Effects of acidification on bryophyte communities in West Virginia mountain streams

Treesearch

Steven L. Stephenson; Susan Moyle Studlar; Carolyn J. McQuattie; Pamela J. Edwards

1995-01-01

Bryophytes (mosses and liverworts) are often more responsive to water chemistry changes than are vascular plants. In this study, the relationships of bryophyte communities to stream pH and water chemistry were studied, using six streams on or near the Fernow Experimental Forest in Tucker County, West Virginia. Streams were surveyed with line transects using stratified...

Element mobilization from Bakken shales as a function of water chemistry.

PubMed

Wang, Lin; Burns, Scott; Giammar, Daniel E; Fortner, John D

2016-04-01

Waters that return to the surface after injection of a hydraulic fracturing fluid for gas and oil production contain elements, including regulated metals and metalloids, which are mobilized through interactions between the fracturing fluid and the shale formation. The rate and extent of mobilization depends on the geochemistry of the formation and the chemical characteristics of the fracturing fluid. In this work, laboratory scale experiments investigated the influence of water chemistry on element mobilization from core samples taken from the Bakken formation, one of the most productive shale oil plays in the US. Fluid properties were systematically varied and evaluated with regard to pH, oxidant level, solid:water ratio, temperature, and chemical additives. Element mobilization strongly depended on solution pH and redox conditions and to a lesser extent on the temperature and solid:water ratio. The presence of oxygen and addition of hydrogen peroxide or ammonium persulfate led to pyrite oxidation, resulting in elevated sulfate concentrations. Further, depending on the mineral carbonates available to buffer the system pH, pyrite oxidation could lower the system pH and enhance the mobility of several metals and metalloids. Copyright © 2016 Elsevier Ltd. All rights reserved.

Impact of water chemistry on surface charge and aggregation of polystyrene microspheres suspensions.

PubMed

Lu, Songhua; Zhu, Kairuo; Song, Wencheng; Song, Gang; Chen, Diyun; Hayat, Tasawar; Alharbi, Njud S; Chen, Changlun; Sun, Yubing

2018-07-15

The discharge of microplastics into aquatic environment poses the potential threat to the hydrocoles and human health. The fate and transport of microplastics in aqueous solutions are significantly influenced by water chemistry. In this study, the effect of water chemistry (i.e., pH, foreign salts and humic acid) on the surface charge and aggregation of polystyrene microsphere in aqueous solutions was conducted by batch, zeta potentials, hydrodynamic diameters, FT-IR and XPS analysis. Compared to Na + and K + , the lower negative zeta potentials and larger hydrodynamic diameters of polystyrene microspheres after introduction of Mg 2+ were observed within a wide range of pH (2.0-11.0) and ionic strength (IS, 0.01-500mmol/L). No effect of Cl - , HCO 3 - and SO 4 2- on the zeta potentials and hydrodynamic diameters of polystyrene microspheres was observed at low IS concentrations (<5mmol/L), whereas the zeta potentials and hydrodynamic diameters of polystyrene microspheres after addition of SO 4 2- were higher than that of Cl - and HCO 3 - at high IS concentrations (>10mmol/L). The zeta potentials of polystyrene microspheres after HA addition were decreased at pH2.0-11.0, whereas the lower hydrodynamic diameters were observed at pH<4.0. According to FT-IR and XPS analysis, the change in surface properties of polystyrene microspheres after addition of hydrated Mg 2+ and HA was attributed to surface electrostatic and/or steric repulsions. These investigations are crucial for understanding the effect of water chemistry on colloidal stability of microplastics in aquatic environment. Copyright © 2018 Elsevier B.V. All rights reserved.

LEAD AND COPPER CONTROL WITH NON-ZINC ORTHOPHOSPHATE

EPA Science Inventory

Successful application of orthophosphate formulations not containing zinc for achieving control of copper and lead corrosion requires careful consideration of the background water chemistry, particularly pH and DIC. Inhibitor performance is extremely dependent upon dosage and pH,...

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

Farmer, R.W.; Dussert, B.W.; Kovacic, S.L.

Laboratory studies have identified the cause of the pH rise, which occurs during water treatment with activated carbon, as an interaction between the naturally occurring anions and protons in the water and the carbon surface. The interaction can be described as an ion exchange type of phenomenon, in which the carbon surface sorbs the anions and corresponding hydronium ions from the water. These studies have shown that the anion sorption and resulting pH increase is independent of the raw material used for the activated carbon production, e.g. bituminous or subbituminous coal, peat, wood or coconut. Also, the pH excursions occurmore » with virgin, reactivated, and acid washed granular carbons. Current pH control technologies focus on adjustment of the wastewater pH prior to discharge or recycle of the initial effluent water until the pH increase abates. However, improved water pH control options have been realized by altering the carbon surface through controlled oxidation rather than the water chemistry or extended preprocessing at the treatment site.« less

Relocation of net-acid-generating waste to improve post-mining water chemistry.

PubMed

Morin, K A; Hutt, N M

2001-01-01

Acidic drainage and metal leaching are long-term environmental liabilities that can persist for many decades to millennia. One technique to improve the water chemistry and ecology of post-mining landscapes is to relocate and submerge net-acid-generating mine materials in a lake or water-retaining impoundment. One example of a carefully executed relocation of waste rock took place at the Eskay Creek Mine in Canada. Pre-relocation studies included an empirical relationship that related (1) the amount of acidity retained by the waste rock during past oxidation to (2) the amount of lime needed in each truckload for neutralization of the acidity and for suppression of metal release. During relocation, thousands of rinse pH measurements indicated net acidity varied significantly over short distances within the waste rock and that acidic rock could not be reliably segregated from near-netural rock. After relocation, water from the watershed continued to be acidic for a few years, then returned to near-neutral pH and near-background concentrations of metals. The chemistry of the lake where the waste rock was submerged remains near background conditions. Therefore, with careful planning and implementation, the relocation and submergence of net-acid-generating materials can greatly improve post-mining water chemistry.

Conducting water chemistry of the secondary coolant circuit of VVER-based nuclear power plant units constructed without using copper containing alloys

NASA Astrophysics Data System (ADS)

Tyapkov, V. F.

2014-07-01

The secondary coolant circuit water chemistry with metering amines began to be put in use in Russia in 2005, and all nuclear power plant units equipped with VVER-1000 reactors have been shifted to operate with this water chemistry for the past seven years. Owing to the use of water chemistry with metering amines, the amount of products from corrosion of structural materials entering into the volume of steam generators has been reduced, and the flow-accelerated corrosion rate of pipelines and equipment has been slowed down. The article presents data on conducting water chemistry in nuclear power plant units with VVER-1000 reactors for the secondary coolant system equipment made without using copper-containing alloys. Statistical data are presented on conducting ammonia-morpholine and ammonia-ethanolamine water chemistries in new-generation operating power units with VVER-1000 reactors with an increased level of pH. The values of cooling water leaks in turbine condensers the tube system of which is made of stainless steel or titanium alloy are given.

Chem I Supplement: Emphasis on Acids and Bases

ERIC Educational Resources Information Center

Journal of Chemical Education Staff

1977-01-01

Provides supplementary notes on acids and bases suitable for secondary school chemistry instruction, including acidity in solid and natural waters, acidity balance in body chemistry, acid and basic foods, pH values of common fluids, examples of drugs, and commercial preparation of nitric acid. (SL)

Long-term stream chemistry monitoring on the fernow experiment forest: implications for sustainable management of hardwood forests

Treesearch

Mary Beth Adams; James N. Kochenderfer

2007-01-01

Long-term monitoring of stream chemistry of forested watersheds on the Fernow Experimental Forest in West Virginia has been conducted to determine the effects of both human induced and natural disturbances on nutrient cycling and stream chemistry. We compare mean annual stream water pH, and nitrate (NO3), sulfate (SO4), and...

Mineralogical transformations controlling acid mine drainage chemistry

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

Peretyazhko, Tetyana; Zachara, John M.; Boily, Jean F.

2009-05-30

The role of Fe(III) minerals in controlling acid mine drainage (AMD) chemistry was studied using samples from two AMD sites [Gum Boot (GB) and Fridays-2 (FR)] located in northern Pennsylvania. Chemical extractions, X-ray diffraction (XRD), scanning electron microscopy (SEM), and Fourier transform infrared spectroscopy (FTIR) were used to identify and characterize Fe(III) phases. The mineralogical analysis revealed that schwertmannite and goethite were the principal Fe(III) phases in the sediments. Schwertmannite transformation occurred at the GB site where poorly-crystallized goethite rich in surface-bound sulfate was initially formed. In contrast, no schwertmannite transformation occurred at the FR site. The goethite in GBmore » sediments had spherical morphology due to preservation of schwertmannite structure by adsorbed sulfate. Results of chemical extractions showed that poorly-crystallized goethite was subject to further crystallization accompanied by sulfate desorption. Changes in sulfate speciation preceded its desorption, with a conversion of bidentate- to monodentate-bound sulfate surface complexes. Laboratory sediment incubation experiments were conducted to evaluate the effect of mineral transformation on water chemistry. Incubation experiments were carried out with schwertmannite-containing sediments and AMD waters with different pH and chemical composition. The pH decreased to 1.9-2.2 in all suspensions and the concentrations of dissolved Fe and S increased significantly. Regardless of differences in the initial water composition, pH, Fe and S were similar in suspensions of the same sediment. XRD measurements revealed that schwertmannite transformed into goethite in GB and FR sediments during laboratory incubation. The incubation experiment demonstrated that schwertmannite transformation controlled AMD water chemistry during “closed system” laboratory contact.« less

Reactive solute transport in an acidic stream: Experimental pH increase and simulation of controls on pH, aluminum, and iron

USGS Publications Warehouse

Broshears, R.E.; Runkel, R.L.; Kimball, B.A.; McKnight, Diane M.; Bencala, K.E.

1996-01-01

Solute transport simulations quantitatively constrained hydrologic and geochemical hypotheses about field observations of a pH modification in an acid mine drainage stream. Carbonate chemistry, the formation of solid phases, and buffering interactions with the stream bed were important factors in explaining the behavior of pH, aluminum, and iron. The precipitation of microcrystalline gibbsite accounted for the behavior of aluminum; precipitation of Fe(OH)3 explained the general pattern of iron solubility. The dynamic experiment revealed limitations on assumptions that reactions were controlled only by equilibrium chemistry. Temporal variation in relative rates of photoreduction and oxidation influenced iron behavior. Kinetic limitations on ferrous iron oxidation and hydrous oxide precipitation and the effects of these limitations on field filtration were evident. Kinetic restraints also characterized interaction between the water column and the stream bed, including sorption and desorption of protons from iron oxides at the sediment-water interface and post-injection dissolution of the precipitated aluminum solid phase.

Influence of bedrock geology on water chemistry of slope wetlands and headwater streams in the southern Rocky Mountains

Treesearch

Monique LaPerriere Nelson; Charles C. Rhoades; Kathleen A. Dwire

2011-01-01

We characterized the water chemistry of nine slope wetlands and adjacent headwater streams in Colorado subalpine forests and compared sites in basins formed on crystalline bedrock with those formed in basins with a mixture of crystalline and sedimentary bedrock. The pH, Ca2+, Mg2+, NH4 +, acid neutralizing capacity, and electrical conductivity of wetland porewater and...

First-Principles pH Theory

NASA Astrophysics Data System (ADS)

Kim, Yong-Hyun; Zhang, S. B.

2006-03-01

Despite being one of the most important macroscopic measures and a long history even before the quantum mechanics, the concept of pH has rarely been mentioned in microscopic theories, nor being incorporated computationally into first-principles theory of aqueous solutions. Here, we formulate a theory for the pH dependence of solution formation energy by introducing the proton chemical potential as the microscopic counterpart of pH in atomistic solution models. Within the theory, the general acid-base chemistry can be cast in a simple pictorial representation. We adopt density-functional molecular dynamics to demonstrate the usefulness of the method by studying a number of solution systems including water, small solute molecules such as NH3 and HCOOH, and more complex amino acids with several functional groups. For pure water, we calculated the auto- ionization constant to be 13.2 with a 95 % accuracy. For other solutes, the calculated dissociation constants, i.e., the so- called pKa, are also in reasonable agreement with experiments. Our first-principles pH theory can be readily applied to broad solution chemistry problems such as redox reactions.

Influence of water chemistry on the acute toxicity of copper and zinc to the cladoceran Ceriodaphnia cf dubia.

PubMed

Hyne, Ross V; Pablo, Fleur; Julli, Moreno; Markich, Scott J

2005-07-01

This study determined the influence of key water chemistry parameters (pH, alkalinity, dissolved organic carbon [DOC], and hardness) on the aqueous speciation of copper and zinc and its relationship to the acute toxicity of these metals to the cladoceran Ceriodaphnia cf dubia. Immobilization tests were performed for 48-h in synthetic or natural waters buffered at various pH values from 5.5 to 8.4 (other chemical parameters held constant). The toxicity of copper to C. cf dubia decreased fivefold with increasing pH, whereas the toxicity of zinc increased fivefold with increasing pH. The effect of DOC on copper and zinc toxicity to C. cf dubia was determined using natural fulvic acid in the synthetic water. Increasing DOC was found to decrease linearly the toxicity of copper, with the mean effect concentration of copper that immobilized 50% of the cladocerans (EC50) value 45 times higher at 10 mg/L, relative to 0.1 mg/L DOC at pH 6.5. In contrast, the addition of 10 mg/L DOC only resulted in a very small (1.3-fold) reduction in the toxicity of zinc to C. cf dubia. Copper toxicity to C. cf dubia generally did not vary as a function of hardness, whereas zinc toxicity was reduced by a factor of only two, with an increase in water hardness from 44 to 374 mg CaCO3/L. Increasing bicarbonate alkalinity of synthetic waters (30-125 mg/L as CaCO3) decreased the toxicity of copper up to fivefold, which mainly could be attributed to the formation of copper-carbonate complexes, in addition to a pH effect. The toxicity of copper added to a range of natural waters with varying DOC content, pH, and hardness was consistent with the toxicity predicted using the data obtained from the synthetic waters.

Measuring restoration progress using pore- and surface-water chemistry across a chronosequence of formerly afforested blanket bogs.

PubMed

Gaffney, Paul P J; Hancock, Mark H; Taggart, Mark A; Andersen, Roxane

2018-08-01

During the restoration of degraded bogs and other peatlands, both habitat and functional recovery can be closely linked with nutrient cycling, which is reflected in pore- and surface-water chemistry. Several peatland restoration studies have shown that the time required for recovery of target conditions is slow (>10 years); for heavily-impacted, drained and afforested peatlands of northern Scotland, recovery time is unknown. We monitored pore- and surface-water chemistry across a chronosequence of formerly drained, afforested bog restoration sites spanning 0-17 years, using a space-for-time substitution, and compared them with open blanket bog control sites. Our aims were to measure rate of recovery towards bog conditions and to identify the best suite of water chemistry variables to indicate recovery. Our results show progress in recovery towards bog conditions over a 0-17 year period post-restoration. Elements scavenged by trees (Mg, Na, S) completely recovered within that period. Many water chemistry variables were affected by the restoration process itself, but recovered within 11 years, except ammonium (NH 4 + ), Zn and dissolved organic carbon (DOC) which remained elevated (when compared to control bogs) 17 years post restoration. Other variables did not completely recover (water table depth (WTD), pH), exhibiting what we term "legacy" effects of drainage and afforestation. Excess N and a lowered WTD are likely to slow the recovery of bog vegetation including key bog plants such as Sphagnum mosses. Over 17 years, we measured near-complete recovery in the chemistry of surface-water and deep pore-water but limited progress in shallow pore-water. Our results suggest that at least >17 years are required for complete recovery of water chemistry to bog conditions. However, we expect that newer restoration methods including conifer harvesting (stem plus brash) and the blocking of plough furrows (to increase the WTD) are likely to accelerate the restoration process (albeit at greater cost); this should be evaluated in future studies. We conclude that monitoring pore- and surface-water chemistry is useful in terms of indicating recovery towards bog conditions and we recommend monitoring WTD, pH, conductivity, Ca, NH 4 + , phosphate (PO 4 3- ), K, DOC, Al and Zn as key variables. Copyright © 2018 Elsevier Ltd. All rights reserved.

Variability of Ecosystem State in Rivers Containing Natural Dams: A Chemical Analysis

NASA Astrophysics Data System (ADS)

Reynolds, Z. A.

2015-12-01

Flooding, and the resulting economic damage to roads and property, is associated with natural dams such as beaver dams or log jams. For this reason, humans often remove natural dams; however, river reaches with natural dams provide very different ecosystem services in comparison with free-flowing river reaches. Therefore, the goal of this project is to assess the differences in ecosystem state between these different river reach types in the northeastern United States. We focused on differences in basic chemistry (e.g., dissolved oxygen, pH, temperature, and organic carbon) to assess the impact of natural dams on river ecosystem state. Study sites include rivers in the White Mountains and southeastern New Hampshire at locations with beaver dams, beaver ponds, beaver meadows, log jams, and free-flowing reaches. Dissolved oxygen, ORP, pH, temperature, and conductivity were measured in the field with a YSI Professional Plus meter. Water samples were collected for subsequent laboratory analysis of total organic carbon with a Shimadzu TOC-L. Preliminary results show that the chemistry of river water varies with feature type. Most significantly, dissolved oxygen concentrations are highest in free-flowing reaches and lowest in beaver ponds. Although beaver ponds are often associated with lower pH, due the increased concentration of organic acids, some beaver ponds can increase pH when compared to free-flowing reaches on the same river. Early results also show that water chemistry returns quickly to the chemistry typical of the free-flowing river reaches after being altered by a natural dam. Overall, natural dams create a river system that has more heterogeneity, and therefore has opportunities to provide more ecosystem functions, than a purely free-flowing river; this can increase the number of supported instream and riparian species. By increasing the understanding of how natural dams affect the chemistry of river water, river engineers can improve their decisions on how to remove problematic natural dams that increase flooding risks; they can also investigate possibilities to mimic the ecosystem state generated by natural dams in places where these dams are regularly removed.

Release behavior of uranium in uranium mill tailings under environmental conditions.

PubMed

Liu, Bo; Peng, Tongjiang; Sun, Hongjuan; Yue, Huanjuan

2017-05-01

Uranium contamination is observed in sedimentary geochemical environments, but the geochemical and mineralogical processes that control uranium release from sediment are not fully appreciated. Identification of how sediments and water influence the release and migration of uranium is critical to improve the prevention of uranium contamination in soil and groundwater. To understand the process of uranium release and migration from uranium mill tailings under water chemistry conditions, uranium mill tailing samples from northwest China were investigated with batch leaching experiments. Results showed that water played an important role in uranium release from the tailing minerals. The uranium release was clearly influenced by contact time, liquid-solid ratio, particle size, and pH under water chemistry conditions. Longer contact time, higher liquid content, and extreme pH were all not conducive to the stabilization of uranium and accelerated the uranium release from the tailing mineral to the solution. The values of pH were found to significantly influence the extent and mechanisms of uranium release from minerals to water. Uranium release was monitored by a number of interactive processes, including dissolution of uranium-bearing minerals, uranium desorption from mineral surfaces, and formation of aqueous uranium complexes. Considering the impact of contact time, liquid-solid ratio, particle size, and pH on uranium release from uranium mill tailings, reducing the water content, decreasing the porosity of tailing dumps and controlling the pH of tailings were the key factors for prevention and management of environmental pollution in areas near uranium mines. Copyright © 2017 Elsevier Ltd. All rights reserved.

Survival of spotted salamander eggs in temporary woodland ponds of coastal Maryland

USGS Publications Warehouse

Albers, P.H.; Prouty, R.M.

1987-01-01

Temporary ponds on the Atlantic Coastal Plain in maryland were characterized according to water chemistry, rain input, phytoplankton, zooplankton and use by the spotted salamander Ambystoma maculatum during March-October 1983-1984. Neither the number of egg masses per unit of pond surface (abundance) nor the survival of spotted salamander embryos was significantly correlated (P>0.05) with pond pH. Rainfall during May-July significantly increased the hydrogen ion concentration of 5 of 11 ponds evaluated for the impact of rainfall during the previous 48h and the previous week. Survival of egg masses transferred among eight ponds with pH3.66-4.45 and one pond with pH5.18 was significantly reduced (P

Computation of iodine species concentrations in water

NASA Technical Reports Server (NTRS)

Schultz, John R.; Mudgett, Paul D.; Flanagan, David T.; Sauer, Richard L.

1994-01-01

During an evaluation of the use of iodine as a water disinfectant and the development of methods for measuring various iodine species in water onboard Space Freedom, it became necessary to compute the concentration of the various species based on equilibrium principles alone. Of particular concern was the case when various amounts of iodine, iodide, strong acid, and strong base are added to water. Such solutions can be used to evaluate the performance of various monitoring methods being considered. The authors of this paper present an overview of aqueous iodine chemistry, a set of nonlinear equations which can be used to model the above case, and a computer program for solving this system of equations using the Newton-Raphson method. The program was validated by comparing results over a range of concentrations and pH values with those previously presented by Gottardi for a given pH. Use of this program indicated that there are multiple roots to many cases and selecting an appropriate initial guess is important. Comparison of program results with laboratory results for the case when only iodine is added to water indicates the program gives high pH values for the iodine concentrations normally used for water disinfection. Extending the model to include the effects of iodate formation results in the computer pH values being closer to those observed, but the model with iodate does not agree well for the case in which base is added in addition to iodine to raise the pH. Potential explanations include failure to obtain equilibrium conditions in the lab, inaccuracies in published values for the equilibrium constants, and inadequate model of iodine chemistry and/or the lack of adequate analytical methods for measuring the various iodine species in water.

Chemistry of Stream Sediments and Surface Waters in New England

USGS Publications Warehouse

Robinson, Gilpin R.; Kapo, Katherine E.; Grossman, Jeffrey N.

2004-01-01

Summary -- This online publication portrays regional data for pH, alkalinity, and specific conductance for stream waters and a multi-element geochemical dataset for stream sediments collected in the New England states of Connecticut, Maine, Massachusetts, New Hampshire, Rhode Island, and Vermont. A series of interpolation grid maps portray the chemistry of the stream waters and sediments in relation to bedrock geology, lithology, drainage basins, and urban areas. A series of box plots portray the statistical variation of the chemical data grouped by lithology and other features.

Naturally acidic surface and ground waters draining porphyry-related mineralized areas of the Southern Rocky Mountains, Colorado and New Mexico

USGS Publications Warehouse

Verplanck, P.L.; Nordstrom, D. Kirk; Bove, D.J.; Plumlee, G.S.; Runkel, R.L.

2009-01-01

Acidic, metal-rich waters produced by the oxidative weathering and resulting leaching of major and trace elements from pyritic rocks can adversely affect water quality in receiving streams and riparian ecosystems. Five study areas in the southern Rocky Mountains with naturally acidic waters associated with porphyry mineralization were studied to document variations in water chemistry and processes that control the chemical variations. Study areas include the Upper Animas River watershed, East Alpine Gulch, Mount Emmons, and Handcart Gulch in Colorado and the Red River in New Mexico. Although host-rock lithologies in all these areas range from Precambrian gneisses to Cretaceous sedimentary units to Tertiary volcanic complexes, the mineralization is Tertiary in age and associated with intermediate to felsic composition, porphyritic plutons. Pyrite is ubiquitous, ranging from ???1 to >5 vol.%. Springs and headwater streams have pH values as low as 2.6, SO4 up to 3700 mg/L and high dissolved metal concentrations (for example: Fe up to 400 mg/L; Cu up to 3.5 mg/L; and Zn up to 14.4 mg/L). Intensity of hydrothermal alteration and presence of sulfides are the primary controls of water chemistry of these naturally acidic waters. Subbasins underlain by intensely hydrothermally altered lithologies are poorly vegetated and quite susceptible to storm-induced surface runoff. Within the Red River study area, results from a storm runoff study documented downstream changes in river chemistry: pH decreased from 7.80 to 4.83, alkalinity decreased from 49.4 to <1 mg/L, SO4 increased from 162 to 314 mg/L, dissolved Fe increased from to 0.011 to 0.596 mg/L, and dissolved Zn increased from 0.056 to 0.607 mg/L. Compared to mine drainage in the same study areas, the chemistry of naturally acidic waters tends to overlap but not reach the extreme concentrations of metals and acidity as some mine waters. The chemistry of waters draining these mineralized but unmined areas can be used to estimate premining conditions at sites with similar geologic and hydrologic conditions. For example, the US Geological Survey was asked to estimate premining ground-water chemistry at the Questa Mo mine, and the proximal analog approach was used because a mineralized but unmined area was located adjacent to the mine property. By comparing and contrasting water chemistry from different porphyry mineralized areas, this study not only documents the range in concentrations of constituents of interest but also provides insight into the primary controls of water chemistry.

The influence of the chemical composition of drinking water on cuprosolvency by biofilm bacteria.

PubMed

Critchley, M M; Cromar, N J; McClure, N C; Fallowfield, H J

2003-01-01

This study investigated the influence of water chemistry on copper solvation (cuprosolvency) by pure culture biofilms of heterotrophic bacteria isolated from copper plumbing. Heterotrophic bacteria isolated from copper plumbing biofilms including Acidovorax delafieldii, Flavobacterium sp., Corynebacterium sp., Pseudomonas sp. and Stenotrophomonas maltophilia were used in laboratory coupon experiments to assess their potential for cuprosolvency. Sterile copper coupons were exposed to pure cultures of bacteria to allow biofilm formation and suspended in drinking waters with different chemical compositions. Sterile coupons not exposed to bacteria were used as controls. After 5 days of incubation, copper release and biofilm accumulation was quantified. The results demonstrated that cuprosolvency in the control experiments was influenced by water pH, total organic carbon (TOC) and conductivity. Cuprosolvency in the presence of biofilms correlated with the chemical composition of the water supplies particularly pH, Langeliers Index, chloride, alkalinity, TOC and soluble phosphate concentrations. The results suggest water quality may influence cuprosolvency by biofilms present within copper plumbing pipes. The potential for water chemistry to influence cuprosolvency by biofilms may contribute to the sporadic nature of copper corrosion problems in distribution systems.

Peroxidase-mediated polymerization of 1-naphthol: impact of solution pH and ionic strength.

PubMed

Bhandari, Alok; Xu, Fangxiang; Koch, David E; Hunter, Robert P

2009-01-01

Peroxidase-mediated oxidation has been proposed as a treatment method for naphthol-contaminated water. However, the impact of solution chemistry on naphthol polymerization and removal has not been documented. This research investigated the impact of pH and ionic strength on peroxidase-mediated removal of 1-naphthol in completely mixed batch reactors. The impact of hydrogen peroxide to 1-naphthol ratio and activity of horseradish peroxidase was also studied. Size exclusion chromatography was used to estimate the molecular weight distribution of oligomeric products, and liquid chromatography/mass spectrometry was used to estimate product structure. Naphthol transformation decreased with ionic strength, and substrate removal was lowest at neutral pHs. Solution pH influenced the size and the composition of the oligomeric products. An equimolar ratio of H(2)O(2):naphthol was sufficient for optimal naphthol removal. Polymerization products included naphthoquinones and oligomers derived from two, three, and four naphthol molecules. Our results illustrate the importance of water chemistry when considering a peroxidase-based approach for treatment of naphthol-contaminated waters.

Introduction to Instrumental Analysis of Water Pollutants. Training Manual.

ERIC Educational Resources Information Center

Office of Water Program Operations (EPA), Cincinnati, OH. National Training and Operational Technology Center.

This course is designed for those requiring an introduction to instruments commonly used in water pollution analyses. Examples are: pH, conductivity, dissolved oxygen meters, spectrophotometers, turbidimeters, carbon analyzer, and gas chromatographs. Students should have a basic knowledge of analytical chemistry. (CO)

Spatiotemporal pH dynamics in concentration polarization near ion-selective membranes.

PubMed

Andersen, Mathias B; Rogers, David M; Mai, Junyu; Schudel, Benjamin; Hatch, Anson V; Rempe, Susan B; Mani, Ali

2014-07-08

We present a detailed analysis of the transient pH dynamics for a weak, buffered electrolyte subject to voltage-driven transport through an ion-selective membrane. We show that pH fronts emanate from the concentration polarization zone next to the membrane and that these propagating fronts change the pH in the system several units from its equilibrium value. The analysis is based on a 1D model using the unsteady Poisson-Nernst-Planck equations with nonequilibrium chemistry and without assumptions of electroneutrality or asymptotically thin electric double layers. Nonequilibrium chemical effects, especially for water splitting, are shown to be important for the dynamical and spatiotemporal evolution of the pH fronts. Nonetheless, the model also shows that at steady state the assumption of chemical equilibrium can still lead to good approximations of the global pH distribution. Moreover, our model shows that the transport of the hydronium ion in the extended space charge region is governed by a balance between electromigration and water self-ionization. On the basis of this observation, we present a simple model showing that the net flux of the hydronium ion is proportional to the length of the extended space charge region and the water self-ionization rate. To demonstrate these effects in practice, we have adopted the experiment of Mai et al. (Mai, J.; Miller, H.; Hatch, A. V. Spatiotemporal Mapping of Concentration Polarization Induced pH Changes at Nanoconstrictions. ACS Nano 2012, 6, 10206) as a model problem, and by including the full chemistry and transport, we show that the present model can capture the experimentally observed pH fronts. Our model can, among other things, be used to predict and engineer pH dynamics, which can be essential to the performance of membrane-based systems for biochemical separation and analysis.

Natural variability of pCO2 and pH in the Atlantic and Pacific coastal margins of the U.S

NASA Astrophysics Data System (ADS)

Sutton, A. J.; Sabine, C. L.; Feely, R. A.; Newton, J.; Salisbury, J.; Vandemark, D. C.; Musielewicz, S. B.; Maenner-Jones, S.; Bott, R.; Lawrence-Slavas, N.

2011-12-01

The discovery that seawater chemistry is changing as a result of carbon dioxide (CO2) emissions, referred to as "ocean acidification", has prompted a large effort to understand how this changing chemistry will impact marine life. Changes in carbon chemistry have been documented in the open ocean; however, in dynamic coastal systems where many marine species live, ocean acidification and the natural biogeochemical variability that organisms are currently exposed to are poorly quantified. In 2010 we began equipping coastal moorings currently measuring pCO2 with pH and other biogeochemical sensors to measure ocean acidification parameters at 3 hour intervals in the surface water. Here we present the magnitude and diurnal to seasonal variability of pCO2 and pH during the first year of observations at 2 sites in the Atlantic and Pacific coastal margins of the U.S.: the Gulf of Maine and outer coast of Washington state. Both the magnitude and range of pCO2 and pH values were much greater at the coastal moorings compared to the open ocean mooring at Ocean Station Papa in the North Pacific and also varied between the two coastal mooring sites. We observed maximum pCO2 values in coastal waters exceeding predicted values for the open ocean at 2x pre-industrial CO2 levels. The range of pCO2 and pH values during this time series was approximately 4 times the range observed at open ocean mooring Papa (2007-2011 time series). In many cases, large variance was observed at short time scales, with values fluctuating more than 200 μatm pCO2 and 0.2 pH between 3-hour cycles. These types of observations are critical for understanding how ocean acidification will manifest in naturally dynamic coastal systems and for informing the experimental design of species response studies that aim to mimic carbon chemistry experienced by coastal marine organisms.

Radiation field control at the latest BWR plants -- design principle, operational experience and future subjects

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

Uchida, Shunsuke; Ohsumi, Katsumi; Takashima, Yoshie

1995-03-01

Improvements of operational procedures to control water chemistry, e.g., nickel/iron control, as well as application of hardware improvements for reducing radioactive corrosion products resulted in an extremely low occupational exposure of less than 0.5 man.Sv/yr without any serious impact on the radwaste system, for BWR plants involved in the Japanese Improvement and Standardization Program. Recently, {sup 60}C radioactively in the reactor water has been increasing due to less crud fixation on the two smooth surfaces of new type high performance fuels and to the pH drop caused by chromium oxide anions released from stainless steel structures and pipings. This increasemore » must be limited by changes in water chemistry, e.g., applications of modified nickel/iron ratio control and weak alkali control. Controlled water chemistry to optimize three points, the plant radiation level and integrities of fuel and structural materials, is the primary future subject for BWR water chemistry.« less

Evolution of the chemistry of Fe bearing waters during CO2 degassing

USGS Publications Warehouse

Geroni, J.N.; Cravotta, C.A.; Sapsford, D.J.

