, and inactivation in the aqueous phase. Batch experiments were conducted under oxic and anoxic conditions at pH values between 5.1 and 7.6, using bacteriophages MS2 and PhiX174 as model viruses. In addition to free and colloid-associated bacteriophages, dissolved and colloidal concentrations of Fe, Al and organic C as well as dissolved Ca were determined. Results showed that regardless of redox conditions, bacteriophages did not adsorb to mobilized colloids, even under favourable charge conditions. Under anoxic conditions, attenuation of bacteriophages was dominated by sorption over inactivation, with MS2 showing a higher degree of sorption than PhiX174. Inactivation in water was low under anoxic conditions for both bacteriophages with about one log10 decrease in concentration during 16 h. Increased Fe/Al concentrations and a low organic carbon content of the sediment led to enhanced bacteriophage removal under anoxic conditions. However, even in the presence of sufficient Fe/A-(hydr)oxides on the solid phase, bacteriophage sorption was low. We presume that organic matter may limit the potential retention of sesquioxides in anoxic sediments and should thus be considered for the risk assessment of virus breakthrough in the subsurface. Copyright © 2015 Elsevier B.V. All rights reserved.

Foraminiferal Metabolism Under Hypoxia: Sub-Cellular NanoSIMS Imaging of Intertidal Ammonia tepida Feeding Behavior

NASA Astrophysics Data System (ADS)

LeKieffre, C.; Spangenberg, J.; Geslin, E.; Meibom, A.

2016-02-01

Hypoxic events particularly affect benthic ecosystems on continental shelves and in coastal areas where renewal of bottom waters slow. Foraminifera living in such environments are among the most tolerant to hypoxia in the meiofauna. Some foraminifera species are able to survive hypoxia, and even anoxia, for weeks to months. Different species must have developed different mechanisms for survival - hypotheses include reduction of the metabolism, symbiosis with bacteria, or denitrification. NanoSIMS (Secondary Ion Mass Spectrometry) imaging is a powerful analytical technique to visualize and quantify the incorporation and transfer of isotopically labeled compounds in organisms with subcellular resolution. We used NanoSIMS imaging, correlated with TEM ultrastructural observations of individual foraminifera, to study the metabolism of intertidal Ammonia tepida, which has shown strongly reduced metabolism under anoxia. Individuals were fed with a 13C-labeled microalgal biofilm and incubated for 4 weeks in oxic and anoxic conditions, respectively. NanoSIMS imaging reveal strongly contrasting cellular-level dynamics of integration and transfer of the ingested biofilm components under the two conditions. In oxic conditions, ingested biofilm components are internalized, metabolized, and used for biosynthesis of different cellular components on a time scale of 24 hours: Lipid droplets are formed, then consumed through respiration. In contrast, upon the onset of anoxia, individual internalized biofilm components remain visible within the cytoplasm after 4 weeks. Lipids of different compositions are initially formed but then not respired. These observations indicate that foraminifera do initially have an active heterotrophic metabolism in the absence of oxygen, but this it is strongly reduced when oxygen is no longer available. Isotopic labeling experiments, NanoSIMS and TEM imaging, and GC-MS will be key to study metabolic mechanisms under anoxic conditions in marine environments.

Biogeochemical probing of microbial communities in a basalt-hosted hot spring at Kverkfjöll volcano, Iceland.

PubMed

Cousins, Claire R; Fogel, Marilyn; Bowden, Roxane; Crawford, Ian; Boyce, Adrian; Cockell, Charles; Gunn, Matthew

2018-06-01

We investigated bacterial and archaeal communities along an ice-fed surficial hot spring at Kverkfjöll volcano-a partially ice-covered basaltic volcano at Vatnajökull glacier, Iceland, using biomolecular (16S rRNA, apsA, mcrA, amoA, nifH genes) and stable isotope techniques. The hot spring environment is characterized by high temperatures and low dissolved oxygen concentrations at the source (68°C and <1 mg/L (±0.1%)) changing to lower temperatures and higher dissolved oxygen downstream (34.7°C and 5.9 mg/L), with sulfate the dominant anion (225 mg/L at the source). Sediments are comprised of detrital basalt, low-temperature alteration phases and pyrite, with <0.4 wt. % total organic carbon (TOC). 16S rRNA gene profiles reveal that organisms affiliated with Hydrogenobaculum (54%-87% bacterial population) and Thermoproteales (35%-63% archaeal population) dominate the micro-oxic hot spring source, while sulfur-oxidizing archaea (Sulfolobales, 57%-82%), and putative sulfur-oxidizing and heterotrophic bacterial groups dominate oxic downstream environments. The δ 13 C org (‰ V-PDB) values for sediment TOC and microbial biomass range from -9.4‰ at the spring's source decreasing to -12.6‰ downstream. A reverse effect isotope fractionation of ~3‰ between sediment sulfide (δ 34 S ~0‰) and dissolved water sulfate (δ 34 S +3.2‰), and δ 18 O values of ~ -5.3‰ suggest pyrite forms abiogenically from volcanic sulfide, followed by abiogenic and microbial oxidation. These environments represent an unexplored surficial geothermal environment analogous to transient volcanogenic habitats during putative "snowball Earth" scenarios and volcano-ice geothermal environments on Mars. © 2018 John Wiley & Sons Ltd.