2012-01-01

The rates of Fe(II) oxidation and precipitation from groundwater are highly pH dependent. Elevated levels of dissolved CO2 can depress pH and cause difficulty in removing dissolved Fe and associated metals during treatment of ferruginous water. This paper demonstrates interdependent changes in pH, dissolved inorganic C species, and Fe(II) oxidation rates that occur as a result of the removal (degassing) of CO2 during aeration of waters discharged from abandoned coal mines. The results of field monitoring of aeration cascades at a treatment facility as well as batchwise aeration experiments conducted using net alkaline and net acidic waters in the UK are combined with geochemical modelling to demonstrate the spatial and temporal evolution of the discharge water chemistry. The aeration cascades removed approximately 67% of the dissolved CO2 initially present but varying the design did not affect the concentration of Fe(II) leaving the treatment ponds. Continued removal of the residual CO2 by mechanical aeration increased pH by as much as 2 units and resulted in large increases in the rates of Fe(II) oxidation and precipitation. Effective exsolution of CO2 led to a reduction in the required lime dose for removal of remaining Fe(II), a very important factor with regard to increasing the sustainability of treatment practices. An important ancillary finding for passive treatment is that varying the design of the cascades had little impact on the rate of CO2 removal at the flow rates measured.

Impact of Environmentally Based Chemical Hardness on Uranium Speciation and Toxicity in Six Aquatic Species

PubMed Central

Goulet, Richard R; Thompson, Patsy A; Serben, Kerrie C; Eickhoff, Curtis V

2015-01-01

Treated effluent discharge from uranium (U) mines and mills elevates the concentrations of U, calcium (Ca), magnesium (Mg), and sulfate (SO42–) above natural levels in receiving waters. Many investigations on the effect of hardness on U toxicity have been experiments on the combined effects of changes in hardness, pH, and alkalinity, which do not represent water chemistry downstream of U mines and mills. Therefore, more toxicity studies with water chemistry encountered downstream of U mines and mills are necessary to support predictive assessments of impacts of U discharge to the environment. Acute and chronic U toxicity laboratory bioassays were realized with 6 freshwater species in waters of low alkalinity, circumneutral pH, and a range of chemical hardness as found in field samples collected downstream of U mines and mills. In laboratory-tested waters, speciation calculations suggested that free uranyl ion concentrations remained constant despite increasing chemical hardness. When hardness increased while pH remained circumneutral and alkalinity low, U toxicity decreased only to Hyalella azteca and Pseudokirchneriella subcapitata. Also, Ca and Mg did not compete with U for the same uptake sites. The present study confirms that the majority of studies concluding that hardness affected U toxicity were in fact studies in which alkalinity and pH were the stronger influence. The results thus confirm that studies predicting impacts of U downstream of mines and mills should not consider chemical hardness. PMID:25475484

Aqua de Ney, California, a spring of unique chemical character

USGS Publications Warehouse

Feth, J.H.; Rogers, S.M.; Roberson, C.E.

1961-01-01

The chemistry of water of Aqua de Ney, a cold spring of unusual character located in Siskiyou County, Calif., has been re-examined as part of a study of the relation of water chemistry to rock environment. The water has a pH of 11??6 and a silica content of 4000 parts per million (p.p.m.), the highest values known to occur in natural ground waters. The rocks exposed nearby consist of two volcanic sequences, one predominantly basaltic in composition, the other highly siliceous. Neither these rocks nor the sedimentary and igneous rocks presumed to underlie the area at depth seem to offer explanation of the unusual mineralization which includes 240 p.p.m. of boron, 1000 p.p.m. of sulphide (as H2S), and 148 p.p.m. of ammonia nitrogen (as NH4) in a water that is predominantly sodium chloride and sodium carbonate in character. By analogy, it is assumed that water from Aqua de Ney is the product of an initial mixture of connate sea water with a calcium magnesium sulphate water. It is postulated that ion exchange has increased the content of sodium and reduced that of calcium and magnesium, and that sulphate reduction has brought about the high alkalinity, high pH, and high content of sulphide. The large silica value is explained as the result of solution of silica by water having the high pH observed. ?? 1961.

The spatial variability of water chemistry and DOC in bog pools: the importance of slope position, diurnal turnover and pool type

NASA Astrophysics Data System (ADS)

Holden, Joseph; Turner, Ed; Baird, Andy; Beadle, Jeannie; Billett, Mike; Brown, Lee; Chapman, Pippa; Dinsmore, Kerry; Dooling, Gemma; Grayson, Richard; Moody, Catherine; Gee, Clare

2017-04-01

We have previously shown that marine influence is an important factor controlling regional variability of pool water chemistry in blanket peatlands. Here we examine within-site controls on pool water chemistry. We surveyed natural and artificial (restoration sites) bog pools at blanket peatland sites in northern Scotland and Sweden. DOC, pH, conductivity, dissolved oxygen, temperature, cations, anions and absorbance spectra from 220-750nm were sampled. We sampled changes over time but also conducted intensive spatial surveys within individual pools and between pools on the same sampling days at individual study sites. Artificial pools had significantly greater DOC concentrations and different spectral absorbance characteristics when compared to natural pools at all sites studied. Within-pool variability in water chemistry tended to be small, even for very large pools ( 400 m2), except where pools had a layer of loose, mobile detritus on their beds. In these instances rapid changes took place between the overlying water column and the mobile sediment layer wherein dissolved oxygen concentrations dropped from values of around 12-10 mg/L to values less than 0.5 mg/L over just 2-3 cm of the depth profile. Such strong contrasts were not observed for pools which had a hard peat floor and which lacked a significant detritus layer. Strong diurnal turnover occurred within the pools on summer days, including within small, shallow pools (e.g. < 30 cm deep, 1 m2 area). For many pools on these summer days there was an evening spike in dissolved oxygen concentrations which originated at the surface and was then cycled downwards as the pool surface waters cooled. Slope location was a significant control on several pool water chemistry variables including pH and DOC concentration with accumulation (higher concentrations) in pools that were located further downslope in both natural and artificial pool systems. These processes have important implications for our interpretation of water chemistry and gas flux data from pool systems, how we design our sampling strategies and how we upscale results.

Daily and seasonal variability of pH, dissolved oxygen, temperature, and specific conductance in the Colorado River between the forebay of Glen Canyon, Dam and Lees Ferry, northeastern Arizona, 1998-99

USGS Publications Warehouse

Flynn, Marilyn E.; Hart, Robert J.; Marzolf, G. Richard; Bowser, Carl J.

2001-01-01

The productivity of the trout fishery in the tailwater reach of the Colorado River downstream from Glen Canyon Dam depends on the productivity of lower trophic levels. Photosynthesis and respiration are basic biological processes that control productivity and alter pH and oxygen concentration. During 1998?99, data were collected to aid in the documentation of short- and long-term trends in these basic ecosystem processes in the Glen Canyon reach. Dissolved-oxygen, temperature, and specific-conductance profile data were collected monthly in the forebay of Glen Canyon Dam to document the status of water chemistry in the reservoir. In addition, pH, dissolved-oxygen, temperature, and specific-conductance data were collected at five sites in the Colorado River tailwater of Glen Canyon Dam to document the daily, seasonal, and longitudinal range of variation in water chemistry that could occur annually within the Glen Canyon reach.

Cognitive disparities, lead plumbing, and water chemistry: prior exposure to water-borne lead and intelligence test scores among World War Two U.S. Army enlistees.

PubMed

Ferrie, Joseph P; Rolf, Karen; Troesken, Werner

2012-01-01

Higher prior exposure to water-borne lead among male World War Two U.S. Army enlistees was associated with lower intelligence test scores. Exposure was proxied by urban residence and the water pH levels of the cities where enlistees lived in 1930. Army General Classification Test scores were six points lower (nearly 1/3 standard deviation) where pH was 6 (so the water lead concentration for a given amount of lead piping was higher) than where pH was 7 (so the concentration was lower). This difference rose with time exposed. At this time, the dangers of exposure to lead in water were not widely known and lead was ubiquitous in water systems, so these results are not likely the effect of individuals selecting into locations with different levels of exposure. Copyright © 2011 Elsevier B.V. All rights reserved.

Transport of soil-aged silver nanoparticles in unsaturated sand.

PubMed

Kumahor, Samuel K; Hron, Pavel; Metreveli, George; Schaumann, Gabriele E; Klitzke, Sondra; Lang, Friederike; Vogel, Hans-Jörg

2016-12-01

Engineered nanoparticles released into soils may be coated with humic substances, potentially modifying their surface properties. Due to their amphiphilic nature, humic coating is expected to affect interaction of nanoparticle at the air-water interface. In this study, we explored the roles of the air-water interface and solid-water interface as potential sites for nanoparticle attachment and the importance of hydrophobic interactions for nanoparticle attachment at the air-water interface. By exposing Ag nanoparticles to soil solution extracted from the upper soil horizon of a floodplain soil, the mobility of the resulting "soil-aged" Ag nanoparticles was investigated and compared with the mobility of citrate-coated Ag nanoparticles as investigated in an earlier study. The mobility was determined as a function of hydrologic conditions and solution chemistry using column breakthrough curves and numerical modeling. Specifically, we compared the mobility of both types of nanoparticles for different unsaturated flow conditions and for pH=5 and pH=9. The soil-aged Ag NP were less mobile at pH=5 than at pH=9 due to lower electrostatic repulsion at pH=5 for both types of interfaces. Moreover, the physical flow field at different water contents modified the impact of chemical forces at the solid-water interface. An extended Derjaguin-Landau-Verwey-Overbeek (eDLVO) model did not provide satisfactory explanation of the observed transport phenomena unlike for the citrate-coated case. For instance, the eDLVO model assuming sphere-plate geometry predicts a high energy barrier (>90 kT) for the solid-water interface, indicating that nanoparticle attachment is less likely. Furthermore, retardation through reversible sorption at the air-water interface was probably less relevant for soil-aged nanoparticles than for citrate-coated nanoparticles. An additional cation bridging mechanism and straining within the flow field may have enhanced nanoparticle retention at the solid-water interface. The results indicate that the mobility of engineered Ag nanoparticles is sensitive to solution chemistry, especially pH and the concentration of multivalent cations, and to the unsaturated flow conditions influencing particle interaction at biogeochemical interfaces. Copyright © 2016 Elsevier B.V. All rights reserved.

Transport of soil-aged silver nanoparticles in unsaturated sand

NASA Astrophysics Data System (ADS)

Kumahor, Samuel K.; Hron, Pavel; Metreveli, George; Schaumann, Gabriele E.; Klitzke, Sondra; Lang, Friederike; Vogel, Hans-Jörg

2016-12-01

Engineered nanoparticles released into soils may be coated with humic substances, potentially modifying their surface properties. Due to their amphiphilic nature, humic coating is expected to affect interaction of nanoparticle at the air-water interface. In this study, we explored the roles of the air-water interface and solid-water interface as potential sites for nanoparticle attachment and the importance of hydrophobic interactions for nanoparticle attachment at the air-water interface. By exposing Ag nanoparticles to soil solution extracted from the upper soil horizon of a floodplain soil, the mobility of the resulting ;soil-aged; Ag nanoparticles was investigated and compared with the mobility of citrate-coated Ag nanoparticles as investigated in an earlier study. The mobility was determined as a function of hydrologic conditions and solution chemistry using column breakthrough curves and numerical modeling. Specifically, we compared the mobility of both types of nanoparticles for different unsaturated flow conditions and for pH = 5 and pH = 9. The soil-aged Ag NP were less mobile at pH = 5 than at pH = 9 due to lower electrostatic repulsion at pH = 5 for both types of interfaces. Moreover, the physical flow field at different water contents modified the impact of chemical forces at the solid-water interface. An extended Derjaguin-Landau-Verwey-Overbeek (eDLVO) model did not provide satisfactory explanation of the observed transport phenomena unlike for the citrate-coated case. For instance, the eDLVO model assuming sphere-plate geometry predicts a high energy barrier (> 90 kT) for the solid-water interface, indicating that nanoparticle attachment is less likely. Furthermore, retardation through reversible sorption at the air-water interface was probably less relevant for soil-aged nanoparticles than for citrate-coated nanoparticles. An additional cation bridging mechanism and straining within the flow field may have enhanced nanoparticle retention at the solid-water interface. The results indicate that the mobility of engineered Ag nanoparticles is sensitive to solution chemistry, especially pH and the concentration of multivalent cations, and to the unsaturated flow conditions influencing particle interaction at biogeochemical interfaces.

Acid-base characteristics of the Grass Pond watershed in the Adirondack Mountains of New York State, USA: interactions among soil, vegetation and surface waters

NASA Astrophysics Data System (ADS)

McEathron, K. M.; Mitchell, M. J.; Zhang, L.

2013-07-01

Grass Pond watershed is located within the southwestern Adirondack Mountain region of New York State, USA. This region receives some of the highest rates of acidic deposition in North America and is particularly sensitive to acidic inputs due to many of its soils having shallow depths and being generally base poor. Differences in soil chemistry and tree species between seven subwatersheds were examined in relation to acid-base characteristics of the seven major streams that drain into Grass Pond. Mineral soil pH, stream water BCS (base-cation surplus) and pH exhibited a positive correlation with sugar maple basal area (p = 0.055; 0.48 and 0.39, respectively). Black cherry basal area was inversely correlated with stream water BCS, ANC (acid neutralizing capacity)c and NO3- (p = 0.23; 0.24 and 0.20, respectively). Sugar maple basal areas were positively associated with watershed characteristics associated with the neutralization of atmospheric acidic inputs while in contrast, black cherry basal areas showed opposite relationships to these same watershed characteristics. Canonical correspondence analysis indicated that black cherry had a distinctive relationship with forest floor chemistry apart from the other tree species, specifically a strong positive association with forest floor NH4, while sugar maple had a distinctive relationship with stream chemistry variables, specifically a strong positive association with stream water ANCc, BCS and pH. Our results provide evidence that sugar maple is acid-intolerant or calciphilic tree species and also demonstrate that black cherry is likely an acid-tolerant tree species.

SNS Resonance Control Cooling Systems and Quadrupole Magnet Cooling Systems DIW Chemistry

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

Magda, Karoly

This report focuses on control of the water chemistry for the Spallation Neutron Source (SNS) Resonance Control Cooling System (RCCS)/Quadrupole Magnet Cooling System (QMCS) deionized water (DIW) cooling loops. Data collected from spring 2013 through spring 2016 are discussed, and an operations regime is recommended.It was found that the RCCS operates with an average pH of 7.24 for all lines (from 7.0 to 7.5, slightly alkaline), the average low dissolved oxygen is in the area of < 36 ppb, and the main loop average resistivity of is > 14 MΩ-cm. The QMCS was found to be operating in a similarmore » regime, with a slightly alkaline pH of 7.5 , low dissolved oxygen in the area of < 45 ppb, and main loop resistivity of 10 to 15 MΩ-cm. During data reading, operational corrections were done on the polishing loops to improve the water chemistry regime. Therefore some trends changed over time.It is recommended that the cooling loops operate in a regime in which the water has a resistivity that is as high as achievable, a dissolved oxygen concentration that is as low as achievable, and a neutral or slightly alkaline pH.« less

Water Reclamation Technology Development at Johnson Space Center

NASA Technical Reports Server (NTRS)

Callahan, Michael R.; Pickering, Karen

2014-01-01

Who We Are: A staff of approximately 14 BS, MS, and PhD-Level Engineers and Scientists with experience in Aerospace, Civil, Environmental, and Mechanical Engineering, Chemistry, Physical Science and Water Pollution Microbiology. Our Primary Objective: To develop the next generation water recovery system technologies that will support NASA's long duration missions beyond low-earth orbit.

Coagulation removal of humic acid-stabilized carbon nanotubes from water by PACl: influences of hydraulic condition and water chemistry.

PubMed

Ma, Si; Liu, Changli; Yang, Kun; Lin, Daohui

2012-11-15

Discharged carbon nanotubes (CNTs) can adsorb the widely-distributed humic acid (HA) in aquatic environments and thus be stabilized. HA-stabilized CNTs can find their way into and challenge the potable water treatment system. This study investigated the efficiency of coagulation and sedimentation techniques in the removal of the HA-stabilized multi-walled carbon nanotubes (MWCNTs) using polyaluminum chloride (PACl) as a coagulant, with a focus on the effects of hydraulic conditions and water chemistry. Stirring speeds in the mixing and reacting stages were gradually changed to examine the effect of the hydraulic conditions on the removal rate. The stirring speed in the reacting stage affected floc formation and thereby had a greater impact on the removal rate than the stirring speed in the mixing stage. Water chemistry factors such as pH and ionic strength had a significant effect on the stability of MWCNT suspension and the removal efficiency. Low pH (4-7) was favorable for saving the coagulant and maintaining high removal efficiency. High ionic strength facilitated the destabilization of the HA-stabilized MWCNTs and thereby lowered the required PACl dosage for the coagulation. However, excessively high ionic strength (higher than the critical coagulation concentration) decreased the maximum removal rate, probably by inhibiting ionic activity of PACl hydrolyzate in water. These results are expected to shed light on the potential improvement of coagulation removal of aqueous stabilized MWCNTs in water treatment systems. Copyright © 2012 Elsevier B.V. All rights reserved.

Buffer capacity, ecosystem feedbacks, and seawater chemistry under global change

NASA Astrophysics Data System (ADS)

Jury, C. P.; Thomas, F. I.; Atkinson, M. J.; Jokiel, P. L.; Onuma, M. A.; Kaku, N.; Toonen, R. J.

2013-12-01

Ocean acidification (OA) results in reduced seawater pH and aragonite saturation state (Ωarag), but also reduced seawater buffer capacity. As buffer capacity decreases, diel variation in seawater chemistry increases. However, a variety of ecosystem feedbacks can modulate changes in both average seawater chemistry and diel seawater chemistry variation. Here we model these effects for a coastal, reef flat ecosystem. We show that an increase in offshore pCO2 and temperature (to 900 μatm and +3°C) can increase diel pH variation by as much as a factor of 2.5 and can increase diel pCO2 variation by a factor of 4.6, depending on ecosystem feedbacks and seawater residence time. Importantly, these effects are different between day and night. With increasing seawater residence time and increasing feedback intensity, daytime seawater chemistry becomes more similar to present-day conditions while nighttime seawater chemistry becomes less similar to present-day conditions. Better constraining ecosystem feedbacks under global change will improve projections of coastal water chemistry, but this study shows the importance of considering changes in both average carbonate chemistry and diel chemistry variation for organisms and ecosystems. Further, we will discuss our recent work examining the effects of diel seawater chemistry variation on coral calcification rates.

Impacts of ocean acidification on the carbonate system at the sediment-water interface: a case-study in the NW Mediterranean Sea

NASA Astrophysics Data System (ADS)

Rassmann, Jens; Lansard, Bruno; Gazeau, Frédéric; Grenz, Christian; Alliouane, Samir; Petit, Franck; Pozzato, Lara; Bombled, Bruno; Rabouille, Christophe

2016-04-01

According to common predictions, carbon dioxide (CO2) uptake from the atmosphere into the oceans will decrease the average pH of seawater by 0.06-0.32 pH units by 2100. Ocean acidification alters chemical equilibria in seawater and thus potentially impacts marine ecosystem structure and functioning. Shelf regions play a key role for an important fraction of marine life and represent an important part of the global carbon cycle. Due to shallow water depth, chemistry in the water column is strongly coupled with biogeochemistry in the sediments. The aim of the present work is to investigate the impact of ocean acidification on carbonate chemistry. It focuses especially on exchange fluxes of dissolved inorganic carbon (DIC), total alkalinity (TA) and calcium through the sediment-water interface, and its impact on calcium carbonate precipitation or dissolution. For this purpose, sediment cores were incubated ex situ with an open flow of CO2 enriched seawater for 22 days (pHT=7,4, pH reported on the total proton scale). In parallel, sediment cores were incubated as a control with untreated seawater. Incubations took place in a water bath in a dark room with controlled temperature (14°C). Oxygen and pH microprofiles were recorded in the top first mm of the sediment during the whole experiment every 3 days. On 7 occasions, cores were isolated and incubated for 12 hours to estimate fluxes of DIC, TA, oxygen and nutrients. Porewater profiles of DIC, TA, calcium and nutrients were analyzed before and after incubation. On the solid phase, the content of particulate organic carbon, the C:N ratio and its isotopic δ15N and δ13C signature have been determined. In addition, total carbon contents have been measured and X-Ray diffraction was used to look for phase shifts between calcite and aragonite. A net decrease of pH was observed in the upper sediment layers, as well as an increase of DIC and TA pore water concentrations. The acidified cores showed higher DIC and TA exchange fluxes during the incubations in isolation, whereas oxygen exchange fluxes were independent of pH. Significant changes in the solid phase of the sediments could not be identified and the calcium pore water concentrations seemed not to be affected by acidification of the overlying waters during the given time scale. These results are put in the framework of coastal ocean acidification and are used to understand how the acidification changes the carbonate chemistry in the pore waters and constrain dissolution/precipitation of calcium carbonate.

Solute sources in stream water during consecutive fall storms in a northern hardwood forest watershed: A combined hydrological, chemical and isotopic approach

USGS Publications Warehouse

Mitchell, M.J.; Piatek, K.B.; Christopher, S.; Mayer, B.; Kendall, C.; McHale, P.

2006-01-01

Understanding the effects of climate change including precipitation patterns has important implications for evaluating the biogeochemical responses of watersheds. We focused on four storms in late summer and early fall that occurred after an exceptionally dry period in 2002. We analyzed not only the influence of these storms on episodic chemistry and the role of different water sources in affecting surface water chemistry, but also the relative contributions of these storms to annual biogeochemical mass balances. The study site was a well studied 135-ha watershed in the Adirondack Park of New York State (USA). Our analyses integrated measurements on hydrology, solute chemistry and the isotopic composition of NO 3- (??15N and ??18O) and SO 42- (??34S and ??18O) to evaluate how these storms affected surface water chemistry. Precipitation amounts varied among the storms (Storm 1: Sept. 14-18, 18.5 mm; Storm 2: Sept. 21-24, 33 mm; Storm 3: Sept. 27-29, 42.9 mm; Storm 4: Oct. 16-21, 67.6 mm). Among the four storms, there was an increase in water yields from 2 to 14%. These water yields were much less than in studies of storms in previous years at this same watershed when antecedent moisture conditions were higher. In the current study, early storms resulted in relatively small changes in water chemistry. With progressive storms the changes in water chemistry became more marked with particularly major changes in Cb (sum of base cations), Si, NO 3- , and SO 42- , DOC and pH. Analyses of the relationships between Si, DOC, discharge and water table height clearly indicated that there was a decrease in ground water contributions (i.e., lower Si concentrations and higher DOC concentrations) as the watershed wetness increased with storm succession. The marked changes in chemistry were also reflected in changes in the isotopic composition of SO 42- and NO 3- . There was a strong inverse relationship between SO 42- concentrations and ??34S values suggesting the importance of S biogeochemical redox processes in contributing to SO 42- export. The isotopic composition of NO 3- in stream water indicated that this N had been microbially processed. Linkages between SO 42- and DOC concentrations suggest that wetlands were major sources of these solutes to drainage waters while the chemical and isotopic response of NO 3- suggested that upland sources were more important. Although these late summer and fall storms did not play a major role in the overall annual mass balances of solutes for this watershed, these events had distinctive chemistry including depressed pH and therefore have important consequences to watershed processes such as episodic acidification, and the linkage of these processes to climate change. ?? Springer 2006.

Plasma-water interactions at atmospheric pressure in a dc microplasma

NASA Astrophysics Data System (ADS)

Patel, Jenish; Němcová, Lucie; Mitra, Somak; Graham, William; Maguire, Paul; Švrček, Vladimir; Mariotti, Davide

2013-09-01

Plasma-liquid interactions generate a variety of chemical species that are very useful for the treatment of many materials and that makes plasma-induced liquid chemistry (PiLC) very attractive for industrial applications. The understanding of plasma-induced chemistry with water can open up a vast range of plasma-activated chemistry in liquid with enormous potential for the synthesis of chemical compounds, nanomaterials synthesis and functionalization. However, this basic understanding of the chemistry occurring at the plasma-liquid interface is still poor. In the present study, different properties of water are analysed when processed by plasma at atmospheric-pressure with different conditions. In particular, pH, temperature and conductivity of water are measured against current and time of plasma processing. We also observed the formation of molecular oxygen (O2) and hydrogen peroxide (H2O2) for the same plasma conditions. The current of plasma processing was found to affect the water properties and the production of hydrogen peroxide in water. The relation between the number of electrons injected from plasma in water and the number of H2O2 molecules was established and based on these results a scenario of reactions channels activated by plasma-water interface is concluded.

Carbonate chemistry of an in-situ free-ocean CO2 enrichment experiment (antFOCE) in comparison to short term variation in Antarctic coastal waters.

PubMed

Stark, J S; Roden, N P; Johnstone, G J; Milnes, M; Black, J G; Whiteside, S; Kirkwood, W; Newbery, K; Stark, S; van Ooijen, E; Tilbrook, B; Peltzer, E T; Berry, K; Roberts, D

2018-02-12

Free-ocean CO 2 enrichment (FOCE) experiments have been deployed in marine ecosystems to manipulate carbonate system conditions to those predicted in future oceans. We investigated whether the pH/carbonate chemistry of extremely cold polar waters can be manipulated in an ecologically relevant way, to represent conditions under future atmospheric CO 2 levels, in an in-situ FOCE experiment in Antarctica. We examined spatial and temporal variation in local ambient carbonate chemistry at hourly intervals at two sites between December and February and compared these with experimental conditions. We successfully maintained a mean pH offset in acidified benthic chambers of -0.38 (±0.07) from ambient for approximately 8 weeks. Local diel and seasonal fluctuations in ambient pH were duplicated in the FOCE system. Large temporal variability in acidified chambers resulted from system stoppages. The mean pH, Ω arag and fCO 2 values in the acidified chambers were 7.688 ± 0.079, 0.62 ± 0.13 and 912 ± 150 µatm, respectively. Variation in ambient pH appeared to be mainly driven by salinity and biological production and ranged from 8.019 to 8.192 with significant spatio-temporal variation. This experiment demonstrates the utility of FOCE systems to create conditions expected in future oceans that represent ecologically relevant variation, even under polar conditions.

Efforts to control radiation build-up in Ringhals

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

Egner, K.; Aronsson, P.O.; Erixon, O.

1995-03-01

It is well known that good control of the primary chemistry in a PWR is essential in order to minimize material problems and fuel damages. It has also been well established that the water chemistry has a great influence on accumulation of corrosion products on the fuel and the radiation build-up on primary system surfaces. Ringhals was one of the pioneers to increase operating pH in order to reduce radiation build-up and has now been operating for ten years with pH at 7.4 or (in later years) 7.2. Our experience is favourable and includes low radiation levels in the newmore » (1989) steam generators of Ringhals 2. Ringhals 4 has operated almost its whole life at pH 7.2 or higher and it remains one of the cleanest PWRs of its vintage. In addition to strict adherence to a stable operating chemistry, Ringhals is now working on a program with the aim to find optimum shut-down and start-up chemistry to reduce activity levels in the primary systems. A particular goal is to use the shut-down and start-up chemistry at the 1994 outage in Ringhals 3 in order to reduce doserates in preparation for the planned steam generator replacement in 1995. The paper summarizes the experience to date of the established operating chemistry, on-going tests with modified shut-down and start-up chemistry and other measures to limit or reduce the activity build-up.« less

Understanding Phosphorous Chemistry in Comets in Light of Rosetta Results

NASA Astrophysics Data System (ADS)

Boice, Daniel C.; de Almeida, Amaury A.

2016-10-01

Introduction: Phosphorous is a key element in all known forms of life. P-bearing compounds have been observed in the ISM and other regions of space. They are ubiquitous in meteorites, have been detected in the dust component in comets 1P/Halley and 81P/Wild 2, and in the gas phase (atomic P) of 67P/Churyumov-Gerasimenko by the Rosetta Mission. We present results from the first quantitative study of P-bearing molecules in comets to aid in future searches for this important element in comets, shedding light on issues of comet formation and prebiotic to biotic evolution of life. Results and Discussion: Our gas dynamics model of cometary comae with chemical kinetics has been adapted to study this problem. We used phosphine (PH3) as a native molecule with a cosmic abundance mixing ratio. Over 100 photo and gas-phase reactions and 30 P-bearing species were added to the chemical network. The chemistry of PH3 in the inner coma shows the major destruction channels are photo-dissociation and protonation with water-group ions, leading to the recycling of PH3 in this region and the eventual production of atomic P. Conclusion: The model identifies the relevant phosphine chemistry in cometary coma. Protonation reactions of PH3 with water-group ions are important due to its high proton affinity. Abundances are found to be on the order of 10-4 relative to water, about the same as isotopic species. The scale length of PH3 in the coma is about 13,000-16,000 km. We also comment on other Rosetta findings (e.g., O2 and H-). Collaborations with observers using modern telescopic facilities (e.g., Keck 2 and Subaru) are underway to search for phosphorus in comets. Acknowledgments: This work was supported by FAPESP under Grant No. 2015/03176-8 and the National Science Foundation Planetary Astronomy Program Grant No. 0908529.

The role of groundwater chemistry in the transport of bacteria to water-supply wells

USGS Publications Warehouse

Harvey, R.W.; Metge, D.W.

1999-01-01

Static mini-columns and in situ injection and recovery tests were used to assess the effects of modest changes in groundwater chemistry upon the pH-dependence of bacterial attachment, a primary determinant of bacterial mobility in drinking water aquifers. In uncontaminated groundwater (<1 mg l-1 dissolved organic carbon, DOC), bacterial attachment to aquifer grain surfaces declined steadily from 93 to 20% in response to an increase in pH from 5.8 to 7.8. However, bacterial attachment in modestly-contaminated groundwater (4 mg l-1 DOC) was relatively insensitive to pH change from pH 3.5 to pH 8, as was bacterial attachment in uncontaminated groundwater amended with only ~3 mg l-1 of purified humic acid. Destruction by UV-oxidation of the DOC in contaminated groundwater partially restored the pH-dependence of bacterial attachment. Results from static column tests and from a small-scale (3.6 m) natural-gradient injection and recovery study suggest that low concentrations of surfactants can also substantively alter the attraction of groundwater bacteria for grain surfaces and, therefore can alter the transport of bacteria to water-supply wells. This phenomenon was pH-sensitive and dependent upon the nature of the surfactant. At pH 7.6, 200 mg l-1 of the non-ionic surfactant, Imbentin, caused a doubling of fractional bacterial attachment in aquifer-sediment columns, but had little effect under slightly acidic conditions (e.g. at pH 5.8). In contrast, 1 mg l-1 of linear alkylbenzene sulphonate (LAS) surfactant, a common sewage-derived contaminant, decreased the fractional bacterial attachment by more than 30% at pH 5.8, but had little effect at pH 7.3.Static mini-columns and in situ injection and recovery tests were used to assess the effects of modest changes in groundwater chemistry upon the pH-dependence of bacterial attachment, a primary determinant of bacterial mobility in drinking water aquifers. In uncontaminated groundwater (<1 mg l-1 dissolved organic carbon, DOC), bacterial attachment to aquifer grain surfaces declined steadily from 93 to 20% in response to an increase in pH from 5.8 to 7.8. However, bacterial attachment in modestly-contaminated groundwater (4 mg l-1 DOC) was relatively insensitive to pH change from pH 3.5 to pH 8, as was bacterial attachment in uncontaminated groundwater amended with only approx. 3 mg l-1 of purified humic acid. Destruction of UV-oxidation of the DOC in contaminated groundwater partially restored the pH-dependence of bacterial attachment. Results from the static column tests and from a small-scale (3.6 m) natural-gradient injection and recovery study suggest that low concentrations of surfactants can also substantively alter the attraction of groundwater bacteria for grain surfaces and, therefore can alter the transport of bacteria to water-supply wells. This phenomenon was pH-sensitive and dependent upon the nature of the surfactant. At pH 7.6, 200 mg l-1 of the non-ionic surfactant, Imbentin, caused a doubling of fractional bacterial attachment in aquifer-sediment columns, but had little effect under slightly acidic conditions (e.g. at pH 5.8). In contrast, 1 mg l-1 of linear alkylbenzene sulphonate (LAS) surfactant, a common sewage-derived contaminant, decreased the fractional bacterial attachment by more than 30% at pH 5.8, but had little effect at pH 7.3.

Changes in the chemistry of small Irish lakes.

PubMed

Burton, Andrew W; Aherne, Julian

2012-03-01

A re-survey of acid-sensitive lakes in Ireland (initial survey 1997) was carried out during spring 2007 (n = 60). Since 1997, atmospheric emissions of sulfur dioxide and deposition of non-marine sulfate (SO(4) (2-)) in Ireland have decreased by ~63 and 36%, respectively. Comparison of water chemistry between surveys showed significant decreases in the concentration of SO(4) (2-), non-marine SO(4) (2-), and non-marine base cations. In concert, alkalinity increased significantly; however, no change was observed in surface water pH and total aluminum. High inter-annual variability in sea salt inputs and increasing (albeit non-significant) dissolved organic carbon may have influenced the response of pH and total aluminum (as ~70% is organic aluminum). Despite their location on the western periphery of Europe, and dominant influence from Atlantic air masses, the repeat survey suggests that the chemistry of small Irish lakes has shown a significant response to reductions in air pollution driven primarily by the implementation of the Gothenburg Protocol under the UNECE Convention on Long-Range Transboundary Air Pollution.

LINKAGES AMONG LAND-USE, WATER QUALITY, PHYSICAL HABITAT CONDITIONS AND LOTIC DIATOM ASSEMBLAGES: A MULTI-SPATIAL SCALE ASSESSMENT

EPA Science Inventory

We assessed the importance of spatial scales (catchment, stream network, and sample reach) on the effects of agricultural land-use on lotic diatom assemblages along a land-use gradient in the agricultural Willamette Valley Ecoregion of Oregon. Periphyton, water chemistry, and ph...

Variability in daily pH scales with coral reef accretion and community structure

NASA Astrophysics Data System (ADS)

Price, N.; Martz, T.; Brainard, R. E.; Smith, J.

2011-12-01

Little is known about natural variability in pH in coastal waters and how resident organisms respond to current nearshore seawater conditions. We used autonomous sensors (SeaFETs) to record temperature and, for the first time, pH with high temporal (hourly observations; 7 months of sampling) resolution on the reef benthos (5-10m depth) at several islands (Kingman, Palmyra and Jarvis) within the newly designated Pacific Remote Island Areas Marine National Monument (PRIMNM) in the northern Line Islands; these islands are uninhabited and lack potentially confounding local impacts (e.g. pollution and overfishing). Recorded benthic pH values were compared with regional means and minimum thresholds based on seasonal amplitude estimated from surrounding open-ocean climatological data, which represent seawater chemistry values in the absence of feedback from the reef. Each SeaFET sensor was co-located with replicate Calcification/Acidification Units (CAUs) designed to quantify species abundances and net community calcification rates so we could determine which, if any, metrics of natural variability in benthic pH and temperature were related to community development and reef accretion rates. The observed range in daily pH encompassed maximums reported from the last century (8.104 in the early evening) to minimums approaching projected levels within the next 100 yrs (7.824 at dawn) for pelagic waters. Net reef calcification rates, measured as calcium carbonate accretion on CAUs, varied within and among islands and were comparable with rates measured from the Pacific and Caribbean using chemistry-based approaches. Benthic species assemblages on the CAUs were differentiated by the presence of calcifying and fleshy taxa (CAP analysis, mean allocation success 80%, δ2 = 0.886, P = <0.001). In general, accretion rates were higher at sites that had a greater number of hours at high pH values each day. Where daily pH failed to exceed climatological seasonal minimum thresholds, net accretion was slower and fleshy, non-calcifying benthic organisms dominated. Natural variation in benthic pH offers a unique opportunity to study ecological consequences of likely future ocean chemistry.

Surface complexation of carboxylate adheres Cryptosporidium parvum öocysts to the hematite-water interface

USGS Publications Warehouse

Gao, X.; Metge, D.W.; Ray, C.; Harvey, R.W.; Chorover, J.

2009-01-01

The interaction of viable Cryptosporidium parvum öocysts at the hematite (α-Fe2O3)−water interface was examined over a wide range in solution chemistry using in situ attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy. Spectra for hematite-sorbed öocysts showed distinct changes in carboxylate group vibrations relative to spectra obtained in the absence of hematite, indicative of direct chemical bonding between carboxylate groups and Fe metal centers of the hematite surface. The data also indicate that complexation modes vary with solution chemistry. In NaCl solution, öocysts are bound to hematite via monodentate and binuclear bidentate complexes. The former predominates at low pH, whereas the latter becomes increasingly prevalent with increasing pH. In a CaCl2 solution, only binuclear bidentate complexes are observed. When solution pH is above the point of zero net proton charge (PZNPC) of hematite, öocyst surface carboxylate groups are bound to the mineral surface via outer-sphere complexes in both electrolyte solutions.

Water or sediment? Partitioning the role of water column and sediment chemistry as drivers of macroinvertebrate communities in an austral South African stream.

PubMed

Dalu, Tatenda; Wasserman, Ryan J; Tonkin, Jonathan D; Mwedzi, Tongayi; Magoro, Mandla L; Weyl, Olaf L F

2017-12-31

Water pollution is a critical management issue, with many rivers and streams draining urban areas being polluted by the disposal of untreated solid waste and wastewater discharge, storm water and agricultural runoff. This has implications for biodiversity, and many rivers in the developing world are now considered compromised. We investigated benthic macroinvertebrate community structure and composition in relation to physico-chemical conditions of the water column and sediments. The study was conducted in an Austral catchment subject to both urban and agricultural pollutants in two different seasons. We assessed whether sediment characteristics were more important drivers of macroinvertebrate community composition than water column characteristics. We expected clear differences in macroinvertebrate community composition and in the associated community metrics due to distinct flow conditions between the two seasons. A combination of multivariate analyses (canonical correspondence analysis (CCA)) and biological indicator analysis were used to examine these patterns. Chironomidae was the most abundant family (>60%) in the upper mainstem river and stream sites. Stream sites were positively associated with CCA axis 2, being characterised by high turbidity and lower pH, salinity, phosphate concentration, channel width and canopy cover. Canopy cover, channel width, substrate embeddedness, phosphate concentration, pH, salinity and turbidity all had a significant effect on macroinvertebrate community composition. Using CCA variation partitioning, water quality was, however, a better predictor of benthic macroinvertebrate composition than sediment chemical conditions. Furthermore, our results suggest that seasonality had little effect on structuring benthic macroinvertebrate communities in this south-eastern zone of South Africa, despite clear changes in sediment chemistry. This likely reflects the relative lack of major variability in water chemistry compared to sediment chemistry between seasons and the relatively muted variability in precipitation between seasons than the more classic Austral temperate climates. Copyright © 2017 Elsevier B.V. All rights reserved.

Chemistry of OH in remote clouds and its role in the production of formic acid and peroxymonosulfate

NASA Technical Reports Server (NTRS)

Jacob, D. J.

1986-01-01

The chemistry of OH in nonprecipitating tropospheric clouds was studied using a coupled gas phase/aqueous phase chemical model. The simulation takes into account the radial dependence of the concentrations of short lived aqueous phase species, in particular, O3(aq) OH(aq). Formic acid is shown to be rapidly produced by the aqueous phase reaction between H2C(OH)2 and OH, but HCOO(-) and OH, but HCOO(-) is in turn rapidly oxidized by OH(aq). The HCOOH concentration in cloud is shown to be strongly dependent on the pH of the cloud water; clouds with pH greater than 5 are not efficient HCOOH sources. A novel mechanism is proposed for the oxidation of S(IV) by OH(aq), with the main product predicted to be peroxymonosulfate, HSO5(-). The latter could contribute significantly to total cloud water sulfur.

Sulfur geochemistry of hydrothermal waters in Yellowstone National Park: IV Acid-sulfate waters

USGS Publications Warehouse

Nordstrom, D. Kirk; McCleskey, R. Blaine; Ball, J.W.

2009-01-01

Many waters sampled in Yellowstone National Park, both high-temperature (30-94 ??C) and low-temperature (0-30 ??C), are acid-sulfate type with pH values of 1-5. Sulfuric acid is the dominant component, especially as pH values decrease below 3, and it forms from the oxidation of elemental S whose origin is H2S in hot gases derived from boiling of hydrothermal waters at depth. Four determinations of pH were obtained: (1) field pH at field temperature, (2) laboratory pH at laboratory temperature, (3) pH based on acidity titration, and (4) pH based on charge imbalance (at both laboratory and field temperatures). Laboratory pH, charge imbalance pH (at laboratory temperature), and acidity pH were in close agreement for pH ??10%, a selection process was used to compare acidity, laboratory, and charge balance pH to arrive at the best estimate. Differences between laboratory and field pH can be explained based on Fe oxidation, H2S or S2O3 oxidation, CO2 degassing, and the temperature-dependence of pK2 for H2SO4. Charge imbalances are shown to be dependent on a speciation model for pH values 350 mg/L Cl) decrease as the Cl- concentration increases from boiling which appears inconsistent with the hypothesis of H2S oxidation as a source of hydrothermal SO4. This trend is consistent with the alternate hypothesis of anhydrite solubility equilibrium. Acid-sulfate water analyses are occasionally high in As, Hg, and NH3 concentrations but in contrast to acid mine waters they are low to below detection in Cu, Zn, Cd, and Pb concentrations. Even concentrations of SO4, Fe, and Al are much lower in thermal waters than acid mine waters of the same pH. This difference in water chemistry may explain why certain species of fly larvae live comfortably in Yellowstone's acid waters but have not been observed in acid rock drainage of the same pH.

Best-fit analysis for future coral reef survivors on Bonaire: A lifeline to the reefs' future in the region

NASA Astrophysics Data System (ADS)

Johnson, C. C.; Elswick, E. R.; Beeker, C. D.; Kauffman, E. G.; Budziak, A. T.; Wiegand, N.

2012-12-01

Given the decline of Caribbean corals and increases in environmental threats and human stressors to the reef ecosystem, it is imperative to document and establish a biological and environmental baseline inventory of coral recruits and environments in which corals live. Our project investigated the association of corals and water chemistry on the leeward side of Bonaire to test for and assess the hypothesis of ocean acidification affecting one of the healthiest reefs in the Caribbean. A dry island such as Bonaire, with no major river input into the leeward side of the island, provides an ideal location for such an analyses as it yields a relatively pure ocean chemistry signal. A multi-year investigation in Bonaire National Marine Park (BNMP) focused on corals growing on mooring buoy anchors created from cement blocks and cement filled, discarded petroleum barrels. We evaluate the persistence of corals on anchors placed in BNMP in the 1960's and 1970's, taking advantage of the maximum timeline for coral recruits. Recruits initiated in the zone occupied initially by Acropora cervicornis and A. palmata, and persisted through the decline of the once dominant acroporids. Thus, our study can be taken as a natural inoculation experiment under ambient field conditions. We collected 200ml water samples at 25 sites and analyzed samples on the Atomic Absorption Spectrometer Analyst 800 and Dionex IC25 Ion Chromatograph instruments to yield elemental data for water chemistry analyses. Depth pH, temperature, salinity and turbidity were recorded per site in rainy and dry seasons over the 5-year, Nov 2007 - April 2011 study. pH measurements were taken by colorimetric and indicator strips. Biologic data collection focused on coral species identifications per site on mooring anchors but sponges, hydrozoans and algae were also noted. Our research reveals no pH changes in these shallow (12.2m) waters over the duration of the study. pH colorimetric averages were 8.0-8.5 for both April/May and Nov/ Dec collections, and pH litmus 8.0 for all sites, all seasons. We further investigated the association of temperature, salinity and turbidity at site-specific locations and recorded differences in cation and anion water chemistry. Seasonal averages for T are 27.2oC for April/May and 28.1oC for Nov/Dec. Salinity seasonal averages are 37.4ppt for April/May and 36.7ppt for Nov/Dec; Mg/Ca (wt. ratio) exhibits seasonal variation; turbidity was 0 JTU for all sites, all collections. Our bioenvironmental database allows for ordination analysis of coral species with specific water chemistry conditions. Family Faviidae (Diploria labrynthiformis, D. strigosa), with origins in the mid-Jurassic geologic record, dominates the occurrences, followed by Family Poritidae (Porites asteroides) and Family Agariciidae, but great variability exists across sites. Nitrates, nitrites and phosphates, local human stressors, have variable effect on coral presence and persistence. The database provides the best-fit analysis for future survivors under climate change conditions and may be the lifeline to the reefs' future in this region.

Arsenic Removal and Its Chemistry in Batch Electrocoagulation Studies.

PubMed

Sharma, Anshul; Adapureddy, Sri Malini; Goel, Sudha

2014-04-01

The aim of this study was to evaluate the impact of different oxidizing agents like light, aeration (by mixing) and electrocoagulation (EC) on the oxidation of As (III) and its subsequent removal in an EC batch reactor. Arsenic solutions prepared using distilled water and groundwater were evaluated. Optimum pH and the effect of varying initial pH on As removal efficiency were also evaluated. MaximumAs (III) removal efficiency with EC, light and aeration was 97% from distilled water and 71% from groundwater. Other results show that EC alone resulted in 90% As removal efficiency in the absence of light and mixing from distilled water and 53.6% from groundwater. Removal with light and mixing but without EC resulted in only 26% As removal from distilled water and 29% from groundwater proving that electro-oxidation and coagulation were more effective in removing arsenic compared to the other oxidizing agents examined. Initial pH was varied from 5 to 10 in distilled water and from 3 to 12 in groundwater for evaluating arsenic removal efficiency by EC. The optimum initial pH for arsenic removal was 7 for distilled water and groundwater. For all initial pHs tested between 5 and 10 in distilled water, the final pH ranged between 7 and 8 indicating that the EC process tends towards near neutral pH under the conditions examined in this study.

Carbonate chemistry in a Kennebec Estuary softshell clam flat: Seasonal variability and implications for blue carbon mitigation

NASA Astrophysics Data System (ADS)

Miller, H. R.; Jurcic, B.; Indrick, R.; LaVigne, M.

2016-12-01

Maine's softshell clam (Mya arenaria) industry brings $20 million to the state annually. Reduced clam flat sediments aragonite saturation state (Ω), a predicted effect of ocean acidification, has been shown to negatively impact shell development in M. arenaria's early life stages. Seagrass restoration has been proposed to benefit Maine clam flats. However, the Gulf of Maine experiences seasonal changes in temperature and freshwater input, and the impacts on the carbonate chemistry of intertidal ecosystems have yet to be quantified. We measured overlying water and surface ( upper 1cm) porewater temperature (T), salinity (S), pH, and alkalinity (TA) biweekly from March to August, 2016 to quantify spatial and seasonal sediment Ω variability in a Kennebec Estuary clam flat (Wyman Bay, Maine). Reduced freshwater flow from spring into summer caused an increase in overlying water S (5-25ppt), TA (400-1800ueq/L), and W (0.09-1.20). Surface sediment pore water S (15-29ppt) and TA (1100-2100ueq/L) also increased in summer; however, Ω was variable and remained well below saturation (<0.40). Overlying water pH (7.38-7.96) and sediment pore water pH (6.85-7.47) showed no seasonal trend. Contrary to the predicted impact of seagrass on clam flat carbonate chemistry, preliminary data show sediment Ω is significantly lower in a site located within S. alterniflora (0.150.05) compared to sites lacking alterniflora (0.210.1) within Wyman Bay. Elevated sediment organic matter concentrations found with grasses (4.6%0.5) vs. without (2.9%0.4) may be produced by the grasses and organisms attracted to the ecosystem, and may result in greater respiration driving pH and Ω down rather than up. The strong correlation between TA and S (R2=0.78-0.99) suggests freshwater flow with spring melt during M. arenaria's planktonic larval stage and rain events (predicted to increase with climate change) can reduce Ω, with potentially negative implications for early M. arenaria life stages.

Impact of environmentally based chemical hardness on uranium speciation and toxicity in six aquatic species.

PubMed

Goulet, Richard R; Thompson, Patsy A; Serben, Kerrie C; Eickhoff, Curtis V

2015-03-01

Treated effluent discharge from uranium (U) mines and mills elevates the concentrations of U, calcium (Ca), magnesium (Mg), and sulfate (SO4 (2-) ) above natural levels in receiving waters. Many investigations on the effect of hardness on U toxicity have been experiments on the combined effects of changes in hardness, pH, and alkalinity, which do not represent water chemistry downstream of U mines and mills. Therefore, more toxicity studies with water chemistry encountered downstream of U mines and mills are necessary to support predictive assessments of impacts of U discharge to the environment. Acute and chronic U toxicity laboratory bioassays were realized with 6 freshwater species in waters of low alkalinity, circumneutral pH, and a range of chemical hardness as found in field samples collected downstream of U mines and mills. In laboratory-tested waters, speciation calculations suggested that free uranyl ion concentrations remained constant despite increasing chemical hardness. When hardness increased while pH remained circumneutral and alkalinity low, U toxicity decreased only to Hyalella azteca and Pseudokirchneriella subcapitata. Also, Ca and Mg did not compete with U for the same uptake sites. The present study confirms that the majority of studies concluding that hardness affected U toxicity were in fact studies in which alkalinity and pH were the stronger influence. The results thus confirm that studies predicting impacts of U downstream of mines and mills should not consider chemical hardness. Environ Toxicol Chem 2015;34:562-574. © 2014 The Authors. Published by Wiley Periodicals, Inc. on behalf of SETAC. © 2014 The Authors. Published by Wiley Periodicals, Inc. on behalf of SETAC.

Natural Pathogen Control Chemistry to Replace Toxic Treatment of Microbes and Biofilm in Cooling Towers

PubMed Central

Brouse, Lon; Brouse, Richard; Brouse, Daniel

2017-01-01

Application of toxic antibacterial agents is considered necessary to control prevalent fresh water microorganisms that grow in evaporative cooling water systems, but can adversely affect the environment and human health. However, natural antibacterial water chemistry has been applied in industrial cooling water systems for over 10 years to inhibit microorganisms with excellent results. The water chemistry method concentrates natural minerals in highly-softened water to produce elevated pH and dissolved solids, while maintaining low calcium and magnesium content. The method provides further benefits in water conservation, and generates a small volume of non-toxic natural salt concentrate for cost efficient separation and disposal if required. This report describes the antimicrobial effects of these chemistry modifications in the cooling water environment and the resultant collective inhibition of microbes, biofilm, and pathogen growth. This article also presents a novel perspective of parasitic microbiome functional relationships, including “Trojan Protozoans” and biofilms, and the function of polyvalent metal ions in the formation and inhibition of biofilms. Reducing global dependence on toxic antibacterial agents discharged to the environment is an emerging concern due to their impact on the natural microbiome, plants, animals and humans. Concurrently, scientists have concluded that discharge of antibacterial agents plays a key role in development of pathogen resistance to antimicrobials as well as antibiotics. Use of natural antibacterial chemistry can play a key role in managing the cooling water environment in a more ecologically sustainable manner. PMID:28420074

Physical and Biological Controls on the Carbonate Chemistry of Coral Reef Waters: Effects of Metabolism, Wave Forcing, Sea Level, and Geomorphology

PubMed Central

Falter, James L.; Lowe, Ryan J.; Zhang, Zhenlin; McCulloch, Malcolm

2013-01-01

We present a three-dimensional hydrodynamic-biogeochemical model of a wave-driven coral-reef lagoon system using the circulation model ROMS (Regional Ocean Modeling System) coupled with the wave transformation model SWAN (Simulating WAves Nearshore). Simulations were used to explore the sensitivity of water column carbonate chemistry across the reef system to variations in benthic reef metabolism, wave forcing, sea level, and system geomorphology. Our results show that changes in reef-water carbonate chemistry depend primarily on the ratio of benthic metabolism to the square root of the onshore wave energy flux as well as on the length and depth of the reef flat; however, they are only weakly dependent on channel geometry and the total frictional resistance of the reef system. Diurnal variations in pCO2, pH, and aragonite saturation state (Ωar) are primarily dependent on changes in net production and are relatively insensitive to changes in net calcification; however, net changes in pCO2, pH, and Ωar are more strongly influenced by net calcification when averaged over 24 hours. We also demonstrate that a relatively simple one-dimensional analytical model can provide a good description of the functional dependence of reef-water carbonate chemistry on benthic metabolism, wave forcing, sea level, reef flat morphology, and total system frictional resistance. Importantly, our results indicate that any long-term (weeks to months) net offsets in reef-water pCO2 relative to offshore values should be modest for reef systems with narrow and/or deep lagoons. Thus, the long-term evolution of water column pCO2 in many reef environments remains intimately connected to the regional-scale oceanography of offshore waters and hence directly influenced by rapid anthropogenically driven increases in pCO2. PMID:23326411

Physical and biological controls on the carbonate chemistry of coral reef waters: effects of metabolism, wave forcing, sea level, and geomorphology.

PubMed

Falter, James L; Lowe, Ryan J; Zhang, Zhenlin; McCulloch, Malcolm

2013-01-01

We present a three-dimensional hydrodynamic-biogeochemical model of a wave-driven coral-reef lagoon system using the circulation model ROMS (Regional Ocean Modeling System) coupled with the wave transformation model SWAN (Simulating WAves Nearshore). Simulations were used to explore the sensitivity of water column carbonate chemistry across the reef system to variations in benthic reef metabolism, wave forcing, sea level, and system geomorphology. Our results show that changes in reef-water carbonate chemistry depend primarily on the ratio of benthic metabolism to the square root of the onshore wave energy flux as well as on the length and depth of the reef flat; however, they are only weakly dependent on channel geometry and the total frictional resistance of the reef system. Diurnal variations in pCO(2), pH, and aragonite saturation state (Ω(ar)) are primarily dependent on changes in net production and are relatively insensitive to changes in net calcification; however, net changes in pCO(2), pH, and Ω(ar) are more strongly influenced by net calcification when averaged over 24 hours. We also demonstrate that a relatively simple one-dimensional analytical model can provide a good description of the functional dependence of reef-water carbonate chemistry on benthic metabolism, wave forcing, sea level, reef flat morphology, and total system frictional resistance. Importantly, our results indicate that any long-term (weeks to months) net offsets in reef-water pCO(2) relative to offshore values should be modest for reef systems with narrow and/or deep lagoons. Thus, the long-term evolution of water column pCO(2) in many reef environments remains intimately connected to the regional-scale oceanography of offshore waters and hence directly influenced by rapid anthropogenically driven increases in pCO(2).

Evaluation of copper toxicity using site specific algae and water chemistry: Field validation of laboratory bioassays.

PubMed

Fawaz, Elyssa G; Salam, Darine A; Kamareddine, Lina

2018-07-15

Studies of metal toxicity to microalgae have predominantly been conducted using single non-target algae species and without due regard for the chemistry of the treated waters, leading to ineffective or excessive algaecide treatments. In this study, indigenous multi-algal species (Scenedesmus quadricauda, and Scenedesmus subspicatus and Oscillatoria agardhii) were used in laboratory toxicity bioassays under simulated field water chemistry (pH = 7.2, hardness = 196 mg L -1 as CaCO 3 , and alkalinity = 222 mg L -1 as CaCO 3 ) to determine the optimum copper sulfate treatment dose to control algae growth in an irrigation canal. Toxicity bioassays were conducted using copper sulfate in chelated (with EDTA) and non-chelated (without EDTA) forms to assess the influence of the use of synthetic chelators in toxicity studies. Also, copper toxicity to the indigenous algae species was measured in the non-modified EPA test medium (pH = 7.5, hardness = 92 mg L -1 as CaCO 3 , alkalinity = 10 mg L -1 as CaCO 3 and EDTA= 300 µg L -1 ) to assess the impact of the water chemistry on algae inhibitory algal dosages. Under simulated water chemistry conditions, lower toxicity was measured in the test flasks with the chelated form of copper (96 h- EC 50 = 386.67 µg L -1 as Cu) as compared to those with the non-chelated metal (96 h-EC 50 = 217.17 µg L -1 as Cu). In addition, higher copper toxicity was measured in the test flasks prepared with the non-modified EPA medium using chelated copper (96 h-EC 50 = 65.93 µg L -1 as Cu) as compared to their analogous microcosms with modified water chemistry (96 h-EC 50 = 386.67 µg L -1 as Cu), the increased water hardness and alkalinity in the latter case contributing to the decrease of the metal bioavailability. Results from laboratory experiments showed good correlation with copper dosages used in a small scale field testing to control algae growth, increasing confidence in laboratory bioassays. Copyright © 2018 Elsevier Inc. All rights reserved.

The response of Antarctic sea ice algae to changes in pH and CO2.

PubMed

McMinn, Andrew; Müller, Marius N; Martin, Andrew; Ryan, Ken G

2014-01-01

Ocean acidification substantially alters ocean carbon chemistry and hence pH but the effects on sea ice formation and the CO2 concentration in the enclosed brine channels are unknown. Microbial communities inhabiting sea ice ecosystems currently contribute 10-50% of the annual primary production of polar seas, supporting overwintering zooplankton species, especially Antarctic krill, and seeding spring phytoplankton blooms. Ocean acidification is occurring in all surface waters but the strongest effects will be experienced in polar ecosystems with significant effects on all trophic levels. Brine algae collected from McMurdo Sound (Antarctica) sea ice was incubated in situ under various carbonate chemistry conditions. The carbon chemistry was manipulated with acid, bicarbonate and bases to produce a pCO2 and pH range from 238 to 6066 µatm and 7.19 to 8.66, respectively. Elevated pCO2 positively affected the growth rate of the brine algal community, dominated by the unique ice dinoflagellate, Polarella glacialis. Growth rates were significantly reduced when pH dropped below 7.6. However, when the pH was held constant and the pCO2 increased, growth rates of the brine algae increased by more than 20% and showed no decline at pCO2 values more than five times current ambient levels. We suggest that projected increases in seawater pCO2, associated with OA, will not adversely impact brine algal communities.

pH-Dependent Surface Chemistry from First Principles: Application to the BiVO4(010)-Water Interface.

PubMed

Ambrosio, Francesco; Wiktor, Julia; Pasquarello, Alfredo

2018-03-28

We present a theoretical formulation for studying the pH-dependent interfacial coverage of semiconductor-water interfaces through ab initio electronic structure calculations, molecular dynamics simulations, and the thermodynamic integration method. This general methodology allows one to calculate the acidity of the individual adsorption sites on the surface and consequently the pH at the point of zero charge, pH PZC , and the preferential adsorption mode of water molecules, either molecular or dissociative, at the semiconductor-water interface. The proposed method is applied to study the BiVO 4 (010)-water interface, yields a pH PZC in excellent agreement with the experimental characterization. Furthermore, from the calculated p K a values of the individual adsorption sites, we construct an ab initio concentration diagram of all adsorbed species at the interface as a function of the pH of the aqueous solution. The diagram clearly illustrates the pH-dependent coverage of the surface and indicates that protons are found to be significantly adsorbed (∼1% of available sites) only in highly acidic conditions. The surface is found to be mostly covered by molecularly adsorbed water molecules in a wide interval of pH values ranging from 2 to 8. Hydroxyl ions are identified as the dominant adsorbed species at pH larger than 8.2.

The calculation of aquifer chemistry in hot-water geothermal systems

USGS Publications Warehouse

Truesdell, Alfred H.; Singers, Wendy

1974-01-01

The temperature and chemical conditions (pH, gas pressure, and ion activities) in a geothermal aquifer supplying a producing bore can be calculated from the enthalpy of the total fluid (liquid + vapor) produced and chemical analyses of water and steam separated and collected at known pressures. Alternatively, if a single water phase exists in the aquifer, the complete analysis (including gases) of a sample collected from the aquifer by a downhole sampler is sufficient to determine the aquifer chemistry without a measured value of the enthalpy. The assumptions made are that the fluid is produced from a single aquifer and is homogeneous in enthalpy and chemical composition. These calculations of aquifer chemistry involving large amounts of ancillary information and many iterations require computer methods. A computer program in PL-1 to perform these calculations is available from the National Technical Information Service as document PB-219 376.

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

NONE

Many times the start up of granular activated carbon adsorption systems for the control of organic contaminants in wastewater cm exhibit unacceptable increases in the adscurber effluent pH. Experience shows that the duration of the pH increase ranges from several hours to several days, during which time several hundred bed volumes of water can be discharged with a pH in excess of 9. Laboratory studies have identified the cause of the pH rise as an interaction between the naturally occurring anions and protons ar the water and the carbon surface. The interaction can be described as an ion exchange typemore » of phenomenon, in which the carbon surface sorbs the anions and corresponding hydronium ions from the water. Capacities of the carbon for the anions range from 2 to 9 mg/g GAC, depending upon the water characteristics, the carbon type, the nature of the anion and its influent concentration. These studies have shown de the anion sorption and resulting pH increase is independent of the raw material used for die activated carbon production, e.g. bituminous or sub-bituminous coal, peat, wood or coconut. Also, the pH excursions occur with virgin, reactivated, and acid washed granular carbons. Current pH control technologies focus on adjustment of wastewater pH prior to discharge or recycle of the initial effluent water until the pH increase abates. However, improved water pH control options have been realized by altering the carbon surface rather than the water chemistry. The change to the carbon surface is accomplished through a controlled oxidation process. This process provides a more acidic carbon surface with a reduced affinity for the anions in the waste water. As a result, the pH excursions above 9 are eliminated and the initial effluent from the adsorption system can be discharged without further treatment.« less

Cibicidodes Pachyderma B/Ca as a Shalow Water Carbonate Saturation State Proxy

NASA Astrophysics Data System (ADS)

Wojcieszek, D. E.; Flower, B. P.; Moyer, R. P.; Byrne, R. H.

2012-12-01

Since the industrial revolution, the oceans have absorbed about 25% of anthropogenic CO2 emissions to the atmosphere, leading to a decrease in seawater pH (termed ocean acidification: OA) as well as many associated effects, including decreased saturation states. Assessment of the effects of OA on marine ecosystems is presently based on <50 years of observations. Reconstructions of past seawater chemistry and its impact on biota over much longer time scales can provide essential context for likely future consequences of OA. Reliable oceanic paleo-proxies for influential chemical variables such as pH and carbonate saturation state are crucial components for examining ancient environments affected by OA. Addition of CO2 to seawater leads to not only decreases in seawater pH and saturation state, but also the extent to which boron (B) is incorporated into CaCO3 during biotic calcification. Consequently, the abundance of B in calcite could reflect pH and/or saturation state of the water in which calcification occurred. Recent studies indicate a linear relationship between the ratio of boron to calcium (B/Ca) in benthic foraminifera shells ( Cibicidoides wuellerstorfi, C. mundulus) and the degree of carbonate saturation (Δ[CO32-]), defined as a difference between [CO32-]in situ and [CO32-]saturation. However, the observed relationship between B/Ca and Δ[CO32-] was only established for depths >1000m. Thus, since OA most immediately affects the upper 1000 m of the water column, a reliable shallow water (<1000 m) carbonate chemistry proxy is desirable. We are testing the utility of B/Ca in Cibicidoides pachyderma as a shallow water Δ[CO32-] proxy. C. pachyderma is an epibenthic species and therefore records the composition of bottom, rather than interstitial, waters. It usually inhabits depths between 200 and 1000 m, and is a common species in the Gulf of Mexico. The gently sloping West Florida Shelf (WFS) is an excellent setting for this kind of study as it provides a full range of depths habitable by C.pachyderma. Nine surface sediment samples were collected along a 150-1400 m depth transect across the WFS. Bottom water pH along the transect ranged between 7.82 and 8.12, corresponding to Δ[CO32-] values between 35 and 200 μmol/kg. Preliminary B/Ca data range between 109 and 174 μmol/mol and display high variability. Our results suggest that WFS bottom water chemistry may be intermittently affected by phenomena such as eutrophication-induced hypoxia or boundary layer differences between the lower water column and the sediment-water interface. Additional B/Ca and bottom water measurements are planned to characterize the relationship between C.pachyderma B/Ca and Δ[CO32-], and extend global benthic foraminifera B/Ca calibrations to depths shallower than 1000 m.