Stratified Bacterial Diversity along Physico-chemical Gradients in High-Altitude Modern Stromatolites

PubMed Central

Toneatti, Diego M.; Albarracín, Virginia H.; Flores, Maria R.; Polerecky, Lubos; Farías, María E.

2017-01-01

At an altitude of 3,570 m, the volcanic lake Socompa in the Argentinean Andes is presently the highest site where actively forming stromatolite-like structures have been reported. Interestingly, pigment and microsensor analyses performed through the different layers of the stromatolites (50 mm-deep) showed steep vertical gradients of light and oxygen, hydrogen sulfide and pH in the porewater. Given the relatively good characterization of these physico-chemical gradients, the aim of this follow-up work was to specifically address how the bacterial diversity stratified along the top six layers of the stromatolites which seems the most metabolically important and diversified zone of the whole microbial community. We herein discussed how, in only 7 mm, a drastic succession of metabolic adaptations occurred: i.e., microbial communities shift from a UV-high/oxic world to an IR-low/anoxic/high H2S environment which force stratification and metabolic specialization of the bacterial community, thus, modulating the chemical faces of the Socompa stromatolites. The oxic zone was dominated by Deinococcus sp. at top surface (0.3 mm), followed by a second layer of Coleofasciculus sp. (0.3 to ∼2 mm). Sequences from anoxygenic phototrophic Alphaproteobacteria, along with an increasing diversity of phyla including Bacteroidetes, Spirochaetes were found at middle layers 3 and 4. Deeper layers (5–7 mm) were mostly occupied by sulfate reducers of Deltaproteobacteria, Bacteroidetes and Firmicutes, next to a high diversity and equitable community of rare, unclassified and candidate phyla. This analysis showed how microbial communities stratified in a physicochemical vertical profile and according to the light source. It also gives an insight of which bacterial metabolic capabilities might operate and produce a microbial cooperative strategy to thrive in one of the most extreme environments on Earth. PMID:28446906

Stratified Bacterial Diversity along Physico-chemical Gradients in High-Altitude Modern Stromatolites.

PubMed

Toneatti, Diego M; Albarracín, Virginia H; Flores, Maria R; Polerecky, Lubos; Farías, María E

2017-01-01

At an altitude of 3,570 m, the volcanic lake Socompa in the Argentinean Andes is presently the highest site where actively forming stromatolite-like structures have been reported. Interestingly, pigment and microsensor analyses performed through the different layers of the stromatolites (50 mm-deep) showed steep vertical gradients of light and oxygen, hydrogen sulfide and pH in the porewater. Given the relatively good characterization of these physico-chemical gradients, the aim of this follow-up work was to specifically address how the bacterial diversity stratified along the top six layers of the stromatolites which seems the most metabolically important and diversified zone of the whole microbial community. We herein discussed how, in only 7 mm, a drastic succession of metabolic adaptations occurred: i.e., microbial communities shift from a UV-high/oxic world to an IR-low/anoxic/high H 2 S environment which force stratification and metabolic specialization of the bacterial community, thus, modulating the chemical faces of the Socompa stromatolites. The oxic zone was dominated by Deinococcus sp. at top surface (0.3 mm), followed by a second layer of Coleofasciculus sp. (0.3 to ∼2 mm). Sequences from anoxygenic phototrophic Alphaproteobacteria, along with an increasing diversity of phyla including Bacteroidetes, Spirochaetes were found at middle layers 3 and 4. Deeper layers (5-7 mm) were mostly occupied by sulfate reducers of Deltaproteobacteria, Bacteroidetes and Firmicutes, next to a high diversity and equitable community of rare, unclassified and candidate phyla. This analysis showed how microbial communities stratified in a physicochemical vertical profile and according to the light source. It also gives an insight of which bacterial metabolic capabilities might operate and produce a microbial cooperative strategy to thrive in one of the most extreme environments on Earth.