Hydrological and chemical budgets in a volcanic caldera lake: Lake Kussharo, Hokkaido, Japan

NASA Astrophysics Data System (ADS)

Chikita, Kazuhisa A.; Nishi, Masataka; Fukuyama, Ryuji; Hamahara, Kazuhiro

2004-05-01

The contribution of groundwater output and input to lake chemistry was examined by estimating the hydrological and chemical budgets of a volcanic caldera lake, Lake Kussharo, Hokkaido, Japan. The lake level, meteorology, river water discharge and water properties were measured in the ice-covered period of February-March and in the open-water period of June-October in 2000. The inorganic chemistry was then analyzed for sporadically sampled surface water and hot spring water. The chemistry of lake water at pH of 6.91-7.57 and EC25 (electric conductivity at 25 °C) of 29.2-32.7 mS/m appears to be controlled by the input of two types of hot spring water: the inflowing Yunokawa River (pH of 2.27-2.54 and EC25 of 197.8-258.0 mS/m) and groundwater discharging directly on the shore (pH of 7.13-8.32, water temperature of 35.0-46.5 °C and EC25 of 53.1-152.0 mS/m). Excluding the days with rainfall or a great change in lake level, the water budget in June-October gave a net groundwater input of -7.41 to 2.97 m 3/s. A combination of the water budget with the chemical budget of two solutes, Na + and Cl -, led to the best estimate of groundwater output, Gout, at 3.82±3.02 m 3/s, the total fresh groundwater input, ∑ Gfresh, at 2.14±1.00 m 3/s, and the total groundwater input of hot springs, ∑ Gspa, at 0.46±0.05 m 3/s. This is comparable to G out=3.87 m3/ s, ∑G fresh=1.49 m3/ s and ∑G spa=0.41 m3/ s during the ice-covered period. The chemical flux by the freshwater input plays an important role in the alkalinity of lake water, as does the chemical flux by the shoreline hot springs. The large groundwater output could occur by the leakage through the highly permeable, underground pumice, distributed from the east-to-south lake basin to southeast of the outlet.

Phytoplankton community response to carbon dioxide enrichment in winter incubation experiments

EPA Science Inventory

Coastal waters are experiencing changes in carbonate chemistry, including pH, in response to increases in atmospheric CO2 concentration and the microbial degradation of surplus organic matter associated with nutrient enrichment. The effects of this change on plankton communities ...

Water balance creates a threshold in soil pH at the global scale.

PubMed

Slessarev, E W; Lin, Y; Bingham, N L; Johnson, J E; Dai, Y; Schimel, J P; Chadwick, O A

2016-11-21

Soil pH regulates the capacity of soils to store and supply nutrients, and thus contributes substantially to controlling productivity in terrestrial ecosystems. However, soil pH is not an independent regulator of soil fertility-rather, it is ultimately controlled by environmental forcing. In particular, small changes in water balance cause a steep transition from alkaline to acid soils across natural climate gradients. Although the processes governing this threshold in soil pH are well understood, the threshold has not been quantified at the global scale, where the influence of climate may be confounded by the effects of topography and mineralogy. Here we evaluate the global relationship between water balance and soil pH by extracting a spatially random sample (n = 20,000) from an extensive compilation of 60,291 soil pH measurements. We show that there is an abrupt transition from alkaline to acid soil pH that occurs at the point where mean annual precipitation begins to exceed mean annual potential evapotranspiration. We evaluate deviations from this global pattern, showing that they may result from seasonality, climate history, erosion and mineralogy. These results demonstrate that climate creates a nonlinear pattern in soil solution chemistry at the global scale; they also reveal conditions under which soils maintain pH out of equilibrium with modern climate.

Water balance creates a threshold in soil pH at the global scale

NASA Astrophysics Data System (ADS)

Slessarev, E. W.; Lin, Y.; Bingham, N. L.; Johnson, J. E.; Dai, Y.; Schimel, J. P.; Chadwick, O. A.

2016-12-01

Soil pH regulates the capacity of soils to store and supply nutrients, and thus contributes substantially to controlling productivity in terrestrial ecosystems. However, soil pH is not an independent regulator of soil fertility—rather, it is ultimately controlled by environmental forcing. In particular, small changes in water balance cause a steep transition from alkaline to acid soils across natural climate gradients. Although the processes governing this threshold in soil pH are well understood, the threshold has not been quantified at the global scale, where the influence of climate may be confounded by the effects of topography and mineralogy. Here we evaluate the global relationship between water balance and soil pH by extracting a spatially random sample (n = 20,000) from an extensive compilation of 60,291 soil pH measurements. We show that there is an abrupt transition from alkaline to acid soil pH that occurs at the point where mean annual precipitation begins to exceed mean annual potential evapotranspiration. We evaluate deviations from this global pattern, showing that they may result from seasonality, climate history, erosion and mineralogy. These results demonstrate that climate creates a nonlinear pattern in soil solution chemistry at the global scale; they also reveal conditions under which soils maintain pH out of equilibrium with modern climate.

Questa baseline and pre-mining ground-water quality investigation. 20. Water chemistry of the Red River and selected seeps, tributaries, and precipitation, Taos County, New Mexico, 2000-2004

USGS Publications Warehouse

Verplanck, P.L.; McCleskey, R. Blaine; Nordstrom, D. Kirk

2006-01-01

As part of a multi-year project to infer the pre-mining ground-water quality at Molycorp's Questa mine site, surface-water samples of the Red River, some of its tributaries, seeps, and snow samples were collected for analysis of inorganic solutes and of water and sulfate stable isotopes in selected samples. The primary aim of this study was to document diel, storm event, and seasonal variations in water chemistry for the Red River and similar variations in water chemistry for Straight Creek, a natural analog site similar in topography, hydrology, and geology to the mine site for inferring pre-mining water-quality conditions. Red River water samples collected between 2000 and 2004 show that the largest variations in water chemistry occur during late summer rainstorms, often monsoonal in nature. Within hours, discharge of the Red River increased from 8 to 102 cubic feet per second and pH decreased from 7.80 to 4.83. The highest concentrations of metals (iron, aluminum, zinc, manganese) and sulfate also occur during such events. Low-pH and high-solute concentrations during rainstorm runoff are derived primarily from alteration 'scar' areas of naturally high mineralization combined with steep topography that exposes continually altered rock because erosion is too rapid for vegetative growth. The year 2002 was one of the driest on record, and Red River discharge reflected the low seasonal snow pack. No snowmelt peak appeared in the hydrograph record, and a late summer storm produced the highest flow for the year. Snowmelt was closer to normal during 2003 and demonstrated the dilution effect of snowmelt on water chemistry. Two diel sampling events were conducted for the Red River, one during low flow and the other during high flow, at two locations, at the Red River gaging station and just upstream from Molycorp's mill site. No discernible diel trends were observed except for dissolved zinc and manganese at the upstream site during low flow. Straight Creek drainage water was sampled periodically from 2001 to 2004 at the down stream end of surface drainage near the point at which it disappeared into the debris fan. This water has a minimal range in pH (2.7 to 3.2) but a substantial concentration range in many solutes; for example, sulfate concentrations varied from 525 to 2,660 mg/L. Many elements covary with sulfate suggesting that dilution is the primary control of the range in solute concentrations. A transect of water samples higher in the scar area were collected in October of 2003. They had a lower range in pH (2.44 to 3.05) and higher solute concentrations than those collected periodically from lower in the catchment. Water isotopes for the upper transect samples indicated slight evaporation, and in part, may account for the higher solute concentrations. Drainage waters also were collected from Hottentot, Junebug, Hansen, Little Hansen, and Goat Hill Gulch drainages. Most constituents from other scar drainage waters showed ranges of concentration similar to those of the Straight Creek waters. An exception was water collected from Goat Hill Gulch, which has some of the highest concentrations of any surface-water sample collected but also contained waste-rock leachates.

Protonation of carboxyl groups in EuDOTA-tetraamide complexes results in catalytic prototropic exchange and quenching of the CEST signal

NASA Astrophysics Data System (ADS)

Zhang, Lei; Evbuomwan, Osasere M.; Tieu, Michael; Zhao, Piyu; Martins, Andre F.; Sherry, A. Dean

2017-10-01

The CEST properties of EuDOTA-tetraamide complexes bearing pendant carboxylate and carboxyl ethyl esters were measured as a function of pH. The CEST signal from the Eu3+-bound water molecule decreased in intensity between pH 8.5 and 4.5 while the proton exchange rates (kex) increased over this same pH range. In comparison, the CEST signal in the corresponding carboxyl ester derivatives was nearly constant. Both observations are consistent with stepwise protonation of the four carboxylic acid groups over this same pH range. This indicates that negative charges on the carboxyl groups above pH 6 facilitate the formation of a strong hydrogen-bonding network in the coordination second sphere above the single Eu3+-bound water molecule, thereby decreasing prototropic exchange of protons on the bound water molecule with bulk water protons. The percentage of square antiprismatic versus twisted square antiprism coordination isomers also decreased as the appended carboxylic acid groups were positioned further away from the amide. The net effect of lowering the pH was an overall increase in kex and a quenching of the CEST signal. This article is part of the themed issue 'Challenges for chemistry in molecular imaging'.

Artificial Metalloproteins Containing Co 4O 4Cubane Active Sites

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

Olshansky, Lisa; Huerta-Lavorie, Raul; Nguyen, Andy I.

Artificial metalloproteins (ArMs) containing Co 4O 4 cubane active sites were constructed via biotin-streptavidin technology. Stabilized by hydrogen bonds (H-bonds), terminal and cofacial Co III-OH 2 moieties are observed crystallographically in a series of immobilized cubane sites. Solution electrochemistry provided correlations of oxidation potential and pH. For variants containing Ser and Phe adjacent to the metallocofactor, 1e -/1H + chemistry predominates until pH 8, above which the oxidation becomes pH-independent. Installation of Tyr proximal to the Co 4O 4 active site provided a single H-bond to one of a set of cofacial Co III-OH 2 groups. With this variant, multi-emore » - /multi-H + chemistry is observed, along with a change in mechanism at pH 9.5 that is consistent with Tyr deprotonation. Finally, with structural similarities to both the oxygen-evolving complex of photosystem II (H-bonded Tyr) and to thin film water oxidation catalysts (Co 4O 4 core), these findings bridge synthetic and biological systems for water oxidation, highlighting the importance of secondary sphere interactions in mediating multi-e - /multi-H + reactivity.« less

Developing Critical Loads of acidity for streams in the Great Smoky Mountains National Park, using PnET-BGC model

NASA Astrophysics Data System (ADS)

Fakhraei, H.

2015-12-01

Acid deposition has impaired acid-sensitive streams and reduced aquatic biotic integrity in Great Smoky Mountains National Park (GRSM) by decreasing pH and acid neutralizing capacity (ANC). Twelve streams in GRSM are listed by the state of Tennessee as impaired due to low stream pH (pH<6.0) under Section 303(d) of the Clean Water Act. A dynamic biogeochemical model, PnET-BGC, was used to evaluate past, current and potential future changes in soil and water chemistry of watersheds of GRSM in response to changes in acid deposition. Calibrating 30 stream-watersheds in GRSM (including 12 listed impaired streams) to the long-term stream chemistry observations, the model was parameterized for the Park. The calibrated model was used to evaluate the level of atmospheric deposition above which harmful effects occur, known as "critical loads", for individual study watersheds. Estimated critical loads and exceedances (levels of deposition above the critical load) of atmospheric sulfur and nitrogen deposition were depicted through geographic information system maps. Accuracy of model simulations in the presence of uncertainties in the estimated model parameters and inputs was assessed using three uncertainty and sensitivity techniques.

Artificial Metalloproteins Containing Co 4O 4Cubane Active Sites

DOE PAGES

Olshansky, Lisa; Huerta-Lavorie, Raul; Nguyen, Andy I.; ...

2018-02-05

Artificial metalloproteins (ArMs) containing Co 4O 4 cubane active sites were constructed via biotin-streptavidin technology. Stabilized by hydrogen bonds (H-bonds), terminal and cofacial Co III-OH 2 moieties are observed crystallographically in a series of immobilized cubane sites. Solution electrochemistry provided correlations of oxidation potential and pH. For variants containing Ser and Phe adjacent to the metallocofactor, 1e -/1H + chemistry predominates until pH 8, above which the oxidation becomes pH-independent. Installation of Tyr proximal to the Co 4O 4 active site provided a single H-bond to one of a set of cofacial Co III-OH 2 groups. With this variant, multi-emore » - /multi-H + chemistry is observed, along with a change in mechanism at pH 9.5 that is consistent with Tyr deprotonation. Finally, with structural similarities to both the oxygen-evolving complex of photosystem II (H-bonded Tyr) and to thin film water oxidation catalysts (Co 4O 4 core), these findings bridge synthetic and biological systems for water oxidation, highlighting the importance of secondary sphere interactions in mediating multi-e - /multi-H + reactivity.« less

Hydrogeochemical Processes Causing Persistent Low pH in Lakes within a Reclaimed Lignite Mine, East Texas

NASA Astrophysics Data System (ADS)

Paul, J. C.; Schwab, P.; Knappett, P.; Deng, Y.

2017-12-01

Surface water pH values ranging from 2.5 to 2.6 have been reported in three lakes at a reclaimed lignite mine located in the Wilcox Formation of East Texas (the site). Traditional neutralization processes using alkaline chemicals to neutralize the surface water were found to be temporary solutions at the site. Low pH conditions usually are caused by oxidation of pyritic materials in the original tailings, but that was not always apparent based on previous studies at this site. The objective of this study is to determine factors contributing to acid seepage to aid in developing pre- and post-mining strategies to mitigate persistent acidity in surface waters at this and other sites. Mineralogy, hydrogeology, and hydrogeochemical reactions were evaluated. A network of 30 wells was used to monitor the water table and chemistry of the shallow, unconfined aquifer surrounding the lakes. Pressure transducers were deployed in 18 of these wells and each of the lakes to measure high frequency water levels over approximately one year. These water levels were contoured to visualize changing hydraulic head over time and determine the correlation in time between ground water flow directions and local rainfall events. Boreholes at 15 of the monitoring wells were continuously cored, and samples were taken at selected depth intervals based on pH measurements. XRD, SEM, and TEM were used to determine the mineralogy of select soil samples. Ion chromatography was used to determine sulfate concentration, and ICP-MS was used to determine solute concentrations from water and digested soil samples. Framboidal and microcrystalline pyrite were identified in the vadose zone in silt and clay-sized fractions; these minerals have high surface area that is conducive to rapid oxidation and acidification as ground water permeates from the vadose into the saturated zone. Morphology in addition to quantity of weatherable pyrite plays a significant role in acidification. Computer models were used to evaluate the effect of dissolving and precipitating solid phases on water chemistry along identified subsurface flow pathways with a focus on metal sulfides and iron oxides as influential to acid mine seepage into the affected lakes.

Tidally driven water column hydro-geochemistry in a remediating acidic wetland

NASA Astrophysics Data System (ADS)

Johnston, Scott G.; Keene, Annabelle F.; Bush, Richard T.; Sullivan, Leigh A.; Wong, Vanessa N. L.

2011-10-01

SummaryManaged tidal inundation is a newly evolved technique for remediating coastal acid sulphate soil (CASS) wetlands. However, there remains considerable uncertainty regarding the hydro-geochemical pathways and spatiotemporal dynamics of residual H + and metal(loid) mobilisation into the tidal fringe surface waters of these uniquely iron-rich landscapes. Here, we examine the hydrology and water column chemistry across the intertidal slope of a remediating CASS wetland during several tide cycles. There was extreme spatial and temporal dynamism in water column chemistry, with pH fluctuating by ˜3 units (˜3.5-6.5) during a single tide cycle. Acute acidity was spatially confined to the upper intertidal slope, reflecting surface sediment properties, and tidal overtopping is an important pathway for mobilisation of residual H + and Al 3+ to the water column. Marine derived HCO3- was depleted from surface waters migrating across the intertidal slope and a strong gradient in HCO3- was observed from the tidal fringe to the adjacent tributary channel and nearby estuary. Tidal forcing generated oscillating hydraulic gradients in the shallow fringing aquifer, favouring ebb-tide seepage and driving rapid, heterogeneous advection of groundwater on the lower intertidal slope via surface connected macropores. A combination of diffusive and advective flux across the sediment-water interface led to persistent, elevated surface water Fe 2+ (˜10-1000 μM). The geochemical processes associated with Fe 2+ mobilisation displayed distinct spatial zonation, with low pH, proton-promoted desorption occurring on the upper intertidal slope, whilst circum-neutral pH, Fe(III)-reducing processes dominated the lower intertidal slope. Arsenic was also mobilised into surface waters on the lower intertidal slope under moderate pH (˜6.0) conditions and was strongly positively correlated with Fe 2+. Saturation index values for aragonite were substantially depressed (-1 to -5) and significantly negatively correlated with elevation, thereby presenting a barrier to re-colonisation of the upper intertidal slope by calcifying benthic organisms. These findings highlight the spatially complex hydrological and geochemical controls on surface water quality that can occur in tidally inundated acid sulphate soil environments.

The pH and ionic composition of stratiform cloud water

NASA Astrophysics Data System (ADS)

Castillo, Raymond A.; Jiusto, James E.; Mclaren, Eugene

Over 50 cloud water samples were collected during five comprehensive case studies of the water chemistry of stratiform clouds at Whiteface Mountain, New York. The water samples were analyzed for pH, conductivity and ions of sodium, potassium, magnesium, calcium, ammonium, sulfate, chloride and nitrate. Trajectory analyses and cloud condensation nucleus concentrations at 0.5 % confirmed that the air masses in all five of these cases represented continental air that was relatively clean (low aerosol concentration) for the northeystern United States. The major ions related to cloud water pH were found to be sulfate, nitrate, potassium, ammonium and calcium. The results revealed a mean hydrogen ion concentration [ H+] = 0.239 meq ℓ -1 ( σ = ± 0.21) which converts to a mean pH = 3.6 for all collected cloud samples. The low pH values are related to a normal background of nitrate ions found in the rural continental air masses plus sulfate ions largely from the industrial emissions of the midwestern United States. The [NO -3], in two of the three cases presented, demonstrates the importance of the nitrate ions' contribution to the pH of cloud water. A dependent means analysis of 40 events yielded a significant difference (0.04 level of significance), with the mean pH of precipitation (4.2) being greater than the mean pH of cloud water (4.0) for event samples. The ion concentrations indicated that the cloud rainout process contributed from 67 % to almost 100% of the total ion concentration of the precipitation. The washout process, i.e. precipitation scavenging below the cloud base, contributed considerably less than the cloud/rainout process of those total precipitation anions associated with air pollution.

Biogenic acidification reduces sea urchin gonad growth and increases susceptibility of aquaculture to ocean acidification.

PubMed

Mos, Benjamin; Byrne, Maria; Dworjanyn, Symon A

2016-02-01

Decreasing oceanic pH (ocean acidification) has emphasised the influence of carbonate chemistry on growth of calcifying marine organisms. However, calcifiers can also change carbonate chemistry of surrounding seawater through respiration and calcification, a potential limitation for aquaculture. This study examined how seawater exchange rate and stocking density of the sea urchin Tripneustes gratilla that were reproductively mature affected carbonate system parameters of their culture water, which in turn influenced growth, gonad production and gonad condition. Growth, relative spine length, gonad production and consumption rates were reduced by up to 67% by increased density (9-43 individuals.m(-2)) and reduced exchange rates (3.0-0.3 exchanges.hr(-1)), but survival and food conversion efficiency were unaffected. Analysis of the influence of seawater parameters indicated that reduced pH and calcite saturation state (ΩCa) were the primary factors limiting gonad production and growth. Uptake of bicarbonate and release of respiratory CO2 by T. gratilla changed the carbonate chemistry of surrounding water. Importantly total alkalinity (AT) was reduced, likely due to calcification by the urchins. Low AT limits the capacity of culture water to buffer against acidification. Direct management to counter biogenic acidification will be required to maintain productivity and reproductive output of marine calcifiers, especially as the ocean carbonate system is altered by climate driven ocean acidification. Copyright © 2015 Elsevier Ltd. All rights reserved.

Effect of water-column pH on sediment-phosphorus release rates in Upper Klamath Lake, Oregon, 2001

USGS Publications Warehouse

Fisher, Lawrence H.; Wood, Tamara M.

2004-01-01

Sediment-phosphorus release rates as a function of pH were determined in laboratory experiments for sediment and water samples collected from Shoalwater Bay in Upper Klamath Lake, Oregon, in 2001. Aerial release rates for a stable sediment/water interface that is representative of the sediment surface area to water column volume ratio (1:3) observed in the lake and volumetric release rates for resuspended sediment events were determined at three different pH values (8.1, 9.2, 10.2). Ambient water column pH (8.1) was maintained by sparging study columns with atmospheric air. Elevation of the water column pH to 9.2 was achieved through the removal of dissolved carbon dioxide by sparging with carbon dioxide-reduced air, partially simulating water chemistry changes that occur during algal photosynthesis. Further elevation of the pH to 10.2 was achieved by the addition of sodium hydroxide, which doubled average alkalinities in the study columns from about 1 to 2 milliequivalents per liter. Upper Klamath Lake sediments collected from the lake bottom and then placed in contact with lake water, either at a stable sediment/water interface or by resuspension, exhibited an initial capacity to take up soluble reactive phosphorus (SRP) from the water column rather than release phosphorus to the water column. At a higher pH this initial uptake of phosphorus is slowed, but not stopped. This initial phase was followed by a reversal in which the sediments began to release SRP back into the water column. The release rate of phosphorus 30 to 40 days after suspension of sediments in the columns was 0.5 mg/L/day (micrograms per liter per day) at pH 8, and 0.9 mg/L/day at pH 10, indicating that the higher pH increased the rate of phosphorus release by a factor of about two. The highest determined rate of release was approximately 10% (percent) of the rate required to explain the annual internal loading to Upper Klamath Lake from the sediments as calculated from a lake-wide mass balance and observed in total phosphorus data collected at individual locations.

Techniques for Teachers Section

ERIC Educational Resources Information Center

Tait, A., Ed.

1973-01-01

Includes a simple technique to demonstrate Millikan's oil drop experiment, an environmental studies experiment to measure dissolved oxygen in water samples, and a technique to demonstrate action-reaction. Science materials described are the Pol-A-Star Tomiscope, Nuffield chemistry film loops, air pucks and pH meters. (JR)

Assessment of selected inorganic constituents in streams in the Central Arizona Basins Study Area, Arizona and northern Mexico, through 1998

USGS Publications Warehouse

Anning, David W.

2003-01-01

Stream properties and water-chemistry constituent concentrations from data collected by the National Water-Quality Assessment and other U.S. Geological Survey water-quality programs were analyzed to (1) assess water quality, (2) determine natural and human factors affecting water quality, and (3) compute stream loads for the surface-water resources in the Central Arizona Basins study area. Stream temperature, pH, dissolved-oxygen concentration and percent saturation, and dissolved-solids, suspended-sediment, and nutrient concentration data collected at 41 stream-water quality monitoring stations through water year 1998 were used in this assessment. Water-quality standards applicable to the stream properties and water-chemistry constituent concentration data for the stations investigated in this study generally were met, although there were some exceedences. In a few samples from the White River, the Black River, and the Salt River below Stewart Mountain Dam, the pH in reaches designated as a domestic drinking water source was higher than the State of Arizona standard. More than half of the samples from the Salt River below Stewart Mountain Dam and almost all of the samples from the stations on the Central Arizona Project Canal?two of the three most important surface-water sources used for drinking water in the Central Arizona Basins study area?exceeded the U.S. Environmental Protection Agency drinking water Secondary Maximum Contaminant Level for dissolved solids. Two reach-specific standards for nutrients established by the State of Arizona were exceeded many times: (1) the annual mean concentration of total phosphorus was exceeded during several years at stations on the main stems of the Salt and Verde Rivers, and (2) the annual mean concentration of total nitrogen was exceeded during several years at the Salt River near Roosevelt and at the Salt River below Stewart Mountain Dam. Stream properties and water-chemistry constituent concentrations were related to streamflow, season, water management, stream permanence, and land and water use. Dissolved-oxygen percent saturation, pH, and nutrient concentrations were dependent on stream regulation, stream permanence, and upstream disposal of wastewater. Seasonality and correlation with streamflow were dependant on stream regulation, stream permanence, and upstream disposal of wastewater. Temporal trends in streamflow, stream properties, and water-chemistry constituent concentrations were common in streams in the Central Arizona Basins study area. Temporal trends in the streamflow of unregulated perennial reaches in the Central Highlands tended to be higher from 1900 through the 1930s, lower from the 1940s through the 1970s, and high again after the 1970s. This is similar to the pattern observed for the mean annual precipitation for the Southwestern United States and indicates long-term trends in flow of streams draining the Central Highlands were driven by long-term trends in climate. Streamflow increased over the period of record at stations on effluent-dependent reaches as a result of the increase in the urban population and associated wastewater returns to the Salt and Gila Rivers in the Phoenix metropolitan area and the Santa Cruz River in the Tucson metropolitan area. Concentrations of dissolved solids decreased in the Salt River below Stewart Mountain Dam and in the Verde River below Bartlett Dam. This decrease represents an improvement in the water quality and resulted from a concurrent increase in the amount of runoff entering the reservoirs. Stream loads of water-chemistry constituents were compared at different locations along the streams with one another, and stream loads were compared to upstream inputs of the constituent from natural and anthropogenic sources to determine the relative importance of different sources and to determine the fate of the water-chemistry constituent. Of the dissolved solids transported into the Basin and Range Lowlands each year

From municipal sewage to drinking water: fate and removal of pharmaceutical residues in the aquatic environment in urban areas.

PubMed

Heberer, Th; Reddersen, K; Mechlinski, A

2002-01-01

Recently, the occurrence and fate of pharmaceutically active compounds (PhACs) in the aquatic environment was recognized as one of the emerging issues in environmental chemistry and as a matter of public concern. Residues of PhACs have been found as contaminants in sewage, surface, and ground- and drinking water samples. Since June 2000, a new long-term monitoring program of sewage, surface, ground- and drinking water has been carried out in Berlin, Germany. Samples, collected periodically from selected sites in the Berlin area, are investigated for residues of PhACs and related contaminants. The purpose of this monitoring is to investigate these compounds over a long time period to get more reliable data on their occurrence and fate in the different aquatic compartments. Moreover, the surface water investigations allow the calculation of season-dependent contaminant loads in the Berlin waters. In the course of the monitoring program, PhACs and some other polar compounds were detected at concentrations up to the microg/L-level in all compartments of the Berlin water cycle. The monitoring is accompanied and supported by several other investigations such as laboratory column experiments and studies on bank filtration and drinking water treatment using conventional or membrane filtration techniques.

Utilization of municipal wastewater for cooling in thermoelectric power plants

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

Safari, Iman; Walker, Michael E.; Hsieh, Ming-Kai

2013-09-01

A process simulation model has been developed using Aspen Plus® with the OLI (OLI System, Inc.) water chemistry model to predict water quality in the recirculating cooling loop utilizing secondary- and tertiary-treated municipal wastewater as the source of makeup water. Simulation results were compared with pilot-scale experimental data on makeup water alkalinity, loop pH, and ammonia evaporation. The effects of various parameters including makeup water quality, salt formation, NH 3 and CO 2 evaporation mass transfer coefficients, heat load, and operating temperatures were investigated. The results indicate that, although the simulation model can capture the general trends in the loopmore » pH, experimental data on the rates of salt precipitation in the system are needed for more accurate prediction of the loop pH. It was also found that stripping of ammonia and carbon dioxide in the cooling tower can influence the cooling loop pH significantly. The effects of the NH 3 mass transfer coefficient on cooling loop pH appear to be more significant at lower values (e.g., k NH3 < 4×10 -3 m/s) when the makeup water alkalinity is low (e.g., <90 mg/L as CaCO 3). The effect of the CO2 mass transfer coefficient was found to be significant only at lower alkalinity values (e.g., k CO2<4×10 -6 m/s).« less

Refuges from ocean acidification: determining tolerances of coralline algae to naturally low-pH water

NASA Astrophysics Data System (ADS)

Cooper, H.; Paytan, A.; Potts, D. C.

2014-12-01

Anthropogenic carbon dioxide dissolving into the world's oceans is causing a profound and rapid shift in ocean chemistry referred to as ocean acidification (OA) that causes carbonate structures to dissolve more readily in seawater with negative effects for organisms relying on calcified skeletons or shells (e.g. corals, mollusks, coralline algae). Crustose coralline algae (CCA) are ubiquitous and essential on coral reefs, providing both ecological and structural benefits to the reefs. However, CCA are adversely affected by low pH water, with severe reductions in recruitment, survival, growth and productivity. The ability of different species of CCA to adapt to low pH waters was tested using a system of natural submarine springs (called "ojos") near Puerto Morelos on the Yucatan Peninsula, Mexico. These ojos continuously discharge groundwater that is close to seawater salinity but more acidic (pH 6.70-7.30) and under saturated (0.3 Ω to 0.97 Ω) than the ambient seawater (pH 8.03, 3.60 Ω ). Both corals and coralline algae grow in the water from these springs, suggesting that some calcifying species differ in their tolerance to low pH waters. Corallines were sampled along a pH gradient at five springs in December 2013 using underwater transects. Differences in percent cover, species abundance and diversity of CCA by pH levels will be discussed. This work utilizes a unique natural laboratory for studying properties of calcifying biota along pH gradients and provides insight into the ability of CCA to tolerate or adapt to future conditions.

Mineralogy and geochemistry of efflorescent minerals on mine tailings and their potential impact on water chemistry.

PubMed

Grover, B P C; Johnson, R H; Billing, D G; Weiersbye, I M G; Tutu, H

2016-04-01

In the gold mining Witwatersrand Basin of South Africa, efflorescent mineral crusts are a common occurrence on and nearby tailings dumps during the dry season. The crusts are readily soluble and generate acidic, metal- and sulphate-rich solutions on dissolution. In this study, the metal content of efflorescent crusts at an abandoned gold mine tailings dump was used to characterise surface and groundwater discharges from the site. Geochemical modelling of the pH of the solution resulting from the dissolution of the crusts was used to better understand the crusts' potential impact on water chemistry. The study involved two approaches: (i) conducting leaching experiments on oxidised and unoxidised tailings using artificial rainwater and dilute sulphuric acid and correlating the composition of crusts to these leachates and (ii) modelling the dissolution of the crusts in order to gain insight into their mineralogy and their potential impact on receiving waters. The findings suggested that there were two chemically distinct discharges from the site, namely an aluminium- and magnesium-rich surface water plume and an iron-rich groundwater plume. The first plume was observed to originate from the oxidised tailings following leaching with rainwater while the second plume originated from the underlying unoxidised tailings with leaching by sulphuric acid. Both groups of minerals forming from the respective plumes were found to significantly lower the pH of the receiving water with simulations of their dissolution found to be within 0.2 pH units of experimental values. It was observed that metals in a low abundance within the crust (for example, iron) had a stronger influence on the pH of the resulting solutions than metals in a greater abundance (aluminium or magnesium). Techniques such as powder X-ray diffraction (PXRD) and in situ mineral determination techniques such as remote sensing can effectively determine the dominant mineralogy. However, the minerals or metals incorporated through solid solution into bulk mineralogy that dominates the chemistry of the solutions upon their dissolution may occur in minor quantities that can only be predicted using chemical analysis. Their mineralogy can be predicted using geochemical modelling and can provide a set of hypothetical minerals that upon dissolution yield a solution similar to that of the actual crusts. This realisation has a bearing on decision-making such as in risk assessment and designing pollutant mitigation strategies.

Characterization and remediation of Soil Contaminated with Explosives: Development of Practical Technologies

DTIC Science & Technology

2001-07-06

Chemistry Agnes Renoux, Ph.D. Ecotoxicology Bernard Lachance, Ph. D. Ecotoxicology Ping Gong, Ph. D. Ecotoxicology Pierre-Yves Robidoux, Ph.D... Ecotoxicology Tamara Sheremata, Ph. D. Env. Engineering Diane Fournier, Ph.D. Microbiology Annamaria Halasz, M.Sc. Chemistry Louise Paquet, B.Sc...12 Chapter 4: Applied Ecotoxicology

PCO2 effects on species composition and growth of an estuarine phytoplankton community

EPA Science Inventory

Ocean and coastal waters are undergoing changes in carbonate chemistry, including pH, in response to increasing atmospheric CO2 concentration and the microbial degradation of organic matter associated with nutrient enrichment. The effects of this change on plankton communities ha...

Formation of Aqueous Suspensions of Fullerenes

EPA Science Inventory

Colloidal suspensions of C60, C70 and a derivative of C60, PCBM ([6,6]-Phenyl C61-butyric acid methyl ester) were produced by extended mixing in water. We examined the contribution of background solution chemistry (pH, ionic strength) on the formation kinetics of colloidal suspe...

In situ generation of ultrafast transient "acid spikes" in the 10B(n,α)7Li radiolysis of water

NASA Astrophysics Data System (ADS)

Islam, Muhammad Mainul; Kanike, Vanaja; Meesungnoen, Jintana; Lertnaisat, Phantira; Katsumura, Yosuke; Jay-Gerin, Jean-Paul

2018-02-01

Monte Carlo track chemistry simulations of the 10B(n,α)7Li radiolysis of water show that the in situ formation of H3O+ by the two He and Li recoiling ions renders the native track regions temporarily very acidic. For these irradiating ions, the pH remains near 0 at times less than ∼100 ps after which the system gradually returns to neutral pH at ∼0.1 ms. These 'acid spikes' have never been invoked in water or in a cellular environment exposed to densely ionizing radiations. The question of their implications in boron neutron capture therapy and, more generally, in hadrontherapy, is discussed briefly.

Richard J. French, Ph.D. | NREL

Science.gov Websites

J. French, Ph.D. Photo of Richard J. French Rick French Researcher IV-Chemistry Richard.French Laboratory equipment design and construction Computer-aided design (CAD) Education Ph.D., Chemistry, Oregon State University B.S., Chemistry, Wheaton College Professional Experience Research Scientist, National

Impact of volcanic plume emissions on rain water chemistry during the January 2010 Nyamuragira eruptive event: implications for essential potable water resources.

PubMed

Cuoco, Emilio; Tedesco, Dario; Poreda, Robert J; Williams, Jeremy C; De Francesco, Stefano; Balagizi, Charles; Darrah, Thomas H

2013-01-15

On January 2, 2010 the Nyamuragira volcano erupted lava fountains extending up to 300 m vertically along an ~1.5 km segment of its southern flank cascading ash and gas on nearby villages and cities along the western side of the rift valley. Because rain water is the only available potable water resource within this region, volcanic impacts on drinking water constitutes a major potential hazard to public health within the region. During the 2010 eruption, concerns were expressed by local inhabitants about water quality and feelings of physical discomfort (e.g. nausea, bloating, indigestion, etc.) after consuming rain water collected after the eruption began. We present the elemental and ionic chemistry of drinking water samples collected within the region on the third day of the eruption (January 5, 2010). We identify a significant impact on water quality associated with the eruption including lower pH (i.e. acidification) and increases in acidic halogens (e.g. F(-) and Cl(-)), major ions (e.g. SO(4)(2-), NH(4)(+), Na(+), Ca(2+)), potentially toxic metals (e.g. Al(3+), Mn(2+), Cd(2+), Pb(2+), Hf(4+)), and particulate load. In many cases, the water's composition significantly exceeds World Health Organization (WHO) drinking water standards. The degree of pollution depends upon: (1) ash plume direction and (2) ash plume density. The potential negative health impacts are a function of the water's pH, which regulates the elements and their chemical form that are released into drinking water. Copyright © 2012 Elsevier B.V. All rights reserved.

Influence of Acid Mine Drainage (AMD) on recent phyto- and zooplankton in "the Anthropogenic Lake District" in south-west Poland

NASA Astrophysics Data System (ADS)

Sienkiewicz, Elwira; Gasiorowski, Michal

2015-04-01

In south-west Poland (central Europe) many the post-mining lakes formed so-called "the Anthropogenic Lake District". Areas, where water comes in contact with lignite beds characterized by high concentration of sulfide minerals are called Acid Mine Drainage (AMD). Pyrite oxidation and other sulfide compounds caused release sulfuric acids and heavy metal ions. These processes caused decline of water pH, sometimes to extremely low pH < 2.8. Presently, pit lakes located in south-west Poland have water pH ranged between 2.7 and 8.9. Differences of water reaction in the mine lakes depend on many factors, such as bedrock buffer capacity, geological structure of carboniferous area, exploitation technique of lignite, methods of filling and water supply of reservoirs and their age. During the evolution of lakes' ecosystems, sulfate-iron-calcium type of waters occurring in acid lakes will transform in alkaline hydrogen-carbonate-calcium type of waters. Due to the different time of the completion of lignite exploitation, lakes' age varied between forty and over one hundred years. Studies showed that younger lakes are more acidic in compare to older. To estimate impact of AMD we analyzed recent diversity of diatoms and Cladocera remains and water chemistry from extremely acidic, relatively young lakes and from alkaline, older water bodies. As we expected, flora and fauna from acidic lakes have shown very low diversity and species richness. Among diatoms, Eunotia exigua (Bréb. ex Kütz.) Rabenhorst and/or E. paludosa Grunow were dominated taxa, while fauna Cladocera did not occurred in lakes with water pH < 3. On this area, exploitation of lignite continued up to 1973. Older lakes were formed in the region where the mine started work in 1880 and lignite mining stopped in 1926. Measurements of pH value in situ point to neutral or alkaline water, but because of the possibility of hysteresis phenomenon, the studies of phyto- and zooplankton have shown if there has already been a widespread neutralization of lake ecosystems, what encompassing both recovery of water chemistry and rebuilding of biota communities. Studies have confirmed, that phyto- and zooplankton living nowadays in lakes located on this area, where exploitation of lignite ended at the beginning of 20th century, indicate completely recovery from acidification caused by coal mine activities. Presently, the lakes were dominated by planktonic diatoms and Cladocera taxa, such as Discostella pseudostelligera (Hust.) Houk & Klee and Bosmina longirostris, respectively.

Symposium on PhD Education in Chemistry: A Four-Year Model for the PhD Degree Program in Chemistry.

ERIC Educational Resources Information Center

Burke, James D.

1988-01-01

Proposes an educational model for chemistry PhD education that emphasizes productivity and centrality of research. Supports greater development of communication skills and suggests a four-year timeline. Listed is a curriculum usable for most sciences. (ML)

Control of the microstructure and surface chemistry of graphene aerogels via pH and time manipulation by a hydrothermal method.

PubMed

García-Bordejé, E; Víctor-Román, S; Sanahuja-Parejo, O; Benito, A M; Maser, W K

2018-02-15

Three-dimensional graphene aerogels of controlled pore size have emerged as an important platform for several applications such as energy storage or oil-water separation. The aerogels of reduced graphene oxide are mouldable and light weight, with a porosity up to 99.9%, consisting mainly of macropores. Graphene aerogel preparation by self-assembly in the liquid phase is a promising strategy due to its tunability and sustainability. For graphene aerogels prepared by a hydrothermal method, it is known that the pH value has an impact on their properties but it is unclear how pH affects the auto-assembly process leading to the final properties. We have monitored the time evolution of the chemical and morphological properties of aerogels as a function of the initial pH value. In the hydrothermal treatment process, the hydrogel is precipitated earlier and with lower oxygen content for basic pH values (∼13 wt% O) than for acidic pH values (∼20 wt% O). Moreover, ∼7 wt% of nitrogen is incorporated on the graphene nanosheets at basic pH generated by NH 3 addition. To our knowledge, there is no precedent showing that the pH value affects the microstructure of graphene nanosheets, which become more twisted and bent for the more intensive deoxygenation occurring at basic pH. The bent nanosheets attained at pH = 11 reduce the stacking by the basal planes and they connect via the borders, hence leading eventually to higher pore volumes. In contrast, the flatter graphene nanosheets attained under acidic pH entail more stacking and higher oxygen content after a long hydrothermal treatment. The gravimetric absorption capacity of non-polar solvents scales directly with the pore volume. The aerogels have proved to be highly selective, recyclable and robust for the absorption of nonpolar solvents in water. The control of the porous structure and surface chemistry by manipulation of pH and time will also pave the way for other applications such as supercapacitors or batteries.

Effects of Solution Chemistry on Nano-Bubbles Transport in Saturated Porous Media

NASA Astrophysics Data System (ADS)

Hamamoto, S.; Takemura, T.; Suzuki, K.; Nihei, N.; Nishimura, T.

2017-12-01

Nano-bubbles (NBs) have a considerable potential for the remediation of soil and groundwater contaminated by organic compounds, especially when used in conjunction with bioremediation technologies. Understanding the transport mechanisms of NBs in soils is essential to optimize NB-based remediation techniques. In this study, one-dimensional column transport experiments using glass beads with 0.1 mm size were conducted, where NBs created by oxygen gas at different pH and ionic strength were injected to the column at the constant flow rate. The NBs concentration in the effluent was quantified using a resonant mass measurement technique. Effects of solution chemistry of the NBs water on NB transport in the porous media were investigated. The results showed that attachment of NBs was enhanced under higher ionic strength and lower pH conditions, caused by the reduced repulsive force between NBs and glass beads. In addition, bubble size distributions in the effluents showed that relatively larger NBs were retained in the column. This trend was more significant at lower pH condition.

Seasonal Variation in Water Chemistry Parameters in the Clayburn - Willband Watershed, Abbotsford, British Columbia.

NASA Astrophysics Data System (ADS)

Gillies, S. L.; Marsh, S. J.; Peucker-Ehrenbrink, B.; Janmaat, A.; Bourdages, M.; Paulson, D.; Bogaerts, P.; Robertson, K.; Clemence, E.; Smith, S.; Yakemchuk, A.; Faber, A.

2017-12-01

Faculty and students from the University of the Fraser Valley (UFV) have conducted time series sampling of the Fraser River at Fort Langley and six Fraser Valley tributaries as a member of the Global Rivers Observatory (GRO, www.globalrivers.org) coordinated by Woods Hole Oceanographic Institution and Woods Hole Research Center. The Clayburn - Willband - Stoney watershed has become a focus of the sampling being conducted by faculty and students from the Geography and Biology Departments at UFV. Water chemistry data (water temperature, dissolved oxygen, conductivity, pH and turbidity) and samples (nutrients, major ions and bacteria) have been collected weekly from sites on these creeks. These watersheds are threatened by increasing urban development, increasing idustrial activity, and expansion of agricultural landuse within the watershed. Documenting the seasonal changes in the water chemistry as measured during the onset of the heavy fall and winter precipitation events, the wet and cool winters and springs, and the hot and dry summers will assist in attempts to protect these important salmon spawning streams from anthropogenic activity.

[Correlationships between the coverage of vegetation and the quality of groundwater in the lower reaches of the Tarim River].

PubMed

Chen, Yong-jin; Chen, Ya-ning; Liu, Jia-zhen

2010-03-01

The variations vegetation coverage is the result of conjunct effects of inner and outer energy of the earth, however, the human activity always makes the coverage of vegetation change a lot. Based on the monitoring data of chemistry of groundwater and the coverage of vegetation from 2002 to 2007 in the lower reaches of Tarim River, relations between vegetation coverage and groundwater chemistry were studied. It is found that vegetation coverage at Sector A was more than 80%, and decreased from sector to sector, the coverage of Sector I was less than 10%. At the same sector, samples near to water source owned high coverage index, and samples far away from the river had low coverage index. The variations of pH in groundwater expressed similar regulation to vegetation coverage, that is, Sectors near the water source had higher pH index comparing than those far away. Regression between groundwater quality and vegetation coverage disclosed that the coverage of Populus euphratica climbed up along with increase of pH in groundwater, change of Tamarix ramosissima coverage expressed an opposite trend to the Populus euphratica with the same environmental factors. This phenomenon can interpret spatial distribution of Populus euphratica and Tamarix ramosissima in lower reaches of the Tarim River.

Acidophilic sulfur disproportionation

NASA Astrophysics Data System (ADS)

Hardisty, Dalton S.; Olyphant, Greg A.; Bell, Jonathan B.; Johnson, Adam P.; Pratt, Lisa M.

2013-07-01

Bacterial disproportionation of elemental sulfur (S0) is a well-studied metabolism and is not previously reported to occur at pH values less than 4.5. In this study, a sediment core from an abandoned-coal-mine-waste deposit in Southwest Indiana revealed sulfur isotope fractionations between S0 and pyrite (Δ34Ses-py) of up to -35‰, inferred to indicate intense recycling of S0 via bacterial disproportionation and sulfide oxidation. Additionally, the chemistry of seasonally collected pore-water profiles were found to vary, with pore-water pH ranging from 2.2 to 3.8 and observed seasonal redox shifts expressed as abrupt transitions from Fe(III) to Fe(II) dominated conditions, often controlled by fluctuating water table depths. S0 is a common product during the oxidation of pyrite, a process known to generate acidic waters during weathering and production of acid mine drainage. The H2S product of S0 disproportionation, fractionated by up to -8.6‰, is rapidly oxidized to S0 near redox gradients via reaction with Fe(III) allowing for the accumulation of isotopically light S0 that can then become subject to further sulfur disproportionation. A mass-balance model for S0 incorporating pyrite oxidation, S0 disproportionation, and S0 oxidation readily explains the range of observed Δ34Ses-py and emphasizes the necessity of seasonally varying pyrite weathering and metabolic rates, as indicated by the pore water chemistry. The findings of this research suggest that S0 disproportionation is potentially a common microbial process at a pH < 4.5 and can create large sulfur isotope fractionations, even in the absence of sulfate reduction.

Linking pulses of atmospheric deposition to DOC release in an upland peat-covered catchment

NASA Astrophysics Data System (ADS)

Worrall, F.; Burt, T. P.; Adamson, J. K.

2008-12-01

Changes in atmospheric deposition have been proposed as one possible explanation of the widespread increase in DOC concentration observed in many Northern Hemisphere catchments. This study uses detailed, long-term, monthly monitoring records of pH, conductivity SO4, and DOC in precipitation, soil water, and runoff chemistry from an upland peat-covered catchment in northern England. By deriving impulse transfer functions this study explores whether changes in deposition lead to significant changes in the occurrence of each component in the soil and runoff water; especially significant changes in DOC. The study shows that (1) impulses in the deposition of acidity have no significant effect upon pH or DOC in soil water or runoff. (2) DOC in soil water and runoff is responsive to impulses in SO4 and conductivity, but only when those impulses are changes in soil water chemistry and not when they are in atmospheric deposition. (3) The effects of changes in SO4 and/or conductivity can easily be overemphasized if memory effects are not accounted for, and their effect is limited to only 1 or 2 months after a severe drought. This study can support the view that changes in ionic strength can result in changes in DOC concentration in soil water or runoff, but the system studied is unresponsive to changes in atmospheric deposition. Impulses in soil water SO4 do not lead to increases in DOC concentrations, and so this mechanism does not provide an explanation for DOC increases.

Review of the inorganic geochemistry of peats and peatland waters

NASA Astrophysics Data System (ADS)

Shotyk, William

1988-06-01

The major floristic and geochemical differences between bogs, fens, and swamps are summarized, and the most common peat types described. This is followed by a critical, historical review of the literature. The methods used to measure the pH of peatland (mire) waters are examined, and the pH range of various peatland types is reported. In addition, horizontal and vertical pH variations are illustrated, and factors affecting the pH of these waters reviewed. The cause of the low pH of surface waters of Sphagnum bogs (approximately pH 4) is critically investigated, and the relative importance of dissolved CO 2 and other inorganic acids, and organic acids to the low pH is assessed. Cation exchange on the surfaces of Sphagnum mosses is found to be a relatively unimportant acidification mechanism, but important to the chemical ecology of the plants. The redox chemistry of mire waters is described in terms of the geochemistry of such redox indicators as O 2, CO 2, CH 4, CO, H 2, H 2S, SO 42-, native Cu, and siderite (FeCO 3). Published studies of Eh in peatlands are cited, and the problems of Eh measurement and interpretation are explored. The chemical composition of mire waters (major and trace metals, and nonmetallic species) is examined, and factors affecting their composition reported. The abundance and distribution of mineral matter in peats is described, and the occurrence and formation of minerals of Fe (pyrite and other sulphides, siderite, vivianite), Cu (chalcopyrite, native Cu, covellite) and Zn (smithsonite and wurtzite) investigated. The abundance and distribution of major elements (Si, Al, Na, K, Mg, Ca) and trace metals (Ni, V, Cr, Fe, Mn, Cu, U, Zn, Pb) is described, and factors affecting their solubility examined.

Silver Dissolution and Release from Ceramic Water Filters.

PubMed

Mittelman, Anjuliee M; Lantagne, Daniele S; Rayner, Justine; Pennell, Kurt D

2015-07-21

Application of silver nanoparticles (nAg) or silver nitrate (AgNO3) has been shown to improve the microbiological efficacy of ceramic water filters used for household water treatment. Silver release, however, can lead to undesirable health effects and reduced filter effectiveness over time. The objectives of this study were to evaluate the contribution of nanoparticle detachment, dissolution, and cation exchange to silver elution, and to estimate silver retention under different influent water chemistries. Dissolved silver (Ag(+)) and nAg release from filter disks painted with 0.03 mg/g casein-coated nAg or AgNO3 were measured as a function of pH (5-9), ionic strength (1-50 mM), and cation species (Na(+), Ca(2+), Mg(2+)). Silver elution was controlled by dissolution as Ag(+) and subsequent cation exchange reactions regardless of the applied silver form. Effluent silver levels fell below the drinking water standard (0.1 mg/L) after flushing with 30-42 pore volumes of pH 7, 10 mM NaNO3 at pH 7. When the influent water was at pH 5, contained divalent cations or 50 mM NaNO3, silver concentrations were 5-10 times above the standard. Our findings support regular filter replacement and indicate that saline, hard, or acidic waters should be avoided to minimize effluent silver concentrations and preserve silver treatment integrity.

Influence of surface chemistry of carbon materials on their interactions with inorganic nitrogen contaminants in soil and water.

PubMed

Sumaraj; Padhye, Lokesh P

2017-10-01

Inorganic nitrogen contaminants (INC) (NH 4 + , NO 3 - , NO 2 - , NH 3 , NO, NO 2 , and N 2 O) pose a growing risk to the environment, and their remediation methods are highly sought after. Application of carbon materials (CM), such as biochar and activated carbon, to remediate INC from agricultural fields and wastewater treatment plants has gained a significant interest since past few years. Understanding the role of surface chemistry of CM in adsorption of various INC is highly critical to increase adsorption efficiency as well as to assess the long term impact of using these highly recalcitrant CM for remediation of INC. Critical reviews of adsorption studies related to INC have revealed that carbon surface chemistry (surface functional groups, pH, Eh, elemental composition, and mineral content) has significant influence on adsorption of INC. Compared to basic functional groups, oxygen containing surface functional groups have been found to be more influential for adsorption of INC. However, basic sites on carbon materials still play an important role in chemisorption of anionic INC. Apart from surface functional groups, pH, Eh and pH zpc of CM and elemental and mineral composition of its surface are important properties capable of altering INC interactions with CM. This review summarizes our current understanding of INC interactions with CM's surface through the known chemisorption mechanisms: electrostatic interaction, hydrogen bonding, electron donor-acceptor mechanism, hydrophobic and hydrophilic interaction, chemisorption aided by minerals, and interactions influenced by pH and elemental composition. Change in surface chemistry of CM in soil during aging is also discussed. Copyright © 2017 Elsevier Ltd. All rights reserved.

Probing the internal calcification chemistry of O. universa using B/Ca

NASA Astrophysics Data System (ADS)

Holland, K.; Eggins, S.; Hoenisch, B.; Haynes, L.; Russell, A. D.

2014-12-01

The B/Ca, U/Ca ratio values of calcitic foraminifer shells are all influenced by seawater carbonate chemistry (seawater [B(OH)4-/HCO3-], [CO32-], and pH respectively), and as such are increasingly being used as proxies to reconstruct past changes in ocean inorganic carbon content, saturation state and pH. However, the behavior of these proxies is subject to modification by foraminifers' efforts to regulate the conditions under which they grow their shells. We have undertaken experiments on Orbulina universa that manipulate synthetic culture water DIC, pH and [Ca] in an effort to disentangle the biological versus environmental influences of seawater carbonate system and saturation state on B/Ca, U/Ca and Mg/Ca ratio into foraminiferal calcite. Experiments were designed to be able determine the extent to which foraminifers are able to modify the chemical composition of their (vacuolized?) internal calcification fluid, in particular by using B/Ca and U/Ca as sensors for calcification chemistry (i.e. internal [B(OH)4-/HCO3-] and [CO32-]) . We have used a high resolution LA-ICPMS depth profiling techniques to characterize the amplitude of B/Ca, U/Ca, Mg/Ca, and Sr/Ca ratio values across and the thickness (calcification rate) of diurnal bands that are developed in individual shells grown under different synthetic seawater compositions. Results indicate Orbulina universa modify the chemistry of their calcification fluid far from that of external seawater, but are not able to mitigate changes in external seawater. This most likely achieved through the interactive effects of internal pH manipulation and a carbon concentration mechanism. Our results are likely to have important implications for the interpretation of Mg/Ca, B/Ca and U/Ca as proxies seawater temperatures and carbonate system parameters.

Summit crater lake observations, and the location, chemistry, and pH of water samples near Mount Chiginagak volcano, Alaska: 2004-2012

USGS Publications Warehouse

Schaefer, Janet R.; Scott, William E.; Evans, William C.; Wang, Bronwen; McGimsey, Robert G.

2013-01-01

Mount Chiginagak is a hydrothermally active volcano on the Alaska Peninsula, approximately 170 km south–southwest of King Salmon, Alaska (fig. 1). This small stratovolcano, approximately 8 km in diameter, has erupted through Tertiary to Permian sedimentary and igneous rocks (Detterman and others, 1987). The highest peak is at an elevation of 2,135 m, and the upper ~1,000 m of the volcano are covered with snow and ice. Holocene activity consists of debris avalanches, lahars, and lava flows. Pleistocene pyroclastic flows and block-and-ash flows, interlayered with andesitic lava flows, dominate the edifice rocks on the northern and western flanks. Historical reports of activity are limited and generally describe “steaming” and “smoking” (Coats, 1950; Powers, 1958). Proximal tephra collected during recent fieldwork suggests there may have been limited Holocene explosive activity that resulted in localized ash fall. A cluster of fumaroles on the north flank, at an elevation of ~1,750 m, commonly referred to as the “north flank fumarole” have been emitting gas throughout historical time (location shown in fig. 2). The only other thermal feature at the volcano is the Mother Goose hot springs located at the base of the edifice on the northwestern flank in upper Volcano Creek, at an elevation of ~160 m (fig. 2, near sites H1, H3, and H4). Sometime between November 2004 and May 2005, a ~400-m-wide, 100-m-deep lake developed in the snow- and ice-filled summit crater of the volcano (Schaefer and others, 2008). In early May 2005, an estimated 3 million cubic meters (3×106 m3) of sulfurous, clay-rich debris and acidic water exited the crater through tunnels at the base of a glacier that breaches the south crater rim. More than 27 km downstream, these acidic flood waters reached approximately 1.3 m above normal water levels and inundated a fertile, salmon-spawning drainage, acidifying the entire water column of Mother Goose Lake from its surface waters to its maximum depth of 45 m (resulting pH ~2.9), and preventing the annual salmon run in the King Salmon River. A simultaneous release of gas and acidic aerosols from the crater caused widespread vegetation damage along the flow path. Since 2005, we have been monitoring the crater lake water that continues to flow into Mother Goose Lake by collecting surface water samples for major cation and anion analysis, measuring surface-water pH of affected drainages, and photo-documenting the condition of the summit crater lake. This report describes water sampling locations, provides a table of chemistry and pH measurements, and documents the condition of the summit crater between 2004 and 2011. In September 2013, the report was updated with results of water-chemistry samples collected in 2011 and 2012, which were added as an addendum.

Hydrology and chemistry of groundwater and seasonal ponds in the Atlantic Coastal Plain in Delaware, USA

USGS Publications Warehouse

Phillips, P.J.; Shedlock, R.J.

1993-01-01

The hydrochemistry of small seasonal ponds was investigated by studying relations between ground-water and surface water in a forested Coastal Plain drainage basin. Observation of changes in the water table in a series of wells equipped with automatic water-level recorders showed that the relation between water-table configuration and basin topography changes seasonally, and particularly in response to spring recharge. Furthermore, in this study area the water table is not a subdued expression of the land surface topography, as is commonly assumed. During the summer and fall months, a water-table trough underlies sandy ridges separating the seasonal ponds, and maximum water-table altitudes prevail in the sediments beneath the dry pond bottoms. As the ponds fill with water during the winter, maximum water-table altitudes shift to the upland-margin zone adjacent to the seasonal ponds. Increases in pond stage are associated with the development of transient water-table mounds at the upland-margin wells during the spring. The importance of small local-flow systems adjacent to the seasonal ponds also is shown by the similarities in the chemistry of the shallow groundwater in the upland margin and water in the seasonal ponds. The upland margin and surface water samples have low pH (generally less than 5.0), and contain large concentrations of dissolved aluminum (generally more than 100 ??g 1-1), and low bicarbonate concentrations (2 mg l4 or less). In contrast, the parts of the surficial aquifer that do not experience transient mounding have higher pH and larger concentrations of bicarbonate. These results suggest that an understanding of the hydrochemistry of seasonally ponded wetlands requires intensive study of the adjacent shallow groundwater-flow system. ?? 1993.

Effect of sewage sludge on formation of acidic ground water at a reclaimed coal mine

USGS Publications Warehouse

Cravotta, C.A.

1998-01-01

Data on rock, ground water, vadose water, and vadose gas chemistry were collected for two years after sewage sludge was applied at a reclaimed surface coal mine in Pennsylvania to determine if surface-applied sludge is an effective barrier to oxygen influx, contributes metals and nutrients to ground water, and promotes the acidification of ground water. Acidity, sulfate, and metals concentrations were elevated in the ground water (6- to 21-m depth) from spoil relative to unmined rock because of active oxidation of pyrite and dissolution of aluminosilicate, carbonate, and Mn-Fe-oxide minerals in the spoil. Concentrations of acidity, sulfate, metals (Fe, Mn, Al, Cd, Cu, Cr, Ni, Zn), and nitrate, and abundances of iron-oxidizing bacteria were elevated in the ground water from sludge-treated spoil relative to untreated spoil having a similar mineral composition; however, gaseous and dissolved oxygen concentrations did not differ between the treatments. Abundances of iron-oxidizing bacteria in the ground water samples were positively correlated with concentrations of ammonia, nitrate, acidity, metals, and sulfate. Concentrations of metals in vadose water samples (<5-m depth) from sludge-treated spoil (pH 5.9) were not elevated relative to untreated spoil (pH 4.4). In contrast, concentrations of nitrate were elevated in vadose water samples from sludge-treated spoil, frequently exceeding 10 mg/L. Downgradient decreases in nitrate to less than 3 mg/L and increases in sulfate concentrations in underlying ground water could result from oxidation of pyrite by nitrate. Thus, sewage sludge added to pyritic spoil can increase the growth of iron-oxidizing bacteria, the oxidation of pyrite, and the acidification of ground water. Nevertheless, the overall effects on ground water chemistry from the sludge were small and probably short-lived relative to the effects from mining only.

Diatom diversity in chronically versus episodically acidified adirondack streams

USGS Publications Warehouse

Passy, S.I.; Ciugulea, I.; Lawrence, G.B.

2006-01-01

The relationship between algal species richness and diversity, and pH is controversial. Furthermore, it is still unknown how episodic stream acidification following atmospheric deposition affects species richness and diversity. Here we analyzed water chemistry and diatom epiphyton dynamics and showed their contrasting behavior in chronically vs. episodically acidic streams in the Adirondack region. Species richness and diversity were significantly higher in the chronically acidic brown water stream, where organic acidity was significantly higher and the ratio of inorganic to organic monomeric aluminum significantly lower. Conversely, in the episodically acidic clear water stream, the inorganic acidity and pH were significantly higher and the diatom communities were very species-poor. This suggests that episodic acidification in the Adirondacks may be more stressful for stream biota than chronic acidity. Strong negative linear relationships between species diversity, Eunotia exigua, and dissolved organic carbon against pH were revealed after the influence of non-linear temporal trends was partialled out using a novel way of temporal modeling. ?? 2006 WILEY-VCH Verlag GmbH & Co. KGaA.

Fallon, Nevada FORGE Fluid Geochemistry

DOE Data Explorer

Blankenship, Doug; Ayling, Bridget

2018-03-13

Fluid geochemistry analysis for wells supporting the Fallon FORGE project. Samples were collected from geothermal wells using standard geothermal water sampling techniques, including filtration and acidification of the cation sample to pH < 2 prior to geochemical analysis. Analyses after 2005 were done in reputable commercial laboratories that follow standard protocols for aqueous chemistry analysis.

Evidence for multiple hydrogen-ion donor systems in rain

Treesearch

Sagar V. Krupa; M. R., Jr. Coscio; F. A. Wood

1976-01-01

An integrated analytical system consisting of combined scanning electron microscopy and x-ray analysis, atomic absorption, colorimetry and coulometry was used to study rain water chemistry. The coulometry facilitated the determination in molarities of strong and non-volatile and volatile weak acids. The pH of individual rains in St. Paul - Minneapolis, Minnesota ranged...

The Effect of Elevated CO2 on the Growth and Food Consumption of Juvenile Winter Flounder Pseudopleuronectes Americanus

EPA Science Inventory

Increasing levels of atmospheric carbon dioxide are causing changes in seawater chemistry in the world’s oceans. In estuarine waters, atmospheric CO2 exacerbates already declining pH due to high productivity and respiration caused by cultural eutrophication. These two sources o...

Graduate Education in Chemistry. The ACS Committee on Professional Training: Surveys of Programs and Participants.

ERIC Educational Resources Information Center

American Chemical Society, Washington, DC.

This document reports on graduate education in chemistry concerning the nature of graduate programs. Contents include: (1) "Graduate Education in Chemistry in the United States: A Snapshot from the Late Twentieth Century"; (2) "A Survey of Ph.D. Programs in Chemistry"; (4) "The Master's Degree in Chemistry"; (5) "A Survey of Ph.D. Recipients in…

Peatland Open-water Pool Biogeochemistry: The Influence of Hydrology and Vegetation

NASA Astrophysics Data System (ADS)

Arsenault, J.; Talbot, J.; Moore, T. R.

2017-12-01

Peatland open-water pools are net sources of carbon to the atmosphere. However, their interaction with the surrounding peat remains poorly known. In a previous study, we showed that shallow pools are richer in nutrients than deep pools. While depth was the main driver of biogeochemistry variations across time and space, analyses also showed that pool's adjacent vegetation may have an influence on water chemistry. Our goal is to understand the relationship between the biogeochemistry of open-water pools and their surroundings in a subboreal ombrotrophic peatland of southern Quebec (Canada). To assess the influence of vegetation on pool water chemistry, we compare two areas covered with different types of vegetation: a forested zone dominated by spruce trees and an open area mostly covered by Sphagnum spp. To evaluate the direction of water (in or out of the pools), we installed capacitance water level probes in transects linking pools in the two zones. Wells were also installed next to each probe to collect peat pore water samples. Samples were taken every month during summer 2017 and analyzed for dissolved organic carbon, nitrogen and phosphorus, pH and specific UV absorbance. Preliminary results show differences in peat water chemistry depending on the dominant vegetation. In both zones, water levels fluctuations are disconnected between peat and the pools, suggesting poor horizontal water movement. Pool water chemistry may be mostly influenced by the immediate surrounding vegetation than by the local vegetation pattern. Climate and land-use change may affect the vegetation structure of peatlands, thus affecting pool biogeochemistry. Considering the impact of pools on the overall peatland capacity to accumulate carbon, our results show that more focus must be placed on pools to better understand peatland stability over time.