Tungsten species in natural ferromanganese oxides related to its different behavior from molybdenum in oxic ocean

NASA Astrophysics Data System (ADS)

Kashiwabara, Teruhiko; Takahashi, Yoshio; Marcus, Matthew A.; Uruga, Tomoya; Tanida, Hajime; Terada, Yasuko; Usui, Akira

2013-04-01

The tungsten (W) species in marine ferromanganese oxides were investigated by wavelength dispersive XAFS method. We found that the W species are in distorted Oh symmetry in natural ferromanganese oxides. The host phase of W is suggested to be Mn oxides by μ-XRF mapping. We also found that the W species forms inner-sphere complexes in hexavalent state and distorted Oh symmetry on synthetic ferrihydrite, goethite, hematite, and δ-MnO2. The molecular-scale information of W indicates that the negatively-charged WO42- ion mainly adsorbs on the negatively-charged Mn oxides phase in natural ferromanganese oxides due to the strong chemical interaction. In addition, preferential adsorption of lighter W isotopes is expected based on the molecular symmetry of the adsorbed species, implying the potential significance of the W isotope systems similar to Mo. Adsorption experiments of W on synthetic ferrihydrite and δ-MnO2 were also conducted. At higher equilibrium concentration, W exhibits behaviors similar to Mo on δ-MnO2 due to their formations of inner-sphere complexes. On the other hand, W shows a much larger adsorption on ferrihydrite than Mo. This is due to the formation of the inner- and outer-sphere complexes for W and Mo on ferrihydrite, respectively. Considering the lower equilibrium concentration such as in oxic seawater, however, the enrichment of W into natural ferromanganese oxides larger than Mo may be controlled by the different stabilities of their inner-sphere complexes on the Mn oxides. These two factors, (i) the stability of inner-sphere complexes on the Mn oxides and (ii) the mode of attachment on ferrihydrite (inner- or outer-sphere complex), are the causes of the different behaviors of W and Mo on the surface of the Fe/Mn (oxyhydr)oxides.

Source identification of nitrous oxide on autotrophic partial nitrification in a granular sludge reactor.

PubMed

Rathnayake, R M L D; Song, Y; Tumendelger, A; Oshiki, M; Ishii, S; Satoh, H; Toyoda, S; Yoshida, N; Okabe, S

2013-12-01

Emission of nitrous oxide (N2O) during biological wastewater treatment is of growing concern since N2O is a major stratospheric ozone-depleting substance and an important greenhouse gas. The emission of N2O from a lab-scale granular sequencing batch reactor (SBR) for partial nitrification (PN) treating synthetic wastewater without organic carbon was therefore determined in this study, because PN process is known to produce more N2O than conventional nitrification processes. The average N2O emission rate from the SBR was 0.32 ± 0.17 mg-N L(-1) h(-1), corresponding to the average emission of N2O of 0.8 ± 0.4% of the incoming nitrogen load (1.5 ± 0.8% of the converted NH4(+)). Analysis of dynamic concentration profiles during one cycle of the SBR operation demonstrated that N2O concentration in off-gas was the highest just after starting aeration whereas N2O concentration in effluent was gradually increased in the initial 40 min of the aeration period and was decreased thereafter. Isotopomer analysis was conducted to identify the main N2O production pathway in the reactor during one cycle. The hydroxylamine (NH2OH) oxidation pathway accounted for 65% of the total N2O production in the initial phase during one cycle, whereas contribution of the NO2(-) reduction pathway to N2O production was comparable with that of the NH2OH oxidation pathway in the latter phase. In addition, spatial distributions of bacteria and their activities in single microbial granules taken from the reactor were determined with microsensors and by in situ hybridization. Partial nitrification occurred mainly in the oxic surface layer of the granules and ammonia-oxidizing bacteria were abundant in this layer. N2O production was also found mainly in the oxic surface layer. Based on these results, although N2O was produced mainly via NH2OH oxidation pathway in the autotrophic partial nitrification reactor, N2O production mechanisms were complex and could involve multiple N2O production pathways. Copyright © 2013 Elsevier Ltd. All rights reserved.

Microbial oxidation of elemental selenium in soil slurries and bacterial cultures

USGS Publications Warehouse

Dowdle, P.R.; Oremland, R.S.