Dynamic coupled metal transport-speciation model: application to assess a zinc-contaminated lake.

PubMed

Bhavsar, Satyendra P; Diamond, Miriam L; Gandhi, Nilima; Nilsen, Joel

2004-10-01

A coupled metal transport and speciation/complexation model (TRANSPEC) has been developed to estimate the speciation and fate of multiple interconverting species in surface aquatic systems. Dynamic-TRANSPEC loosely, sequentially couples the speciation/complexation and fate modules that, for the unsteady state formulation, run alternatively at every time step. The speciation module first estimates species abundance using, in this version, MINEQL+ considering time-dependent changes in water and pore-water chemistry. The fate module is based on the quantitative water air sediment interaction (QWASI) model and fugacity/aquivalence formulation, with the option of using a pseudo-steady state solution to account for past discharges. Similarly to the QWASI model for organic contaminants, TRANSPEC assumes the instantaneous equilibrium distribution of metal species among dissolved, colloidal, and particulate phases based on ambient chemistry parameters that can be collected through conventional field methods. The model is illustrated with its application to Ross Lake (Manitoba, Canada) that has elevated Zn concentrations due to discharges over 70 years from a mining operation. Using measurements from field studies, the model reproduces year-round variations in Zn water concentrations. A 10-year projection for current conditions suggests decreasing Zn remobilization and export from the lake. Decreasing Zn loadings increases sediment-to-water transport but decreases water concentrations, and vice versa. Species distribution is affected by pH such that a decrease in pH increases metal export from the lake and vice versa.

The effect of dissolution of volcanic glass on the water chemistry in a tuffaceous aquifer, Rainier Mesa, Nevada

USGS Publications Warehouse

White, Art F.; Claassen, H.C.; Benson, Larry V.

1980-01-01

Geochemistry of ground water associated with the Tertiary tuffs within Rainier Mesa, southern Nevada, was investigated to determine the relative importance of glass dissolution in controlling water chemistry. Water samples were obtained both from interstitial pores in core sections and from free-flowing fractures. Cation com- positions showed that calcium and magnesium decreased as a function of depth in the mesa, as sodium increased. The maximum effect occurs within alteration zones containing clinoptilolite and montmorillonite, suggesting these minerals effectively remove bivalent cations from the system. Comparisons are made between compositions of ground waters found within Rainier Mesa that apparently have not reacted with secondary minerals and compositions of waters produced by experimental dissolution of vitric and crystalline tufts which comprise the principal aquifers in the area. The two tuff phases have the same bulk chemistry but produce aqueous solutions of different chemistry. Rapid parabolic dissolution of sodium and silica from, and the retention of, potassium within the vitric phase verify previous predictions concerning water compositions associated with vitric volcanic rocks. Parabolic dissolution of the crystalline phase results in solutions high in calcium and magnesium and low in silica. Extrapolation of the parabolic dissolution mechanism for the vitric tuff to long times successfully reproduces, at com- parable pH, cation ratios existing in Rainier Mesa ground water. Comparison of mass- transfer rates of the vitric and crystalline tuffs indicates that the apparent higher glass-surface to aqueous-volume ratio associated with the vitric rocks may account for dominance of the glass reaction.

Education: Chemistry Faculties Gain Women Slowly.

ERIC Educational Resources Information Center

Chemical and Engineering News, 1984

1984-01-01

Highlights survey results on the status of females in full-time, tenured or tenure track faculty positions in chemistry. Indicates that males still dominate PhD-granting chemistry faculties and that, although the number of women is increasing, the increase is not proportionate to the rate at which they are earning chemistry PhDs. (JM)

Factors affecting water quality and net flux of solutes in two stream basins in the Quabbin Reservoir drainage basin, central Massachusetts,1983-85

USGS Publications Warehouse

Rittmaster, R.L.; Shanley, J.B.

1995-01-01

The factors that affect stream-water quality were studied at West Branch Swift River (Swift River), and East Branch Fever Brook (Fever Brook), two forested watersheds that drain into the Quabbin Reservoir, central Massachusetts, from December 1983 through August 1985. Spatial and temporal variations of chemistry of precipitation, surface water; and ground water and the linkages between chemical changes and hydrologic processes were used to identify the mechanisms that control stream chemistry. Precipitation chemistry was dominated by hydrogen ion (composite p.H 4.23), sulfate, and nitrate. Inputs of hydrogen and nitrate from pre- cipitation were almost entirely retained in the basins, whereas input of sulfate was approximately balanced by export by streamflow draining the basins. Both streams were poorly buffered, with mean pH near 5.7, mean alkalinity less than 30 microequivalents per liter, and sulfate concen- trations greater than 130 microequivalents per liter. Sodium and chloride, derived primarily from highway deicing salts, were the dominant solutes at Fever Brook. After adjustments for deicing salts, fluxes of base cations during the 21-month study were 2,014 and 1,429 equivalents per hectare in Swift River and Fever Brook, respectively. Base cation fluxes were controlled primarily by weathering of hornblende (Fever Brook) and plagioclase (Swift River). The overall weathering rate was greater in the Swift River Basin because easily weathered gabbro underlies one subbasin which comprises 11.2 percent of the total basin area but contributed about 77 percent of the total alkalinity. Alkalinity export was nearly equal in the two basins, however, because some alkalinity was generated in wetlands in the Fever Brook Basin through bacterial sulfate reduction coupled with organic-carbon oxidation.

Production and carbonate dynamics of Halimeda incrassata (Ellis) Lamouroux altered by Thalassia testudinum Banks and Soland ex König

NASA Astrophysics Data System (ADS)

Barry, S.; Frazer, T.; Jacoby, C.

2013-05-01

Ocean acidification poses a serious threat to a broad suite of calcifying organisms. Scleractinian corals and calcareous algae that occupy shallow, tropical waters are vulnerable to global changes in ocean chemistry because they already are subject to stressful and variable carbon dynamics at the local scale. For example, net heterotrophy increases carbon dioxide concentrations, and pH varies with diurnal fluctuations in photosynthesis and respiration. Few researchers, however, have investigated the possibility that carbon dioxide consumption during photosynthesis by non-calcifying photoautotrophs, such as seagrasses, can ameliorate deleterious effects of ocean acidification on sympatric calcareous algae. Naturally occurring variations in the density of seagrasses and associated calcareous algae provide an ecologically relevant test of the hypothesis that diel fluctuations in water chemistry driven by cycles of photosynthesis and respiration within seagrass beds create microenvironments that enhance macroalgal calcification. In Grape Tree Bay off Little Cayman Island BWI, we quantified net production and characterized calcification for thalli of the calcareous green alga Halimeda incrassata growing within beds of Thalassia testudinum with varying shoot densities. Results indicated that individual H. incrassata thalli were ~6% more calcified in dense seagrass beds. On an areal basis, however, far more calcium carbonate was produced by H. incrassata in areas where seagrasses were less dense due to higher rates of production. In addition, diel pH regimes in vegetated and unvegetated areas within the lagoon were not significantly different, suggesting water exchange and mixing throughout the lagoon. These results suggest that, especially in well-mixed lagoons, carbonate production by calcareous algae may be more related to biotic interactions between seagrasses and calcareous algae than to seagrass-mediated changes in local water chemistry.

Optimizing buffering chemistry to maintain near neutral pH of broiler feed during pre-enrichment for Salmonella.

PubMed

Berrang, M E; Cosby, D E; Cox, N A; Cason, J A; Richardson, K E

2015-12-01

Salmonella is a human pathogen that can accompany live broilers to the slaughter plant, contaminating fully processed carcasses. Feed is one potential source of Salmonella to growing broilers. Monitoring feed for the presence of Salmonella is part of good agricultural practice. The first step in culturing feed for Salmonella (which may be at low numbers and sub-lethally stressed) is to add it to a pre-enrichment broth which is incubated for 24 h. During the course of pre-enrichment, extraneous bacteria metabolize carbohydrates in some feed and excrete acidic byproducts, causing the pH to drop dramatically. An acidic pre-enrichment pH can injure or kill Salmonella resulting in a failure to detect, even if it is present and available to infect chickens. The objective of this study was to test an array of buffering chemistries to prevent formation of an injurious acidic environment during pre-enrichment of feed in peptone water. Five grams of feed were added to 45 mL of peptone water buffered with carbonate, Tris pH 8, and phosphate buffering ingredients individually and in combination. Feed was subjected to a pre-enrichment at 35°C for 24 h; pH was measured at 0, 18, and 24 h. Standard phosphate buffering ingredients at concentrations up to 4 times the normal formulation were unable to fully prevent acidic conditions. Likewise, carbonate and Tris pH 8 were not fully effective. The combination of phosphate, carbonate, and Tris pH 8 was the most effective buffer tested. It is recommended that a highly buffered pre-enrichment broth be used to examine feed for the presence of Salmonella. Published by Oxford University Press on behalf of Poultry Science Association 2015. This work is written by (a) US Government employee(s) and is in the public domain in the US.

Autogenous Metallic Pipe Leak Repair in Potable Water Systems.

PubMed

Tang, Min; Triantafyllidou, Simoni; Edwards, Marc A

2015-07-21

Copper and iron pipes have a remarkable capability for autogenous repair (self-repair) of leaks in potable water systems. Field studies revealed exemplars that metallic pipe leaks caused by nails, rocks, and erosion corrosion autogenously repaired, as confirmed in the laboratory experiments. This work demonstrated that 100% (N = 26) of 150 μm leaks contacting representative bulk potable water in copper pipes sealed autogenously via formation of corrosion precipitates at 20-40 psi, pH 3.0-11.0, and with upward and downward leak orientations. Similar leaks in carbon steel pipes at 20 psi self-repaired at pH 5.5 and 8.5, but two leaks did not self-repair permanently at pH 11.0 suggesting that water chemistry may control the durability of materials that seal the leaks and therefore the permanence of repair. Larger 400 μm holes in copper pipes had much lower (0-33%) success of self-repair at pH 3.0-11.0, whereas all 400 μm holes in carbon steel pipes at 20 psi self-repaired at pH 4.0-11.0. Pressure tests indicated that some of the repairs created at 20-40 psi ambient pressure could withstand more than 100 psi without failure. Autogenous repair has implications for understanding patterns of pipe failures, extending the lifetime of decaying infrastructure, and developing new plumbing materials.

Rock-Bound Arsenic Influences Ground Water and Sediment Chemistry Throughout New England

USGS Publications Warehouse

Robinson, Gilpin R.; Ayotte, Joseph D.

2007-01-01

The information in this report was presented at the Northeastern Region Geological Society of America meeting held March 11-14, 2007, in Durham, New Hampshire. In the New England crystalline bedrock aquifer, concentrations of arsenic that exceed the drinking water standard of 10 ?g/L occur most frequently in ground water from wells sited in specific metamorphic and igneous rock units. Geochemical investigations indicate that these geologic units typically have moderately elevated whole-rock concentrations of arsenic compared to other rocks in the region. The distribution of ground water wells with As > 5 ?g/L has a strong spatial correlation with specific bedrock units where average whole-rock concentrations of arsenic exceed 1.1 mg/kg and where geologic and geochemical factors produce high pH ground water. Arsenic concentrations in stream sediments collected from small drainages reflect the regional distribution of this natural arsenic source and have a strong correlation with both rock chemistry and the distribution of bedrock units with elevated arsenic chemistry. The distribution of ground water wells with As > 5 ?g/L has a strong spatial correlation with the distribution of stream sediments where concentrations of arsenic exceed 6 mg/kg. Stream sediment chemistry also has a weak correlation with the distribution of agricultural lands where arsenical pesticides were used on apple, blueberry, and potato crops. Elevated arsenic concentrations in bedrock wells, however, do not correlate with agricultural areas where arsenical pesticides were used. These results indicate that both stream sediment chemistry and the solubility and mobility of arsenic in ground water in bedrock are influenced by host-rock arsenic concentrations. Stream sediment chemistry and the distribution of geologic units have been found to be useful parameters to predict the areas of greatest concern for elevated arsenic in ground water and to estimate the likely levels of human exposure to elevated arsenic in drinking water in New England. However, the extreme local variability of arsenic concentrations in ground water from these rock sources indicate that arsenic concentrations in ground water are affected by other factors in addition to arsenic concentrations in rock.

An evaluation of the effects of acid rain on low conductivity headwater streams in Pennsylvania

USGS Publications Warehouse

Ritter, John R.; Brown, Ann E.

1981-01-01

Analyses of water collected at 32 sites on headwater streams in Pennsylvania during low-flow conditions in 1970-80 were compared to pre-1971 data to evaluate whether acid rain had changed the chemistry of the streams in the previous decade. Most pH, alkalinity, and sulfate values of the samples collected in 1970-80 fell within the ranges of values for samples collected before 1971. The limited data indicate, however, that pH may have increased and alkalinity and sulfate may have decreased with time.

Surfactant-enhanced alkaline flooding: Buffering at intermediate alkaline pH

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

Rudin, J.; Wasan, D.T.

1993-11-01

The alkaline flooding process involves injecting alkaline agents into the reservoir to produce more oil than is produced through conventional waterflooding. The interaction of the alkali in the flood water with the naturally occurring acids in the reservoir oil results in in-situ formation of soaps, which are partially responsible for lowering IFT and improving oil recovery. The extent to which IFT is lowered depends on the specific oil and injection water properties. Numerous investigators have attempted to clarify the relationship between system chemical composition and IFT. An experimental investigation of buffered alkaline flooding system chemistry was undertaken to determine themore » influence of various species present on interfacial tension (IFT) as a function of pH and ionic strength. IFT was found to go through an ultralow minimum in certain pH ranges. This synergism results from simultaneous adsorption of un-ionized and ionized acid species on the interface.« less

Relationships between acid deposition, watershed characteristics, and stream chemistry in Maryland's coastal plain. Final report. Volume 1. Text. Report for May 1984-June 1985

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

Campbell, S.; Bartoshesky, J.; Heimbuch, D.

1987-06-01

Precipitation and stream-water chemistry data were collected from three watersheds in the Coastal Plain region of Maryland during the period May 1984 through June 1985 in an attempt to determine the potential effects of acidic deposition on the chemistry of these streams. The study streams included Lyons Creek, Morgan Creek, and Granny Finley Branch; these streams were chosen based on their differential responses to storm events observed in a survey of Coastal Plain streams in the spring of 1983. Lyons Creek typically exhibited lower pH, acid-neutralizing capacity, and concentrations of base cations than observed in the other streams. Sulfate massmore » balances suggest that the soils in the Lyons Creek watershed also have less affinity for sulfur retention than do soils of the other watersheds. Acidic pulses were observed in all three streams during the spring months; however, the magnitude of these pulses was less than that observed in 1983. Modeling of the relationships between precipitation chemistry, watershed interactions, and stream chemistry suggests that precipitation acidity can influence stream-water acidity, depending upon hydrological conditions and availabiility of acid-neutralizing materials in the watersheds.« less

Macroinvertebrate abundance, water chemistry, and wetland characteristics affect use of wetlands by avian species in Maine

USGS Publications Warehouse

Longcore, J.R.; McAuley, D.G.; Pendelton, G.W.; Bennatti, C.R.; Mingo, T.M.; Stromborg, K.L.

2006-01-01

Our objective was to determine use by avian species (e.g., piscivores, marsh birds, waterfowl, selected passerines) of 29 wetlands in areas with low (<200 μeq l−1) acid-neutralizing capacity (ANC) in southeastern Maine. We documented bird, pair, and brood use during 1982–1984 and in 1982 we sampled 10 wetlands with a sweep net to collect invertebrates. We related mean numbers of invertebrates per wetland to water chemistry, basin characteristics, and avian use of different wetland types. Shallow, beaver (Castor canadensis)-created wetlands with the highest phosphorus levels and abundant and varied macrophyte assemblages supported greater densities of macroinvertebrates and numbers of duck broods (88.3% of all broods) in contrast to deep, glacial type wetlands with sparse vegetation and lower invertebrate densities that supported fewer broods (11.7%). Low pH may have affected some acid-intolerant invertebrate taxa (i.e., Ephemeroptera), but high mean numbers of Insecta per wetland were recorded from wetlands with a pH of 5.51. Other Classes and Orders of invertebrates were more abundant on wetlands with pH > 5.51. All years combined use of wetlands by broods was greater on wetlands with pH ≤ 5.51 (77.4%) in contract to wetlands with pH > 5.51 that supported 21.8% of the broods. High mean brood density was associated with mean number of Insecta per wetland. For lentic wetlands created by beaver, those habitats contained vegetative structure and nutrients necessary to provide cover to support invertebrate populations that are prey of omnivore and insectivore species. The fishless status of a few wetlands may have affected use by some waterfowl species and obligate piscivores.

Influence of pH on Drug Absorption from the Gastrointestinal Tract: A Simple Chemical Model

NASA Astrophysics Data System (ADS)

Hickman, Raymond J. S.; Neill, Jane

1997-07-01

A simple model of the gastrointestinal tract is obtained by placing ethyl acetate in contact with water at pH 2 and pH 8 in separate test tubes. The ethyl acetate corresponds to the lipid material lining the tract while the water corresponds to the aqueous contents of the stomach (pH 2) and intestine (pH 8). The compounds aspirin, paracetamol and 3-aminophenol are used as exemplars of acidic, neutral and basic drugs respectively to illustrate the influence which pH has on the distribution of each class of drug between the aqueous and organic phases of the model. The relative concentration of drug in the ethyl acetate is judged by applying microlitre-sized samples of ethyl acetate to a layer of fluorescent silica which, after evaporation of the ethyl acetate, is viewed under an ultraviolet lamp. Each of the three drugs, if present in the ethyl acetate, becomes visible as a dark spot on the silica layer. The observations made in the model system correspond well to the patterns of drug absorption from the gastrointestinal tract described in pharmacology texts and these observations are convincingly explained in terms of simple acid-base chemistry.

Inverse Modeling of Water-Rock-CO2 Batch Experiments: Potential Impacts on Groundwater Resources at Carbon Sequestration Sites.

PubMed

Yang, Changbing; Dai, Zhenxue; Romanak, Katherine D; Hovorka, Susan D; Treviño, Ramón H

2014-01-01

This study developed a multicomponent geochemical model to interpret responses of water chemistry to introduction of CO2 into six water-rock batches with sedimentary samples collected from representative potable aquifers in the Gulf Coast area. The model simulated CO2 dissolution in groundwater, aqueous complexation, mineral reactions (dissolution/precipitation), and surface complexation on clay mineral surfaces. An inverse method was used to estimate mineral surface area, the key parameter for describing kinetic mineral reactions. Modeling results suggested that reductions in groundwater pH were more significant in the carbonate-poor aquifers than in the carbonate-rich aquifers, resulting in potential groundwater acidification. Modeled concentrations of major ions showed overall increasing trends, depending on mineralogy of the sediments, especially carbonate content. The geochemical model confirmed that mobilization of trace metals was caused likely by mineral dissolution and surface complexation on clay mineral surfaces. Although dissolved inorganic carbon and pH may be used as indicative parameters in potable aquifers, selection of geochemical parameters for CO2 leakage detection is site-specific and a stepwise procedure may be followed. A combined study of the geochemical models with the laboratory batch experiments improves our understanding of the mechanisms that dominate responses of water chemistry to CO2 leakage and also provides a frame of reference for designing monitoring strategy in potable aquifers.

The behaviour of REE and Zr-Hf fractionation in the volcanic waters of Nevado del Ruiz system (Colombia)

NASA Astrophysics Data System (ADS)

Inguaggiato, Claudio; Censi, Paolo; Zuddas, Pierpaolo; Makario Londoño, John; Chacón, Zoraida; Alzate, Diego; Brusca, Lorenzo; D'Alessandro, Walter

2015-04-01

The geochemical behaviour of Rare Earth Element (REE), Zr and Hf have been investigated in the thermal waters of Nevado del Ruiz volcanic system. These fluids are characterised by a wide range of pH ranging between 1.0 and 8.8. The acidic waters are sulphate dominated with different Cl/SO4 ratios. The Nevado del Ruiz waters allowed to investigate the behaviour of investigated elements in a wide spectrum of pH and chemical composition of water. The important role of the pH and the ionic complexes have been evidenced in the distribution of REE, Zr and Hf in the aqueous phase. The pH rules the precipitation of authigenic oxyhydroxides of Fe, Al producing changes in REE, Zr, Hf amount and strong anomalies of Cerium and Europium. Y-Ho and Zr-Hf (twin pairs) have different behaviour in strong acidic waters with respect to the water with higher pH. Yttrium and Ho have the same behaviour of Zr and Hf in waters with pH near neutral-to-neutral, showing super-chondritic ratios. The twin pairs showed to be sensitive to the co-precipitation and/or adsorption onto the surface of authigenic particulate suggesting an enhanced scavenging of Ho and Hf respect to Y and Zr, leading to super-chondritic ratios. In acidic waters a different behaviour of twin pairs occurs with chondritic Y/Ho ratios (reflecting the Y/Ho ratio of average local rock) and sub-chondritic Zr/Hf ratios. For the first time, Zr and Hf have been investigated in natural acidic fluids to understand the behaviour of these elements in extreme acidic conditions and different major anions chemistry. Zr/Hf molar ratio changes from 4.75 to 49.29 in water with pH<3.6. In strong acidic waters, a different fractionation of Zr and Hf have been recognised as function of major anion contents (Cl and SO4), suggesting the formation of complexes leading to sub-chondritic Zr/Hf molar ratios.

Aggregation of asbestos fibers in water: role of solution chemistry

NASA Astrophysics Data System (ADS)

Wu, L.; Ortiz, C. P.; Jerolmack, D. J.

2016-12-01

Aggregation kinetics and stability of colloidal particles have been extensively studied using bulk techniques such as dynamic light scattering; these techniques involve large ensembles of particles and interpretation of results is difficult when particles are non-spherical and poorly characterized, as is always the case with non-ideal natural hazardous materials such as asbestos fibers. These difficulties hinder greatly progress on fundamental understanding of whether the classic colloidal aggregation theories can be applied to natural materials and how the heterogeneity of particles (e.g., shape) affects the colloidal aggregation kinetics and structure. By using in-situ microscopy and particle tracking techniques, we were able to observe the particle-by-particle growth of aggregated formed by elongated particles (synthetic glass rods and natural asbestos fibers) and demonstrated the rod-shaped geometry induced novel structures and growth dynamics that challenge existing theory. In this study, we continue to use asbestos as model system of elongated colloidal contaminant, and investigate the effects of changing solution chemistry (e.g., ionic strength, pH, and natural organic matter (NOM)), on growth dynamics and aggregates structure. The results show that aggregate growth curves are self-similar with a characteristic timescale that increases with increasing pH. By varying ionic strength for fixed pH values, we determine that the ccc is sensitive to pH. Fractal dimension decreases slightly with increasing pH and decreasing ionic strength, indicating that stronger inter-particle repulsion create sparser aggregates; however, the magnitude of the solution chemistry effects is much smaller than that of colloid shape. In monovalent solutions, regardless of their concentration, HA drastically reduces the aggregation kinetics of asbestos fiber. This work may lead to enhanced prediction of the colloidal contaminants' mobility in the environment, bioavailability, and toxicity to organisms.

Calcium nephrolithiasis: effect of water hardness on urinary electrolytes.

PubMed

Schwartz, Bradley F; Schenkman, Noah S; Bruce, Jeremy E; Leslie, Stephen W; Stoller, Marshall L

2002-07-01

To analyze the impact of water hardness from public water supplies on calcium stone incidence and 24-hour urine chemistries in patients with known calcium urinary stone formation. Patients are frequently concerned that their public water supply may contribute to urinary stone disease. Investigators have documented an inverse relationship between water hardness and calcium lithogenesis. Others have found no such association. Patients who form calcium stones (n = 4833) were identified geographically by their zip code. Water hardness information from distinct geographic public water supplies was obtained, and patient 24-hour urine chemistries were evaluated. Drinking water hardness was divided into decile rankings on the basis of the public water supply information obtained from the Environmental Protection Agency. These data were compared with patient questionnaires and 24-hour urine chemistries. The calcium and magnesium levels in the drinking water were analyzed as independent variables. The number of total lifetime stone episodes was similar between patients residing in areas with soft public water and hard public water. Patients consuming the softest water decile formed 3.4 lifetime stones and those who consumed the hardest water developed 3.0 lifetime stones (P = 0.0017). The 24-hour urine calcium, magnesium, and citrate levels increased directly with drinking water hardness, and no significant change was found in urinary oxalate, uric acid, pH, or volume. The impact of water hardness on urinary stone formation remains unclear, despite a weak correlation between water hardness and urinary calcium, magnesium, and citrate excretion. Tap water, however, can change urinary electrolytes in patients who form calcium stones.

Influence of Collector Surface Composition and Water Chemistry on the Deposition of Cerium Dioxide Nanoparticles: QCM-D and Column Experiment Approaches

EPA Science Inventory

The deposition behavior of cerium dioxide (CeO2) nanoparticles (NPs) in dilute NaCl solutions was investigated as a function of collector surface composition, pH, ionic strength, and organic matter (OM). Sensors coated separately with silica, iron oxide, and alumina were applied ...

The Feasibility of Using Hydrogen Peroxide Decomposition Studies for High School Chemistry.

ERIC Educational Resources Information Center

Carter, Gillian E.

1986-01-01

Highlights difficulties that occur when teachers attempt to devise new experiments (use of hydrogen peroxide decomposition) and how seemingly useless results can be turned into productive student projects. Considers effects of ions present in tap water, pH, dust, and nature of vessel's surface. Reaction order and safety precautions are noted. (JN)

Chemistry of Sulfur-Contaminated Soil Substrate from a Former Frasch Extraction Method Sulfur Mine Leachate with Various Forms of Litter in a Controlled Experiment.

PubMed

Likus-Cieślik, Justyna; Pietrzykowski, Marcin; Chodak, Marcin

2018-01-01

The impact of tree litter on soil chemistry leachate and sulfurous substrates of mine soils from former Jeziórko sulfur mine was investigated. Composites were used: soil substrate (less contaminated at mean 5090 mg kg -1  S or high contaminated at 42,500 mg kg -1  S) + birch or pine litter and control substrate (no litter). The composites were rinsed with distilled water over 12 weeks. In the obtained leachate, pH, EC, dissolved organic carbon, N, Ca, Mg, Al, and S were determined. Physicochemical parameters of the substrates and their basal respiration rate were determined. Rinsing and litter application lowered sulfur concentration in high contamination substrates. Pine litter application decreased EC and increased pH of the low-contaminated substrate. The substrate pH remained at low phytotoxic level (i.e., below 3.0), resulting in the low biological activity of the composites. Birch litter application increased leaching of N and Mg, indicating the possibility of an intensification of soil-forming processes in contaminated sites.

Impact of Water Chemistry, Pipe Material and Stagnation on the Building Plumbing Microbiome.

PubMed

Ji, Pan; Parks, Jeffrey; Edwards, Marc A; Pruden, Amy

2015-01-01

A unique microbiome establishes in the portion of the potable water distribution system within homes and other buildings (i.e., building plumbing). To examine its composition and the factors that shape it, standardized cold water plumbing rigs were deployed at the treatment plant and in the distribution system of five water utilities across the U.S. Three pipe materials (copper with lead solder, CPVC with brass fittings or copper/lead combined pipe) were compared, with 8 hour flush cycles of 10 minutes to simulate typical daily use patterns. High throughput Illumina sequencing of 16S rRNA gene amplicons was employed to profile and compare the resident bulk water bacteria and archaea. The utility, location of the pipe rig, pipe material and stagnation all had a significant influence on the plumbing microbiome composition, but the utility source water and treatment practices were dominant factors. Examination of 21 water chemistry parameters suggested that the total chlorine concentration, pH, P, SO42- and Mg were associated with the most of the variation in bulk water microbiome composition. Disinfectant type exerted a notably low-magnitude impact on microbiome composition. At two utilities using the same source water, slight differences in treatment approaches were associated with differences in rare taxa in samples. For genera containing opportunistic pathogens, Utility C samples (highest pH of 9-10) had the highest frequency of detection for Legionella spp. and lowest relative abundance of Mycobacterium spp. Data were examined across utilities to identify a true universal core, special core, and peripheral organisms to deepen insight into the physical and chemical factors that shape the building plumbing microbiome.

Impact of Water Chemistry, Pipe Material and Stagnation on the Building Plumbing Microbiome

PubMed Central

Ji, Pan; Parks, Jeffrey; Edwards, Marc A.; Pruden, Amy

2015-01-01

A unique microbiome establishes in the portion of the potable water distribution system within homes and other buildings (i.e., building plumbing). To examine its composition and the factors that shape it, standardized cold water plumbing rigs were deployed at the treatment plant and in the distribution system of five water utilities across the U.S. Three pipe materials (copper with lead solder, CPVC with brass fittings or copper/lead combined pipe) were compared, with 8 hour flush cycles of 10 minutes to simulate typical daily use patterns. High throughput Illumina sequencing of 16S rRNA gene amplicons was employed to profile and compare the resident bulk water bacteria and archaea. The utility, location of the pipe rig, pipe material and stagnation all had a significant influence on the plumbing microbiome composition, but the utility source water and treatment practices were dominant factors. Examination of 21 water chemistry parameters suggested that the total chlorine concentration, pH, P, SO4 2- and Mg were associated with the most of the variation in bulk water microbiome composition. Disinfectant type exerted a notably low-magnitude impact on microbiome composition. At two utilities using the same source water, slight differences in treatment approaches were associated with differences in rare taxa in samples. For genera containing opportunistic pathogens, Utility C samples (highest pH of 9–10) had the highest frequency of detection for Legionella spp. and lowest relative abundance of Mycobacterium spp. Data were examined across utilities to identify a true universal core, special core, and peripheral organisms to deepen insight into the physical and chemical factors that shape the building plumbing microbiome. PMID:26495985

Causes of acidification of four streams on Laurel Hilld in southwestern Pennsylvania

USGS Publications Warehouse

Sharpe, William E.; DeWalle, David R.; Leibfried, Robert T.; Dinicola, Richard S.; Kimmel, William G.; Sherwin, Lysle S.

1984-01-01

Atmospheric deposition, soils developed from bedrock, a natural bog, gas wells, and a ski area were all investigated as possible sources of water quality degradation for four streams on Laurel Hill in southwestern Pennsylvania where fish kills have been reported since 1960. An intensive study of the chemistry of atmospheric deposition, soil leachate, and stream water and fish populations was conducted on these basins during 1980–1981 with emphasis on dormant season periods with runoff from snowmelt and rain. Although bedrock geology was found to control the natural buffering capacity of these streams, only acid precipitation could be linked to sharp drops in pH and increases in total Al concentrations observed during stormflows in the poorly buffered streams. Three poorly buffered streams exhibited drops to pH 4.4 to 4.5 and increases in total Al concentrations up to 1.5 mg/L during observed peak flows. Mineral soil leachate from the three major soil series on the basins during this time exhibited a low pH of 4.3 and mean total Al concentrations of 3.6 mg/L, indicating stream response during storms was closely linked to chemistry of soil leachate. Poorly buffered streams did not support reproducing populations of trout (Salmonidae sp.) or other fishes. In contrast, one well-buffered stream (20 mg/L CaCO3) exhibited drops to pH 5.5 during peak flow and supported reproducing trout and sculpin (Cottus bairdi) populations. The acidification of the four streams studied was attributed to atmospheric deposition.