1998-01-01

The microbial oxidation of elemental selenium [Se(O)] was studied by employing 75Se(O) as a tracer. Live, oxic soil slurries demonstrated a linear production of mostly Se(IV), with the formation of smaller quantities of Se(VI). Production of both Se(IV) and Se(VI) was inhibited by autoclaving, formalin, antibiotics, azide, and 2,4-dinitrophenol, thereby indicating the involvement of microbes. Oxidation of Se(O) in slurries was enhanced by addition of acetate, glucose, or sulfide, which implied involvement of chemoheterotrophs as well as chemoautotrophic thiobacilli. Cultures of Thiobacillus ASN-1, Leptothrix MnB1, and a heterotrophic soil enrichment all oxidized Se(O) with Se(VI) observed as the major product rather than Se(IV). This indicated that microbial oxidation in soils is partly constrained by the adsorption of Se(IV) onto soil surfaces. Rate constants for unamended soil slurry Se(O) oxidation ranged from 0.0009 to 0.0117 day-1 which were 3-4 orders of magnitude lower than those reported for dissimilatory Se(VI) reduction in organic-rich, anoxic sediments.The microbial oxidation of elemental selenium [Se(0)] was studied by employing 75Se(0) as a tracer. Live, oxic soil slurries demonstrated a linear production of mostly Se(IV), with the formation of smaller quantities of Se(VI). Production of both Se(IV) and Se(VI) was inhibited by autoclaving, formalin, antibiotics, azide, and 2,4-dinitrophenol, thereby indicating the involvement of microbes. Oxidation of Se(O) in slurries was enhanced by addition of acetate, glucose, or sulfide, which implied involvement of chemoheterotrophs as well as chemoautotrophic thiobacilli. Cultures of Thiobacillus ASN-1, Leptothrix MnB1, and a heterotrophic soil enrichment all oxidized Se(O) with Se(VI) observed as the major product rather than Se(IV). This indicated that microbial oxidation in soils is partly constrained by the adsorption of Se(IV) onto soil surfaces. Rate constants for unamended soil slurry Se(O) oxidation ranged from 0.0009 to 0.0117 day-1 which were 3-4 orders of magnitude lower than those reported for dissimilatory Se(VI) reduction in organic-rich, anoxic sediments.

Metalimnetic oxygen minima alter the vertical profiles of carbon dioxide and methane in a managed freshwater reservoir.

PubMed

McClure, Ryan P; Hamre, Kathleen D; Niederlehner, B R; Munger, Zackary W; Chen, Shengyang; Lofton, Mary E; Schreiber, Madeline E; Carey, Cayelan C

2018-04-30

Metalimnetic oxygen minimum zones (MOMs) commonly develop during the summer stratified period in freshwater reservoirs because of both natural processes and water quality management. While several previous studies have examined the causes of MOMs, much less is known about their effects, especially on reservoir biogeochemistry. MOMs create distinct redox gradients in the water column which may alter the magnitude and vertical distribution of dissolved methane (CH 4 ) and carbon dioxide (CO 2 ). The vertical distribution and diffusive efflux of CH 4 and CO 2 was monitored for two consecutive open-water seasons in a eutrophic reservoir that develops MOMs as a result of the operation of water quality engineering systems. During both summers, elevated concentrations of CH 4 accumulated within the anoxic MOM, reaching a maximum of 120 μM, and elevated concentrations of CO 2 accumulated in the oxic hypolimnion, reaching a maximum of 780 μM. Interestingly, the largest observed diffusive CH 4 effluxes occurred before fall turnover in both years, while peak diffusive CO 2 effluxes occurred both before and during turnover. Our data indicate that MOMs can substantially change the vertical distribution of CH 4 and CO 2 in the water column in reservoirs, resulting in the accumulation of CH 4 in the metalimnion (vs. at the sediments) and CO 2 in the hypolimnion. Copyright © 2018 Elsevier B.V. All rights reserved.

Cenomanian-Turonian transition in a shallow water sequence of the Sinai, Egypt

NASA Astrophysics Data System (ADS)

Gertsch, B.; Keller, G.; Adatte, T.; Berner, Z.; Kassab, A. S.; Tantawy, A. A. A.; El-Sabbagh, A. M.; Stueben, D.

2010-01-01

Environmental and depositional changes across the Late Cenomanian oceanic anoxic event (OAE2) in the Sinai, Egypt, are examined based on biostratigraphy, mineralogy, δ13C values and phosphorus analyses. Comparison with the Pueblo, Colorado, stratotype section reveals the Whadi El Ghaib section as stratigraphically complete across the late Cenomanian-early Turonian. Foraminifera are dominated by high-stress planktic and benthic assemblages characterized by low diversity, low-oxygen and low-salinity tolerant species, which mark shallow-water oceanic dysoxic conditions during OAE2. Oyster biostromes suggest deposition occurred in less than 50 m depths in low-oxygen, brackish, and nutrient-rich waters. Their demise prior to the peak δ13C excursion is likely due to a rising sea-level. Characteristic OAE2 anoxic conditions reached this coastal region only at the end of the δ13C plateau in deeper waters near the end of the Cenomanian. Increased phosphorus accumulations before and after the δ13C excursion suggest higher oxic conditions and increased detrital input. Bulk-rock and clay mineralogy indicate humid climate conditions, increased continental runoff and a rising sea up to the first δ13C peak. Above this interval, a dryer and seasonally well-contrasted climate with intermittently dry conditions prevailed. These results reveal the globally synchronous δ13C shift, but delayed effects of OAE2 dependent on water depth.