Environmental Fate and Transport of a New Energetic Material, CL-20

DTIC Science & Technology

2006-03-01

Microbiology M.Sc. Biochemistry M.Sc. Chemistry Ph.D. Chemistry Ph.D. Ecotoxicology M.Sc.A. Environmental Engineering B.Sc. Chemistry B.Sc...Determine enzymes responsible for initiating the degradation of CL-20. 5. Conduct a battery of ecotoxicological tests to determine the toxic effects of...chrysosporium. The strain ATCC 24725 was maintained on Yeast Peptone Dextrose (YPD) plates and was cultivated in the modified Kirk’s nitrogen- limited medium (pH

Improvement of chemical monitoring of water-chemistry conditions at thermal power stations based on electric conductivity and pH measurements

NASA Astrophysics Data System (ADS)

Larin, A. B.; Larin, B. M.

2016-05-01

The increased requirements to the quality of the water heat conductor for working superhigh (SHP) and supercritical (SCP) pressure power plants and promising units, including combined-cycle gas turbine (CCGT) units and power plants with ultrasupercritical parameters (USCPs), can largely be satisfied through specific electric conductivity and pH measurements for cooled heat conductor samples combined with calculations of ionic equilibria and indirect measurements of several specified and diagnostic parameters. The possibility of calculating the ammonia and chloride concentrations and the total concentration of hardness and sodium cations in the feed water of drum-type boilers and the phosphate and salt contents in boiler water was demonstrated. An equation for evaluating the content of potentially acid substances in the feed water of monotube boilers was suggested. The potential of the developed procedure for evaluating the state of waterchemistry conditions (WCCs) in power plants with CCGT units was shown.

Dissolution and time-dependent compaction of albite sand: experiments at 100°C and 160°C in pH-buffered organic acids and distilled water

NASA Astrophysics Data System (ADS)

Hajash, Andrew; Carpenter, Thomas D.; Dewers, Thomas A.

1998-09-01

Aqueous fluids are important in the diagenesis and deformation of crustal rocks. Both chemical and physical interactions are involved and often they are strongly coupled. For example, pore waters not only dissolve, transport, and precipitate chemical species, but they also substantially affect the mechanical behavior of the rocks that contain them. Stresses magnified at grain contacts by differences in pore-fluid pressure ( Pp) and confining pressure ( Pc) can, in turn, influence the rate and extent of chemical exchange. To begin investigation of these coupled systems, compaction experiments were conducted using albite sand (250-500 μm) and distilled water (pH 5.8), 0.07 M acetate (pH 4.7), and 0.07 M acetate + 0.005 M citrate (pH 4.4) solutions in a hydrothermal flow-through system at conditions that simulate diagenesis. Pore-fluid chemistry and pore-volume loss were monitored to quantify the effects of organic acids on time-dependent compaction rates. The effects of stress and fluid chemistry on the dissolution kinetics were also examined. Albite dissolution rates, monitored by steady-state fluid chemistry, increased when an effective pressure ( Pe= Pc- Pp) was applied, probably due to increases in total surface area caused by grain breakage at contacts. These effects were transient in distilled water, however, Si and Al concentrations remained elevated in the acetate pore fluid. The average Si-based release rates indicate ≈35% increase in reactive surface area by application of Pe=34.5 MPa. At 100°C with Pe=34.5 MPa, steady-state Si concentrations were ≈2.3 times higher in 0.07 M acetate and 5.8 times higher in 0.07 M acetate + 0.005 M citrate than in distilled water. Al increased by even larger factors (3× in the acetate buffer and 10× in the citrate solution). These changes in fluid chemistry are attributed to both pH and ligand-enhanced reactions. Albite dissolution appears to be controlled by surface complexation reactions at Al sites. Rapid dissolution of albite in the organic acid solutions is probably due to the ability of organic acid ligands to selectively complex with aluminum. Time-dependent compaction was observed at 100 and 160°C with Pe=34.5 MPa. Strain rates increased with temperature from ≈10 -9 s -l at 100°C to ≈10 -8 s -l at 160°C and decreased with strain in all pore fluids, especially at 100°C. Compaction rates in distilled water and in the acetate solution had similar magnitudes and strain dependencies; however, small amounts of citrate species apparently enhance compaction compared to the other fluids at similar strains. Textural data indicate that time-dependent compaction of the albite sand occurred primarily by brittle mechanisms at these temperatures. However, the deformation is clearly thermally activated and may be chemically assisted by the aqueous pore fluid.

Phoenix's Wet Chemistry Lab

NASA Technical Reports Server (NTRS)

2008-01-01

This is an illustration of the analytical procedure of NASA's Phoenix Mars Lander's Wet Chemistry Lab (WCL) on board the Microscopy, Electrochemistry, and Conductivity Analyzer (MECA) instrument. By dissolving small amounts of soil in water, WCL can determine the pH, the abundance of minerals such as magnesium and sodium cations or chloride, bromide and sulfate anions, as well as the conductivity and redox potential.

The Phoenix Mission is led by the University of Arizona, Tucson, on behalf of NASA. Project management of the mission is by NASA's Jet Propulsion Laboratory, Pasadena, Calif. Spacecraft development is by Lockheed Martin Space Systems, Denver.

Phoenix's Wet Chemistry Lab

NASA Technical Reports Server (NTRS)

2008-01-01

This is an illustration of soil analysis on NASA's Phoenix Mars Lander's Wet Chemistry Lab (WCL) on board the Microscopy, Electrochemistry, and Conductivity Analyzer (MECA) instrument. By dissolving small amounts of soil in water, WCL will attempt to determine the pH, the abundance of minerals such as magnesium and sodium cations or chloride, bromide and sulfate anions, as well as the conductivity and redox potential.

The Phoenix Mission is led by the University of Arizona, Tucson, on behalf of NASA. Project management of the mission is by NASA's Jet Propulsion Laboratory, Pasadena, Calif. Spacecraft development is by Lockheed Martin Space Systems, Denver.

Coral calcifying fluid pH is modulated by seawater carbonate chemistry not solely seawater pH.

PubMed

Comeau, S; Tambutté, E; Carpenter, R C; Edmunds, P J; Evensen, N R; Allemand, D; Ferrier-Pagès, C; Tambutté, S; Venn, A A

2017-01-25

Reef coral calcification depends on regulation of pH in the internal calcifying fluid (CF) in which the coral skeleton forms. However, little is known about calcifying fluid pH (pH CF ) regulation, despite its importance in determining the response of corals to ocean acidification. Here, we investigate pH CF in the coral Stylophora pistillata in seawater maintained at constant pH with manipulated carbonate chemistry to alter dissolved inorganic carbon (DIC) concentration, and therefore total alkalinity (A T ). We also investigate the intracellular pH of calcifying cells, photosynthesis, respiration and calcification rates under the same conditions. Our results show that despite constant pH in the surrounding seawater, pH CF is sensitive to shifts in carbonate chemistry associated with changes in [DIC] and [A T ], revealing that seawater pH is not the sole driver of pH CF Notably, when we synthesize our results with published data, we identify linear relationships of pH CF with the seawater [DIC]/[H + ] ratio, [A T ]/ [H + ] ratio and [[Formula: see text

Oil/water/rock wettability: Influencing factors and implications for low salinity water flooding in carbonate reservoirs

DOE PAGES

Chen, Yongqiang; Xie, Quan; Sari, Ahmad; ...

2017-11-21

Wettability of the oil/brine/rock system is an essential petro-physical parameter which governs subsurface multiphase flow behaviour and the distribution of fluids, thus directly affecting oil recovery. Recent studies [1–3] show that manipulation of injected brine composition can enhance oil recovery by shifting wettability from oil-wet to water-wet. However, what factor(s) control system wettability has not been completely elucidated due to incomplete understanding of the geochemical system. To isolate and identify the key factors at play we used in this paper SO 4 2—free solutions to examine the effect of salinity (formation brine/FB, 10 times diluted formation brine/10 dFB, and 100more » times diluted formation brine/100 dFB) on the contact angle of oil droplets at the surface of calcite. We then compared contact angle results with predictions of surface complexation by low salinity water using PHREEQC software. We demonstrate that the conventional dilution approach likely triggers an oil-wet system at low pH, which may explain why the low salinity water EOR-effect is not always observed by injecting low salinity water in carbonated reservoirs. pH plays a fundamental role in the surface chemistry of oil/brine interfaces, and wettability. Our contact angle results show that formation brine triggered a strong water-wet system (35°) at pH 2.55, yet 100 times diluted formation brine led to a strongly oil-wet system (contact angle = 175°) at pH 5.68. Surface complexation modelling correctly predicted the wettability trend with salinity; the bond product sum ([>CaOH 2 +][–COO -] + [>CO 3 -][–NH +] + [>CO 3 -][–COOCa +]) increased with decreasing salinity. Finally, at pH < 6 dilution likely makes the calcite surface oil-wet, particularly for crude oils with high base number. Yet, dilution probably causes water wetness at pH > 7 for crude oils with high acid number.« less

Oil/water/rock wettability: Influencing factors and implications for low salinity water flooding in carbonate reservoirs

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

Chen, Yongqiang; Xie, Quan; Sari, Ahmad

Wettability of the oil/brine/rock system is an essential petro-physical parameter which governs subsurface multiphase flow behaviour and the distribution of fluids, thus directly affecting oil recovery. Recent studies [1–3] show that manipulation of injected brine composition can enhance oil recovery by shifting wettability from oil-wet to water-wet. However, what factor(s) control system wettability has not been completely elucidated due to incomplete understanding of the geochemical system. To isolate and identify the key factors at play we used in this paper SO 4 2—free solutions to examine the effect of salinity (formation brine/FB, 10 times diluted formation brine/10 dFB, and 100more » times diluted formation brine/100 dFB) on the contact angle of oil droplets at the surface of calcite. We then compared contact angle results with predictions of surface complexation by low salinity water using PHREEQC software. We demonstrate that the conventional dilution approach likely triggers an oil-wet system at low pH, which may explain why the low salinity water EOR-effect is not always observed by injecting low salinity water in carbonated reservoirs. pH plays a fundamental role in the surface chemistry of oil/brine interfaces, and wettability. Our contact angle results show that formation brine triggered a strong water-wet system (35°) at pH 2.55, yet 100 times diluted formation brine led to a strongly oil-wet system (contact angle = 175°) at pH 5.68. Surface complexation modelling correctly predicted the wettability trend with salinity; the bond product sum ([>CaOH 2 +][–COO -] + [>CO 3 -][–NH +] + [>CO 3 -][–COOCa +]) increased with decreasing salinity. Finally, at pH < 6 dilution likely makes the calcite surface oil-wet, particularly for crude oils with high base number. Yet, dilution probably causes water wetness at pH > 7 for crude oils with high acid number.« less

Estimation of Scale Deposition in the Water Walls of an Operating Indian Coal Fired Boiler: Predictive Modeling Approach Using Artificial Neural Networks

NASA Astrophysics Data System (ADS)

Kumari, Amrita; Das, Suchandan Kumar; Srivastava, Prem Kumar

2016-04-01

Application of computational intelligence for predicting industrial processes has been in extensive use in various industrial sectors including power sector industry. An ANN model using multi-layer perceptron philosophy has been proposed in this paper to predict the deposition behaviors of oxide scale on waterwall tubes of a coal fired boiler. The input parameters comprises of boiler water chemistry and associated operating parameters, such as, pH, alkalinity, total dissolved solids, specific conductivity, iron and dissolved oxygen concentration of the feed water and local heat flux on boiler tube. An efficient gradient based network optimization algorithm has been employed to minimize neural predictions errors. Effects of heat flux, iron content, pH and the concentrations of total dissolved solids in feed water and other operating variables on the scale deposition behavior have been studied. It has been observed that heat flux, iron content and pH of the feed water have a relatively prime influence on the rate of oxide scale deposition in water walls of an Indian boiler. Reasonably good agreement between ANN model predictions and the measured values of oxide scale deposition rate has been observed which is corroborated by the regression fit between these values.

Lake Recovery Through Reduced Sulfate Deposition: A New Paradigm for Drinking Water Treatment.

PubMed

Anderson, Lindsay E; Krkošek, Wendy H; Stoddart, Amina K; Trueman, Benjamin F; Gagnon, Graham A

2017-02-07

This study examined sulfate deposition in Nova Scotia from 1999 to 2015, and its association with increased pH and organic matter in two protected surface water supplies (Pockwock Lake and Lake Major) located in Halifax, Nova Scotia. The study also examined the effect of lake water chemistry on drinking water treatment processes. Sulfate deposition in the region decreased by 68%, whereas pH increased by 0.1-0.4 units over the 16-year period. Average monthly color concentrations in Pockwock Lake and Lake Major increased by 1.7 and 3.8×, respectively. Accordingly, the coagulant demand increased by 1.5 and 3.8× for the water treatment plants supplied by Pockwock Lake and Lake Major. Not only was this coagulant increase costly for the utility, it also resulted in compromised filter performance, particularly for the direct-biofiltration plant supplied by Pockwock Lake that was found to already be operating at the upper limit of the recommended direct filtration thresholds for color, total organic carbon and coagulant dose. Additionally, in 2012-2013 geosmin occurred in Pockwock Lake, which could have been attributed to reduced sulfate deposition as increases in pH favor more diverse cyanobacteria populations. Overall, this study demonstrated the impact that ambient air quality can have on drinking water supplies.

Modeling the acid-base surface chemistry of montmorillonite.

PubMed

Bourg, Ian C; Sposito, Garrison; Bourg, Alain C M

2007-08-15

Proton uptake on montmorillonite edge surfaces can control pore water pH, solute adsorption, dissolution kinetics and clay colloid behavior in engineered clay barriers and natural weathering environments. Knowledge of proton uptake reactions, however, is currently limited by strong discrepancies between reported montmorillonite titration data sets and by conflicting estimates of edge structure, reactivity and electrostatics. In the present study, we show that the apparent discrepancy between titration data sets results in large part from the widespread use of an erroneous assumption of zero specific net proton surface charge at the onset of titration. Using a novel simulation scheme involving a surface chemistry model to simulate both pretreatment and titration, we find that montmorillonite edge surface chemistry models that account for the "spillover" of electrostatic potential from basal onto edge surfaces and for the stabilization of deprotonated Al-Si bridging sites through bond-length relaxation at the edge surface can reproduce key features of the best available experimental titration data (the influence of pretreatment conditions on experimental results, the absence of a point of zero salt effect, buffer capacity in the acidic pH range). However, no combination of current models of edge surface structure, reactivity and electrostatics can quantitatively predict, without fitted parameters, the experimental titration data over the entire range of pH (4.5 to 9) and ionic strength (0.001 to 0.5 mol dm(-3)) covered by available data.

A spatial and seasonal assessment of river water chemistry across North West England.

PubMed

Rothwell, J J; Dise, N B; Taylor, K G; Allott, T E H; Scholefield, P; Davies, H; Neal, C

2010-01-15

This paper presents information on the spatial and seasonal patterns of river water chemistry at approximately 800 sites in North West England based on data from the Environment Agency regional monitoring programme. Within a GIS framework, the linkages between average water chemistry (pH, sulphate, base cations, nutrients and metals) catchment characteristics (topography, land cover, soil hydrology, base flow index and geology), rainfall, deposition chemistry and geo-spatial information on discharge consents (point sources) are examined. Water quality maps reveal that there is a clear distinction between the uplands and lowlands. Upland waters are acidic and have low concentrations of base cations, explained by background geological sources and land cover. Localised high concentrations of metals occur in areas of the Cumbrian Fells which are subjected to mining effluent inputs. Nutrient concentrations are low in the uplands with the exception sites receiving effluent inputs from rural point sources. In the lowlands, both past and present human activities have a major impact on river water chemistry, especially in the urban and industrial heartlands of Greater Manchester, south Lancashire and Merseyside. Over 40% of the sites have average orthophosphate concentrations >0.1mg-Pl(-1). Results suggest that the dominant control on orthophosphate concentrations is point source contributions from sewage effluent inputs. Diffuse agricultural sources are also important, although this influence is masked by the impact of point sources. Average nitrate concentrations are linked to the coverage of arable land, although sewage effluent inputs have a significant effect on nitrate concentrations. Metal concentrations in the lowlands are linked to diffuse and point sources. The study demonstrates that point sources, as well as diffuse sources, need to be considered when targeting measures for the effective reduction in river nutrient concentrations. This issue is clearly important with regards to the European Union Water Framework Directive, eutrophication and river water quality. Copyright 2009 Elsevier B.V. All rights reserved.

The role of water chemistry and geomorphic control in the presence of Didymosphenia geminata in Quebec

NASA Astrophysics Data System (ADS)

Gillis, C.; Gabor, R. S.; Cullis, J. D.; Ran, L.; Hassan, M. A.

2010-12-01

Didymosphenia geminata (didymo), an invasive diatom, was first officially observed and identified in the Matapedia River in Eastern Quebec in July 2006. This Atlantic salmon fishing river has several characteristics shown to favor didymo's ability to form thick, extensive benthic mats, including stable flow and oligotrophic nutrient conditions. Since the incursion, rapid colonization and inter-catchment transfer processes were observed, notably in surrounding watersheds on the Gaspé Peninsula as well as in northern New-Brunswick. All affected watersheds share favorable characteristics for didymo growth, including high light, low nutrient waters, and stable substrate. The nearby North Shore of the St. Lawrence, which also contains rivers with conditions that would favor didymo growth, has not yet shown didymo presence. This system provides a comparison to identify necessary parameters for didymo growth, with differences primarily due to geology-driven water chemistry. Pre-incursion water chemistry was compared between the two regions. Rivers in the region where didymo is present displayed a high alkalinity and corresponding higher pH, due to increases concentrations of magnesium and calcium, than rivers in regions where didymo has not appeared. Also, rivers with didymo show a lower amount of color-causing compounds, such as organic carbon, and clearer water, which supports the theory that high light levels encourage didymo growth. In addition to water chemistry, channel morphology, bed stability and flow patterns are also believed to be key elements in determining the presence of this benthic diatom. In 2007, channel morphology, bed texture, bankfull depth and width, local bed slope and didymo presence were surveyed on a 65 km stretch of the Matapedia River. Relative frequency of didymo presence showed that didymo blooms are most likely to appear in cobble-riffles than in any other morphologies. In fact, cobble riffles promote didymo establishment due to shallow waters which offer high solar radiation as well as stable riverbed. Both water chemistry and geomorphic factors appear to control Didymosphenia geminata spatial patterns and occurrence.

Photogenerated Lectin Sensors Produced by Thiol-Ene/Yne Photo-Click Chemistry in Aqueous Solution

PubMed Central

Norberg, Oscar; Lee, Irene H.; Aastrup, Teodor; Yan, Mingdi; Ramström, Olof

2012-01-01

The photoinitiated radical reactions between thiols and alkenes/alkynes (thiol-ene and thiol-yne chemistry) have been applied to a functionalization methodology to produce carbohydrate-presenting surfaces for analyses of biomolecular interactions. Polymer-coated quartz surfaces were functionalized with alkenes or alkynes in a straightforward photochemical procedure utilizing perfluorophenylazide (PFPA) chemistry. The alkene/alkyne surfaces were subsequently allowed to react with carbohydrate thiols in water under UV-irradiation. The reaction can be carried out in a drop of water directly on the surface without photoinitiator and any disulfide side products were easily washed away after the functionalization process. The resulting carbohydrate-presenting surfaces were evaluated in real-time studies of protein-carbohydrate interactions using a quartz crystal microbalance flow-through system with recurring injections of selected lectins with intermediate regeneration steps using low pH buffer. The resulting methodology proved fast, efficient and scalable to high-throughput analysis formats, and the produced surfaces showed significant protein binding with expected selectivities of the lectins used in the study. PMID:22341757

Hydrogeochemical features of surface water and groundwater contaminated with acid mine drainage (AMD) in coal mining areas: a case study in southern Brazil.

PubMed

Galhardi, Juliana Aparecida; Bonotto, Daniel Marcos

2016-09-01

Effects of acid mine drainage (AMD) were investigated in surface waters (Laranjinha River and Ribeirão das Pedras stream) and groundwaters from a coal mining area sampled in two different seasons at Figueira city, Paraná State, Brazil. The spatial data distribution indicated that the acid effluents favor the chemical elements leaching and transport from the tailings pile into the superficial water bodies or aquifers, modifying their quality. The acid groundwaters in both sampling periods (dry: pH 2.94-6.04; rainy: pH 3.25-6.63) were probably due to the AMD generation and infiltration, after the oxidation of sulfide minerals. Such acid effluents cause an increase of the solubilization rate of metals, mainly iron and aluminum, contributing to both groundwater and surface water contamination. Sulfate in high levels is a result of waters' pollution due to AMD. In some cases, high sulfate and low iron contents, associated with less acidic pH values, could indicate that AMD, previously generated, is nowadays being neutralized. The chemistry of the waters affected by AMD is controlled by the pH, sulfide minerals' oxidation, oxygen, iron content, and microbial activity. It is also influenced by seasonal variations that allow the occurrence of dissolution processes and the concentration of some chemical elements. Under the perspective of the waters' quality evaluation, the parameters such as conductivity, dissolved sodium, and sulfate concentrations acted as AMD indicators of groundwaters and surface waters affected by acid effluents.

Sphagnum establishment in alkaline fens: Importance of weather and water chemistry.

PubMed

Vicherová, Eliška; Hájek, Michal; Šmilauer, Petr; Hájek, Tomáš

2017-02-15

Sphagnum expansion to alkaline fens has accelerated during the last decades in Europe, leading to changes in diversity, habitat distributions and carbon storage. The causes are still not clearly understood and involve an interplay between climate change, hydrology, nutrient supply and Sphagnum physiology. We conducted a 4-year field experiment in eight fens in Central European highlands and assessed survival and establishment of individual apical shoot fragments of S. flexuosum, S. warnstorfii and S. squarrosum transplanted along the microtopographical gradient. In a laboratory experiment, we tested combined effects of desiccation and high calcium bicarbonate concentration on Sphagnum survival. We found that in unflooded positions, living shoots of Sphagnum and brown mosses lowered [Ca 2+ ] and pH in their capillary water, in contrast to dead fragments; yet without differences between species. Survival and expansion of Sphagnum fragments, which did not die of acute calcium toxicity during first weeks/months, was negatively affected by dry weather and alkaline water chemistry, reflecting Sphagnum intolerance to desiccation and to combined high [Ca 2+ ] and pH. Shoot fragments expanded to patches only when precipitation was high. Interestingly, non-toxic concentration of calcium bicarbonate reduced desiccation damage in Sphagnum, probably through protection of membranes or other cell components. This mechanism would facilitate Sphagnum survival in elevated, frequently desiccated microhabitats of calcareous fens such as brown-moss hummocks. However, since water-retaining capacity of few Sphagnum shoots is insufficient to change water chemistry in its surroundings, surface acidification may occur only once the environment (e.g. sufficient humidity) enabled expansion to larger mats. Then, the retained rainwater together with hardly decomposable Sphagnum litter would separate mire surface from groundwater, speeding up successional shift towards poor fens. Sphagnum expansion to alkaline fens is therefore more likely in humid regions. Copyright © 2016 Elsevier B.V. All rights reserved.

Recovery from chronic and snowmelt acidification: Long-term trends in stream and soil water chemistry at the Hubbard Brook Experimental Forest, New Hampshire, USA

NASA Astrophysics Data System (ADS)

Fuss, Colin B.; Driscoll, Charles T.; Campbell, John L.

2015-11-01

Atmospheric acid deposition of sulfate and nitrate has declined markedly in the northeastern United States due to emissions controls. We investigated long-term trends in soil water (1984-2011) and stream water (1982-2011) chemistry along an elevation gradient of a forested watershed to evaluate the progress of recovery of drainage waters from acidic deposition at the Hubbard Brook Experimental Forest in the White Mountains of New Hampshire, USA. We found slowed losses of base cations from soil and decreased mobilization of dissolved inorganic aluminum. Stream water pH at the watershed outlet increased at a rate of 0.01 units yr-1, and the acid neutralizing capacity (ANC) gained 0.88 µeq L-1 yr-1. Dissolved organic carbon generally decreased in stream water and soil solutions, contrary to trends observed at many North American and European sites. We compared whole-year hydrochemical trends with those during snowmelt, which is the highest-flow and lowest ANC period of the year, indicative of episodic acidification. Stream water during snowmelt had long-term trends of increasing ANC and pH at a rate very similar to the whole-year record, with closely related steady decreases in sulfate. A more rapid decline in stream water nitrate during snowmelt compared with the whole-year trend may be due, in part, to the marked decrease in atmospheric nitrate deposition during the last decade. The similarity between the whole-year trends and those of the snowmelt period is an important finding that demonstrates a consistency between recovery from chronic acidification during base flow and abatement of snowmelt acidification.

Leaching potential of pervious concrete and immobilization of Cu, Pb and Zn using pervious concrete.

PubMed

Solpuker, U; Sheets, J; Kim, Y; Schwartz, F W

2014-06-01

This paper investigates the leaching potential of pervious concrete and its capacity for immobilizing Cu, Pb and Zn, which are common contaminants in urban runoff. Batch experiments showed that the leachability of Cu, Pb and Zn increased when pH<8. According to PHREEQC equilibrium modeling, the leaching of major ions and trace metals was mainly controlled by the dissolution/precipitation and surface complexation reactions, respectively. A 1-D reactive transport experiment was undertaken to better understand how pervious concrete might function to attenuate contaminant migration. A porous concrete block was sprayed with low pH water (pH=4.3±0.1) for 190 h. The effluent was highly alkaline (pH~10 to 12). In the first 50 h, specific conductance and trace-metal were high but declined towards steady state values. PHREEQC modeling showed that mixing of interstitial alkaline matrix waters with capillary pore water was required in order to produce the observed water chemistry. The interstitial pore solutions seem responsible for the high pH values and relatively high concentrations of trace metals and major cations in the early stages of the experiment. Finally, pervious concrete was sprayed with a synthetic contaminated urban runoff (10 ppb Cu, Pb and Zn) with a pH of 4.3±0.1 for 135 h. It was found that Pb immobilization was greater than either Cu or Zn. Zn is the most mobile among three and also has the highest variation in the observed degree of immobilization. Copyright © 2014 Elsevier B.V. All rights reserved.

Questa baseline and pre-mining ground-water quality investigation. 5. Well installation, water-level data, and surface- and ground-water geochemistry in the Straight Creek drainage basin, Red River Valley, New Mexico, 2001-03

USGS Publications Warehouse

Naus, Cheryl A.; McCleskey, R. Blaine; Nordstrom, D. Kirk; Donohoe, Lisa C.; Hunt, Andrew G.; Paillet, Frederick L.; Morin, Roger H.; Verplanck, Philip L.

2005-01-01

The U.S. Geological Survey, in cooperation with the New Mexico Environment Department, is investigating the pre-mining ground-water chemistry at the Molycorp molybdenum mine in the Red River Valley, northern New Mexico. The primary approach is to determine the processes controlling ground-water chemistry at an unmined, off-site, proximal analog. The Straight Creek drainage basin, chosen for this purpose, consists of the same quartz-sericite-pyrite altered andesitic and rhyolitic volcanic rock of Tertiary age as the mine site. The weathered and rugged volcanic bedrock surface is overlain by heterogeneous debris-flow deposits that interfinger with alluvial deposits near the confluence of Straight Creek and the Red River. Pyritized rock in the upper part of the drainage basin is the source of acid rock drainage (pH 2.8-3.3) that infiltrates debris-flow deposits containing acidic ground water (pH 3.0-4.0) and bedrock containing water of circumneutral pH values (5.6-7.7). Eleven observation wells were installed in the Straight Creek drainage basin. The wells were completed in debris-flow deposits, bedrock, and interfingering debris-flow and Red River alluvial deposits. Chemical analyses of ground water from these wells, combined with chemical analyses of surface water, water-level data, and lithologic and geophysical logs, provided information used to develop an understanding of the processes contributing to the chemistry of ground water in the Straight Creek drainage basin. Surface- and ground-water samples were routinely collected for determination of total major cations and selected trace metals; dissolved major cations, selected trace metals, and rare-earth elements; anions and alkalinity; and dissolved-iron species. Rare-earth elements were determined on selected samples only. Samples were collected for determination of dissolved organic carbon, mercury, sulfur isotopic composition (34S and 18O of sulfate), and water isotopic composition (2H and 18O) during selected samplings. One set of ground-water samples was collected for helium-3/tritium and chlorofluorocarbon (CFC) age dating. Several lines of evidence indicate that surface water is the primary input to the Straight Creek ground-water system. Straight Creek streamflow and water levels in wells closest to the apex of the Straight Creek debris fan and closest to Straight Creek itself appear to respond to the same seasonal inputs. Oxygen and hydrogen isotopic compositions in Straight Creek surface water and ground water are similar, and concentrations of most dissolved constituents in most Straight Creek surface-water and shallow (debris-flow and alluvial) aquifer ground-water samples correlate strongly with sulfate (concentrations decrease linearly with sulfate in a downgradient direction). After infiltration of surface water, dilution along the flow path is the dominant mechanism controlling ground-water chemistry. However, concentrations of some constituents can be higher in ground water than can be accounted for by concentrations in Straight Creek surface water, and additional sources of these constituents must therefore be inferred. Constituents for which concentrations in ground water can be high relative to surface water include calcium, magnesium, strontium, silica, sodium, and potassium in ground water from debris-flow and alluvial aquifers and manganese, calcium, magnesium, strontium, sodium, and potassium in ground water from the bedrock aquifer. All ground water is a calcium sulfate type, often at or near gypsum saturation because of abundant gypsum in the aquifer material developed from co-existing calcite and pyrite mineralization. Calcite dissolution, the major buffering mechanism for bedrock aquifer ground water, also contributes to relatively higher calcium concentrations in some ground water. The main source of the second most abundant cation, magnesium, is probably dissolution of magnesium-rich carbonates or silicates. Strontium may also be

Water chemistry of surface waters affected by the Fourmile Canyon wildfire, Colorado, 2010-2011

USGS Publications Warehouse

McCleskey, R. Blaine; Writer, Jeffrey H.; Murphy, Sheila F.

2012-01-01

In September 2010, the Fourmile Canyon fire burned about 23 percent of the Fourmile Creek watershed in Boulder County, Colo. Water-quality sampling of Fourmile Creek began within a month after the wildfire to assess its effects on surface-water chemistry. Water samples were collected from five sites along Fourmile Creek (above, within, and below the burned area) monthly during base flow, twice weekly during snowmelt runoff, and at higher frequencies during storm events. Stream discharge was also monitored. Water-quality samples were collected less frequently from an additional 6 sites on Fourmile Creek, from 11 tributaries or other inputs, and from 3 sites along Boulder Creek. The pH, electrical conductivity, temperature, specific ultraviolet absorbance, total suspended solids, and concentrations (dissolved and total) of major cations (calcium, magnesium, sodium, and potassium), anions (chloride, sulfate, alkalinity, fluoride, and bromide), nutrients (nitrate, ammonium, and phosphorus), trace metals (aluminum, arsenic, boron, barium, beryllium, cadmium, cobalt, chromium, copper, iron, mercury, lithium, manganese, molybdenum, nickel, lead, rubidium, antimony, selenium, strontium, vanadium, and zinc), and dissolved organic carbon are here reported for 436 samples collected during 2010 and 2011.

Water-Chemistry and Its Utility Systems in CCP Power Units (Review)

NASA Astrophysics Data System (ADS)

Larin, B. M.

2018-01-01

Damageability of heat transfer surfaces of waste heat recovery steam generators (HRSG) of combined- cycle plants (CCP) can be reduced due to an increase in the quality of make-up and feed water, the use of phosphate-alkaline or amino compound water chemistry (WC), and improved chemical quality control of the heat carrier and make-up water preparation techniques. Temporary quality standards for the heat medium developed by the All-Russia Thermal Engineering institute (VTI) for CCP power units are presented in comparison with the IAPWS standards; preferences for the choice of a WC type for some power units commissioned in Russia in the first decade of this century are shown; and operational data on the quality of feed, boiler water, and steam for two large CCP-450 and CCP-425 power units are given. The state and prospects for the development of chemical-technological monitoring systems and CCP water treatment plants are noted. Estimability of some CCP diagnostic parameters by measuring specific electric conductivity and pH is shown. An extensive bibliography on this topic is given.

Effects of pH on nano-bubble stability and transport in saturated porous media

NASA Astrophysics Data System (ADS)

Hamamoto, Shoichiro; Takemura, Takato; Suzuki, Kenichiro; Nishimura, Taku

2018-01-01

An understanding of nano-scale bubble (NB) transport in porous media is important for potential application of NBs in soil/groundwater remediation. It is expected that the solution chemistry of NB water highly influences the surface characteristics of NBs and porous media and the interaction between them, thus affecting the stability and transport characteristics of NB. In this study, in addition to stability experiments, one-dimensional column transport experiments using glass beads were conducted to investigate the effects of pH on the NB transport behavior. The results showed that the NBs were more stable under higher pH. Column transport experiments revealed that entrapment of NBs, especially larger ones, was enhanced in lower-pH water, likely suggesting pH-dependent NB attachment and physical straining, both of which are also probably influenced by bubble size. Although relatively smaller NBs were released after switching the eluting fluid to one with lower ionic strength, most of the NBs in lower-pH water were still retained in the porous media even altering the chemical condition.

Effects of pH on nano-bubble stability and transport in saturated porous media.

PubMed

Hamamoto, Shoichiro; Takemura, Takato; Suzuki, Kenichiro; Nishimura, Taku

2018-01-01

An understanding of nano-scale bubble (NB) transport in porous media is important for potential application of NBs in soil/groundwater remediation. It is expected that the solution chemistry of NB water highly influences the surface characteristics of NBs and porous media and the interaction between them, thus affecting the stability and transport characteristics of NB. In this study, in addition to stability experiments, one-dimensional column transport experiments using glass beads were conducted to investigate the effects of pH on the NB transport behavior. The results showed that the NBs were more stable under higher pH. Column transport experiments revealed that entrapment of NBs, especially larger ones, was enhanced in lower-pH water, likely suggesting pH-dependent NB attachment and physical straining, both of which are also probably influenced by bubble size. Although relatively smaller NBs were released after switching the eluting fluid to one with lower ionic strength, most of the NBs in lower-pH water were still retained in the porous media even altering the chemical condition. Copyright © 2017 Elsevier B.V. All rights reserved.

Fog water chemistry in Shanghai

NASA Astrophysics Data System (ADS)

Li, Pengfei; Li, Xiang; Yang, Chenyu; Wang, Xinjun; Chen, Jianmin; Collett, Jeffrey L., Jr.

2011-08-01

With the aim of understanding the fog chemistry in a Chinese megacity, twenty-six fog water samples were collected in urban Shanghai from March 2009 to March 2010. The following parameters were measured: pH, electrical conductivity (EC), ten inorganic major ions ( SO42-, NO3-, NO2-, F -, Cl -, Na +, K +, Ca 2+, Mg 2+, NH4+) and four major organic acids (CH 3COO -, HCOO -, CO42-, MSA). The total ionic concentration (TIC) and EC of fog samples were one or two orders of magnitude higher than those often found in Europe, North America and other Asian countries. Pollutants were expected to be mainly from local sources, including factories, motor vehicle emissions and civil construction. Non-local sources such as moderate- and long-range transport of sea salt also contributed to pollution levels in fog events as indicated by back trajectory analysis. The pH of the fog water collected during the monitoring period varied from 4.68 to 6.58; acidic fogs represented about 30.8% of the total fog events during this period. The fog water was characterized by high concentrations of SO42- (20.0% of measured TIC), NO3- (17.1%), NH4+ (28.3%) and Ca 2+ (14.4%). SO42- and NO3-, the main precursors of fog acidity, were related to burning fossil fuels and vehicle emissions, respectively. NH4+, originating from the scavenging of gaseous ammonia and particulate ammonium nitrate and ammonium sulfate, and Ca 2+, originating from the scavenging of coarse particles, acted as acid neutralizers and were the main cause for the relatively high pH of fogs in Shanghai. The ratio of ( SO42- + NO3-)/( NH4+ + Ca 2+) was lower than 1, indicating the alkaline nature of the fog water. A high ratio of NO3-/ SO42- and low ratio of HCOO -/CH 3COO - were consistent with large contributions from vehicular emissions that produce severe air pollution in megacities.

Coral records of reef-water pH across the central Great Barrier Reef, Australia: assessing the influence of river runoff on inshore reefs

NASA Astrophysics Data System (ADS)

D'Olivo, J. P.; McCulloch, M. T.; Eggins, S. M.; Trotter, J.

2014-07-01

The boron isotopic (δ11Bcarb) compositions of long-lived Porites coral are used to reconstruct reef-water pH across the central Great Barrier Reef (GBR) and assess the impact of river runoff on inshore reefs. For the period from 1940 to 2009, corals from both inner as well as mid-shelf sites exhibit the same overall decrease in δ11Bcarb of 0.086 ± 0.033‰ per decade, equivalent to a~decline in seawater pH (pHsw) of ~ 0.017 ± 0.007 pH units per decade. This decline is consistent with the long-term effects of ocean acidification based on estimates of CO2 uptake by surface waters due to rising atmospheric levels. We also find that compared to the mid-shelf corals, the δ11Bcarb compositions for inner shelf corals subject to river discharge events, have higher and more variable values and hence higher inferred pHsw values. These higher δ11Bcarb values for inner-shelf corals are particularly evident during wet years, despite river waters having lower pH. The main effect of river discharge on reef-water carbonate chemistry thus appears to be from higher nutrients driving increased phytoplankton productivity, resulting in the drawdown of pCO2 and increase in pHsw. Increased primary production therefore has the potential to counter the more transient effects of low pH river water (pHrw) discharged into near-shore environments. Importantly however, inshore reefs also show a consistent pattern of sharply declining coral growth that coincides with periods of high river discharge. This occurs despite these reefs having higher pHsw values and hence higher seawater aragonite saturation states, demonstrating the over-riding importance of local reef-water quality on coral reef health.

Acid rock drainage in Nevado Pastoruri glacier area (Huascarán National Park, Perú): hydrochemical and mineralogical characterization and associated environmental implications.

PubMed

Santofimia, Esther; López-Pamo, Enrique; Palomino, Edwin Julio; González-Toril, Elena; Aguilera, Ángeles

2017-11-01

The generation of acid rock drainage (ARD) was observed in an area of Nevado Pastoruri as a result of the oxidative dissolution of pyrite-rich lutites and sandstones. These ARDs are generated as abundant pyrite becomes exposed to atmospheric conditions as a result of glacier retreat. The proglacial zone contains lagoons, springs, streams and wetlands, scant vegetation, and intense fluvioglacial erosion. This work reports a comprehensive identification and the results of sampling of the lagoons and springs belonging to the microbasin, which is the headwaters of the Pachacoto River, as well as mapping results based on the hydrochemical data obtained in our study. The physical properties and water chemistry of 12 springs and 22 lagoons from the proglacial zone are also presented. Water springs are far from being chemically uniform, with pH and EC values ranging between 2.55-6.42 and 23-1110 μS/cm respectively, which suggests a strong geologic control on water chemistry. Fe-SO 4 -2 concentrations confirm the intense process of pyrite oxidative dissolution. Many of the lagoons are affected by ARD, with low pH (~ 3), and high EC (256-1092 μS/cm) values when compared with unaffected lagoons (EC between 7 and 59 μS/cm), indicating a high degree of mineralization. The affected lagoons show higher concentrations of SO 4 2- and SiO 2 , and elements as Fe, Al, Mg, Mn, Zn, Co, and Ni, which are related to the alteration of pyrite and the dissolution of aluminosilicate minerals. Schwertmannite-goethite appears to be the most important mineral phases controlling the Fe solubility at a pH of 2-3.5. Moreover, they act as a sorbent of trace elements (As, Sb, V, Pb, Zn, Cr), which is an efficient mechanism of natural attenuation. Despite of this, the water flowing out from the basin is acid (pH 3.1) and contains significant concentrations of Fe (0.98 mg/L) and Al (3.76 mg/L) that confer mineral acidity to water. The Pachacoto River located 5.5 km downstream from this point showed a strong natural attenuation, with a pH of 6.9 and low concentration of metals. This mitigating process is possible due to (i) the formation of precipitates that retain toxic elements and (ii) the mixing with natural waters that promote dilution, which favor the increase of pH until circumneutral conditions.

Pore-water chemistry explains zinc phytotoxicity in soil.

PubMed

Kader, Mohammed; Lamb, Dane T; Correll, Ray; Megharaj, Mallavarapu; Naidu, Ravi

2015-12-01

Zinc (Zn) is a widespread soil contaminant arising from a numerous anthropogenic sources. However, adequately predicting toxicity of Zn to ecological receptors remains difficult due to the complexity of soil characteristics. In this study, we examined solid-solution partitioning using pore-water data and toxicity of Zn to cucumber (Cucumis sativus L.) in spiked soils. Pore-water effective concentration (ECx, x=10%, 20% and 50% reduction) values were negatively related to pH, indicating lower Zn pore water concentration were needed to cause phytotoxicity at high pH soils. Total dissolved zinc (Znpw) and free zinc (Zn(2+)) in soil-pore water successfully described 78% and 80.3% of the variation in relative growth (%) in the full dataset. When the complete data set was used (10 soils), the estimated EC50pw was 450 and 79.2 µM for Znpw and Zn(2+), respectively. Total added Zn, soil pore water pH (pHpw) and dissolve organic carbon (DOC) were the best predictors of Znpw and Zn(2+) in pore-water. The EC10 (total loading) values ranged from 179 to 5214 mg/kg, depending on soil type. Only pH measurements in soil were related to ECx total Zn data. The strongest relationship to ECx overall was pHca, although pHw and pHpw were in general related to Zn ECx. Similarly, when a solution-only model was used to predict Zn in shoot, DOC was negatively related to Zn in shoot, indicating a reduction in uptake/ translocation of Zn from solution with increasing DOC. Copyright © 2015 Elsevier Inc. All rights reserved.

Physiological characterisation of a pH- and calcium-dependent sodium uptake mechanism in the freshwater crustacean, Daphnia magna.

PubMed

Glover, Chris N; Wood, Chris M

2005-03-01

Daphnia are highly sensitive to sodium metabolism disruption caused by aquatic acidification and ionoregulatory toxicants, due to their finely balanced ion homeostasis. Nine different water chemistries of varying pH (4, 6 and 8) and calcium concentration (0, 0.5 and 1 mmol l(-1)) were used to delineate the mechanism of sodium influx in Daphnia magna. Lowering water pH severely inhibited sodium influx when calcium concentration was high, but transport kinetic analysis revealed a stimulated sodium influx capacity (J(max)) when calcium was absent. At low pH increasing water calcium levels decreased J(max) and raised K(m) (decreased sodium influx affinity), while at high pH the opposite pattern was observed (elevated J(max) and reduced K(m)). These effects on sodium influx were mirrored by changes in whole body sodium levels. Further examination of the effect of calcium on sodium influx showed a severe inhibition of sodium uptake by 100 micromol l(-1) calcium gluconate at both low (50 micromol l(-1)) and high (1000 micromol l(-1)) sodium concentrations. At high sodium concentrations, stimulated sodium influx was noted with elevated calcium levels. These results, in addition to data showing amiloride inhibition of sodium influx (K(i)=180 micromol l(-1)), suggest a mechanism of sodium influx in Daphnia magna that involves the electrogenic 2Na(+)/1H(+) exchanger.

Removing lead in drinking water with activated carbon

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

Taylor, R.M.; Kuennen, R.W.

A point-of-use (POU) granular activated carbon (GAC) fixed bed adsorber (FBA) was evaluated for reduction of soluble and insoluble lead from drinking water. Some of the factors which affect lead removal by GAC were evaluated, such as carbon type, solution pH, and a limited amount of work on competitive interactions. The design criteria for lead reduction by a POU device are also addressed. Minicolumns were used to evaluate the capacity of carbon for lead under a variety of conditions. The importance of surface chemistry of the carbon and the relationship with the pH of the water for lead reduction wasmore » demonstrated. Results indicate that a properly designed POU-GAC-FBA can reduce lead in drinking water to below the EPA action level of 15 ppb while being tested under a variety of conditions as specified under the National Sanitation Foundation (NSF) International Standard 53 test protocol. 37 refs., 9 figs., 1 tab.« less

Geochemical detection of carbon dioxide in dilute aquifers

PubMed Central

2009-01-01

Background Carbon storage in deep saline reservoirs has the potential to lower the amount of CO2 emitted to the atmosphere and to mitigate global warming. Leakage back to the atmosphere through abandoned wells and along faults would reduce the efficiency of carbon storage, possibly leading to health and ecological hazards at the ground surface, and possibly impacting water quality of near-surface dilute aquifers. We use static equilibrium and reactive transport simulations to test the hypothesis that perturbations in water chemistry associated with a CO2 gas leak into dilute groundwater are important measures for the potential release of CO2 to the atmosphere. Simulation parameters are constrained by groundwater chemistry, flow, and lithology from the High Plains aquifer. The High Plains aquifer is used to represent a typical sedimentary aquifer overlying a deep CO2 storage reservoir. Specifically, we address the relationships between CO2 flux, groundwater flow, detection time and distance. The CO2 flux ranges from 103 to 2 × 106 t/yr (0.63 to 1250 t/m2/yr) to assess chemical perturbations resulting from relatively small leaks that may compromise long-term storage, water quality, and surface ecology, and larger leaks characteristic of short-term well failure. Results For the scenarios we studied, our simulations show pH and carbonate chemistry are good indicators for leakage of stored CO2 into an overlying aquifer because elevated CO2 yields a more acid pH than the ambient groundwater. CO2 leakage into a dilute groundwater creates a slightly acid plume that can be detected at some distance from the leak source due to groundwater flow and CO2 buoyancy. pH breakthrough curves demonstrate that CO2 leaks can be easily detected for CO2 flux ≥ 104 t/yr within a 15-month time period at a monitoring well screened within a permeable layer 500 m downstream from the vertical gas trace. At lower flux rates, the CO2 dissolves in the aqueous phase in the lower most permeable unit and does not reach the monitoring well. Sustained pumping in a developed aquifer mixes the CO2-affected water with the ambient water and enhances pH signal for small leaks (103 t/yr) and reduces pH signal for larger leaks (≥ 104t/yr). Conclusion The ability to detect CO2 leakage from a storage reservoir to overlying dilute groundwater is dependent on CO2 solubility, leak flux, CO2 buoyancy, and groundwater flow. Our simulations show that the most likely places to detect CO2 are at the base of the confining layer near the water table where CO2 gas accumulates and is transported laterally in all directions, and downstream of the vertical gas trace where groundwater flow is great enough to transport dissolved CO2 laterally. Our simulations show that CO2 may not rise high enough in the aquifer to be detected because aqueous solubility and lateral groundwater transport within the lower aquifer unit exceeds gas pressure build-up and buoyancy needed to drive the CO2 gas upwards. PMID:19323832

Geochemical detection of carbon dioxide in dilute aquifers.

PubMed

Carroll, Susan; Hao, Yue; Aines, Roger

2009-03-26

Carbon storage in deep saline reservoirs has the potential to lower the amount of CO2 emitted to the atmosphere and to mitigate global warming. Leakage back to the atmosphere through abandoned wells and along faults would reduce the efficiency of carbon storage, possibly leading to health and ecological hazards at the ground surface, and possibly impacting water quality of near-surface dilute aquifers. We use static equilibrium and reactive transport simulations to test the hypothesis that perturbations in water chemistry associated with a CO2 gas leak into dilute groundwater are important measures for the potential release of CO2 to the atmosphere. Simulation parameters are constrained by groundwater chemistry, flow, and lithology from the High Plains aquifer. The High Plains aquifer is used to represent a typical sedimentary aquifer overlying a deep CO2 storage reservoir. Specifically, we address the relationships between CO2 flux, groundwater flow, detection time and distance. The CO2 flux ranges from 10(3) to 2 x 10(6) t/yr (0.63 to 1250 t/m2/yr) to assess chemical perturbations resulting from relatively small leaks that may compromise long-term storage, water quality, and surface ecology, and larger leaks characteristic of short-term well failure. For the scenarios we studied, our simulations show pH and carbonate chemistry are good indicators for leakage of stored CO2 into an overlying aquifer because elevated CO2 yields a more acid pH than the ambient groundwater. CO2 leakage into a dilute groundwater creates a slightly acid plume that can be detected at some distance from the leak source due to groundwater flow and CO2 buoyancy. pH breakthrough curves demonstrate that CO2 leaks can be easily detected for CO2 flux >or= 10(4) t/yr within a 15-month time period at a monitoring well screened within a permeable layer 500 m downstream from the vertical gas trace. At lower flux rates, the CO2 dissolves in the aqueous phase in the lower most permeable unit and does not reach the monitoring well. Sustained pumping in a developed aquifer mixes the CO2-affected water with the ambient water and enhances pH signal for small leaks (10(3) t/yr) and reduces pH signal for larger leaks (>or= 10(4) t/yr). The ability to detect CO2 leakage from a storage reservoir to overlying dilute groundwater is dependent on CO2 solubility, leak flux, CO2 buoyancy, and groundwater flow. Our simulations show that the most likely places to detect CO2 are at the base of the confining layer near the water table where CO2 gas accumulates and is transported laterally in all directions, and downstream of the vertical gas trace where groundwater flow is great enough to transport dissolved CO2 laterally. Our simulations show that CO2 may not rise high enough in the aquifer to be detected because aqueous solubility and lateral groundwater transport within the lower aquifer unit exceeds gas pressure build-up and buoyancy needed to drive the CO2 gas upwards.

CPT Special Report: Survey of Ph.D. Programs in Chemistry.

ERIC Educational Resources Information Center

Journal of Chemical Education, 1997

1997-01-01

Presents preliminary results from a survey taken by the American Chemical Society (ACS) Committee on Professional Training (CPT) to determine the current practices among 155 Ph.D. programs in chemistry. (DKM)

Controls on dripwater chemistry of Oregon Caves National Monument, northwestern United States

NASA Astrophysics Data System (ADS)

Rushdi, Ahmed I.; Ersek, Vasile; Mix, Alan C.; Clark, Peter U.

2018-02-01

Cave dripwater chemistry of Oregon Caves National Monument (OCNM) was studied, where the parameters pH, total alkalinity, calcium, magnesium, strontium, sodium and barium were analyzed at quasi-monthly intervals from 2005 to 2007. Different statistical analyses have been used to investigate the variability of the chemical parameters in the different sites in the OCNM cave system. The dripwater varies in response to seasonal changes in rainfall. The drip rates range from zero in summer to continuous flow in winter, closely following the rainfall intensity. Spatial variations of dripwater chemistry, which is nonlinearly related to dripwater discharge likely, reflect the chemical composition of bedrock and overlying soil, and the residence time of the ground water within the aquifer. The residence time of infiltrated water in bedrock cracks control the dissolution carbonate bedrock, reprecipitation of calcium carbonate and the degree of saturation of dripwater with respect to calcium carbonate minerals. Spatiotemporal fluctuations of dripwater Mg/Ca and Sr/Ca ratios are controlled by dissolution of carbonate bedrock and the degree of calcite reprecipitation in bedrock cracks. This suggests that trace elements in speleothem deposits at the OCNM may serve as paleoclimatological proxies for precipitation, if interpreted within the context of understanding local bedrock chemistry.

Coral calcifying fluid pH is modulated by seawater carbonate chemistry not solely seawater pH

PubMed Central

Tambutté, E.; Carpenter, R. C.; Edmunds, P. J.; Evensen, N. R.; Allemand, D.; Ferrier-Pagès, C.; Tambutté, S.; Venn, A. A.

2017-01-01

Reef coral calcification depends on regulation of pH in the internal calcifying fluid (CF) in which the coral skeleton forms. However, little is known about calcifying fluid pH (pHCF) regulation, despite its importance in determining the response of corals to ocean acidification. Here, we investigate pHCF in the coral Stylophora pistillata in seawater maintained at constant pH with manipulated carbonate chemistry to alter dissolved inorganic carbon (DIC) concentration, and therefore total alkalinity (AT). We also investigate the intracellular pH of calcifying cells, photosynthesis, respiration and calcification rates under the same conditions. Our results show that despite constant pH in the surrounding seawater, pHCF is sensitive to shifts in carbonate chemistry associated with changes in [DIC] and [AT], revealing that seawater pH is not the sole driver of pHCF. Notably, when we synthesize our results with published data, we identify linear relationships of pHCF with the seawater [DIC]/[H+] ratio, [AT]/ [H+] ratio and []. Our findings contribute new insights into the mechanisms determining the sensitivity of coral calcification to changes in seawater carbonate chemistry, which are needed for predicting effects of environmental change on coral reefs and for robust interpretations of isotopic palaeoenvironmental records in coral skeletons. PMID:28100813

The Drenchwater deposit, Alaska: An example of a natural low pH environment resulting from weathering of an undisturbed shale-hosted Zn-Pb-Ag deposit

USGS Publications Warehouse

Graham, G.E.; Kelley, K.D.

2009-01-01

The Drenchwater shale-hosted Zn-Pb-Ag deposit and the immediate vicinity, on the northern flank of the Brooks Range in north-central Alaska, is an ideal example of a naturally low pH system. The two drainages, Drenchwater and False Wager Creeks, which bound the deposit, differ in their acidity and metal contents. Moderately acidic waters with elevated concentrations of metals (pH ??? 4.3, Zn ??? 1400 ??g/L) in the Drenchwater Creek drainage basin are attributed to weathering of an exposed base-metal-rich massive sulfide occurrence. Stream sediment and water chemistry data collected from False Wager Creek suggest that an unexposed base-metal sulfide occurrence may account for the lower pH (2.7-3.1) and very metal-rich waters (up to 2600 ??g/L Zn, ??? 260 ??g/L Cu and ???89 ??g/L Tl) collected at least 2 km upstream of known mineralized exposures. These more acidic conditions produce jarosite, schwertmannite and Fe-hydroxides commonly associated with acid-mine drainage. The high metal concentrations in some water samples from both streams naturally exceed Alaska state regulatory limits for freshwater aquatic life, affirming the importance of establishing base-line conditions in the event of human land development. The studies at the Drenchwater deposit demonstrate that poor water quality can be generated through entirely natural weathering of base-metal occurrences, and, possibly unmineralized black shale.

Installation Restoration Program. Phase 2. Confirmation/Quantification Stage 1. US Air Force Plant Number 42, Palmdale, California. Volume 1

DTIC Science & Technology

1987-02-20

Bacteriology; 8 years professional experience; served as Project Health and Safety Officer. 1-37 o Duane R. Boline - Ph.D. in Analytical Chemistry ; M.S. in... Chemistry ; B.S.E. in Physical Science; 18 years professional experience; served as Project Quality Assurance Officer. Complete biographical data...University, 1962 M.S., Chemistry , Einporia State University 1965 Ph.D., Analytical Chemistry , Kansas State University, 1975

Relations of habitat-specific algal assemblages to land use and water chemistry in the Willamette Basin, Oregon

USGS Publications Warehouse

Carpenter, K.D.; Waite, I.R.

2000-01-01

Benthic algal assemblages, water chemistry, and habitat were characterized at 25 stream sites in the Willamette Basin, Oregon, during low flow in 1994. Seventy-three algal samples yielded 420 taxa - Mostly diatoms, blue-green algae, and green algae. Algal assemblages from depositional samples were strongly dominated by diatoms (76% mean relative abundance), whereas erosional samples were dominated by blue-green algae (68% mean relative abundance). Canonical correspondence analysis (CCA) of semiquantitative and qualitative (presence/absence) data sets identified four environmental variables (maximum specific conductance, % open canopy, pH, and drainage area) that were significant in describing patterns of algal taxa among sites. Based on CCA, four groups of sites were identified: Streams in forested basins that supported oligotrophic taxa, such as Diatoma mesodon; small streams in agricultural and urban basins that contained a variety of eutrophic and nitrogen-heterotrophic algal taxa; larger rivers draining areas of mixed land use that supported planktonic, eutrophic, and nitrogen-heterotrophic algal taxa; and streams with severely degraded or absent riparian vegetation (> 75% open canopy) that were dominated by other planktonic, eutrophic, and nitrogen-heterotrophic algal taxa. Patterns in water chemistry were consistent with the algal autecological interpretations and clearly demonstrated relationships between land use, water quality, and algal distribution patterns.

Heterogeneous Atmospheric Chemistry of Lead Oxide Particles with Nitrogen Dioxide Increases Lead Solubility: Environmental and Health Implications

PubMed Central

Baltrusaitis, Jonas; Chen, Haihan; Rubasinghege, Gayan

2012-01-01

Heterogeneous chemistry of nitrogen dioxide with lead-containing particles is investigated to better understand lead metal mobilization in the environment. In particular, PbO particles, a model lead-containing compound due to its wide spread presence as a component of lead paint and as naturally occurring minerals, massicot and litharge, are exposed to nitrogen dioxide at different relative humidity. X-ray photoelectron spectroscopy (XPS) shows that upon exposure to nitrogen dioxide the surface of PbO particles react to form adsorbed nitrates and lead nitrate thin films with the extent of formation of nitrate relative humidity dependent. Surface adsorbed nitrate increases the amount of dissolved lead. These reacted particles are found to have an increase in the amount of lead that dissolves in aqueous suspensions at circumneutral pH compared to unreacted particles. These results point to the potential importance and impact that heterogeneous chemistry with trace atmospheric gases can have on increasing solubility and therefore the mobilization of heavy metals, such as lead, in the environment. This study also show that surface intermediates, such as adsorbed nitrates, that form can yield higher concentrations of lead in water systems. In the environment, these water systems can include drinking water, ground water, estuaries and lakes. PMID:23057678

Breeding biology of the spotted salamander Ambystoma maculatum (Shaw) in acidic temporary ponds at Cape Cod, USA

USGS Publications Warehouse

Portnoy, J.W.

1990-01-01

The relationship between water chemistry and breeding success of spotted salamanders Ambystoma maculatum (Shaw) was examined in temporary woodland ponds on outer Cape Cod, Massachusetts in 1985 and 1986. Most pond waters were dilute (3median coductivity = 57 umhos cm-1 (1 umhos cm-1 = 0?1 mSm-1)), acidic (median pH = 4?82), and highly colored (median = 140 Pt-Co units). Most acidity was due to abundant organic acids. Salamander survival to hatching was over 80% at 8 of 12 ponds monitored. Complete mortality, preceded by gross abnormalities, was observed only among embryos in the most acidic spawning pond (pH 4?3-4?5) in both years. Embryo transfers between ponds and laboratory studies indicated that reduced survival was due to the interaction of low pH with high tannin-lignin concentration. The use of amphibian embryonic survival to indicate acid rain effects is complicated by multiple habitat parameters and should only be attempted in conjunction with long-term population monitoring.

Bacterial Abundance and Activity across Sites within Two Northern Wisconsin Sphagnum Bogs.

PubMed

Fisher; Graham; Graham

1998-11-01

Abstract Bacterial abundance, temperature, pH, and dissolved organic carbon (DOC) concentration were compared across surface sites within and between two northern Wisconsin Sphagnum peatlands over the summer seasons in 1995 and 1996. Sites of interest were the Sphagnum mat surface, the water-filled moat (lagg) at the bog margin, and the bog lake littoral zone. Significant differences in both bacterial populations and water chemistry were observed between sites. pH was highest in the lake and lowest in the mat at both bogs; the opposite was true for DOC. Large populations of bacteria were present in surface interstitial water from the mat; abundance in this site was consistently higher than in the moat or lake. Bacterial abundance also increased across sites of increasing DOC concentration and declining pH. Bacterial activities (rates of [3H]leucine incorporation) and growth in dilution cultures (with grazers removed) were also assessed in lake, moat, and mat sites. Results using these measures generally supported the trends observed in abundance, although high rates of [3H]leucine incorporation were recorded in the moat at one of the bogs. Our results indicate that bacterial populations in Sphagnum peatlands are not adversely affected by acidity, and that DOC may be more important than pH in determining bacterial abundance in these environments.

Microbial population in cloud water at the Puy de Dôme: Implications for the chemistry of clouds

NASA Astrophysics Data System (ADS)

Amato, Pierre; Ménager, Matthieu; Sancelme, Martine; Laj, Paolo; Mailhot, Gilles; Delort, Anne-Marie

Airborne micro-organisms are ubiquitous in the atmosphere where they can remain alive and be transported over long distances, thus colonizing new environments. Despite their great importance in relation to ecological and socio-economical issues (bio-terrorism, health, etc.) very few studies have been carried out in this field. In this study, the structure of the microbial community present in atmospheric water samples from clouds at the Puy de Dôme (alt 1465 m, Massif Central, France) is described and the metabolic potential of some bacteria is investigated. The total microflora has been quantified by epifluorescence microscopy, while the cultivable aerobic micro-organisms were isolated. Bacteria were identified by 16S DNA sequencing and fungi by morphological criteria. The total bacterial count reached about 3×10 4 cells m -3 of cloud volume (1×10 5 cells mL -1 of cloud water), of which less than 1% are cultivable. Most of the isolated micro-organisms, including 12 fungal and 17 bacterial strains, are described here for the first time in atmospheric water. Many bacterial strains seem to be adapted to the extreme conditions found in cloud water (pH, T°, UV radiations, etc.). Comparison of the two samples (March 2003) shows that pH can be a major factor controlling the structure of this community: an acidic pH (Sample 1: pH=4, 9) favours the presence of fungi and spore-forming bacteria, while a more neutral pH (Sample 2: pH=5, 8) favours greater biodiversity. We have also shown, using in situ 1H NMR, that most of the isolated bacteria are able to degrade various organic substrates such as formate, acetate, lactate, methanol and formaldehyde which represent the major organic compounds present in cloud water. In addition, the detection of intermediates indicated preferential metabolic routes for some of the strains.

Calcification responses to diurnal variation in seawater carbonate chemistry by the coral Acropora formosa

NASA Astrophysics Data System (ADS)

Chan, W. Y.; Eggins, S. M.

2017-09-01

Significant diurnal variation in seawater carbonate chemistry occurs naturally in many coral reef environments, yet little is known of its effect on coral calcification. Laboratory studies on the response of corals to ocean acidification have manipulated the carbonate chemistry of experimental seawater to compare calcification rate changes under present-day and predicted future mean pH/Ωarag conditions. These experiments, however, have focused exclusively on differences in mean chemistry and have not considered diurnal variation. The aim of this study was to compare calcification responses of branching coral Acropora formosa under conditions with and without diurnal variation in seawater carbonate chemistry. To achieve this aim, we explored (1) a method to recreate natural diurnal variation in a laboratory experiment using the biological activities of a coral-reef mesocosm, and (2) a multi-laser 3D scanning method to accurately measure coral surface areas, essential to normalize their calcification rates. We present a cost- and time-efficient method of coral surface area estimation that is reproducible within 2% of the mean of triplicate measurements. Calcification rates were compared among corals subjected to a diurnal range in pH (total scale) from 7.8 to 8.2, relative to those at constant pH values of 7.8, 8.0 or 8.2. Mean calcification rates of the corals at the pH 7.8-8.2 (diurnal variation) treatment were not statistically different from the pH 8.2 treatment and were 34% higher than the pH 8.0 treatment despite similar mean seawater pH and Ωarag. Our results suggest that calcification of adult coral colonies may benefit from diurnal variation in seawater carbonate chemistry. Experiments that compare calcification rates at different constant pH without considering diurnal variation may have limitations.

Adsorption of aquatic humic substances on colloidal-size aluminum oxide particles: Influence of solution chemistry

NASA Astrophysics Data System (ADS)

Schlautman, Mark A.; Morgan, James J.

1994-10-01

The adsorption of Suwannee River humic substances (HS) on colloidal-size aluminum oxide particles was examined as a function of solution chemistry. The amount of humic acid (HA) or fulvic acid (FA) adsorbed decreased with increasing pH for all solutions of constant ionic strength. In NaCl solutions at fixed pH values, the adsorption of HA and FA increased with increasing ionic strength. The presence of Ca 2+ enhanced the adsorption of HA but had little effect on FA. For identical solution conditions, the amount (by mass) of HA adsorbed to alumina was always greater than FA. Adsorption densities for both HA and FA showed good agreement with the Langmuir equation, and interpretations of adsorption processes were made from the model parameters. For FA, ligand exchange appears to be the dominant adsorption reaction for the conditions studied here. Ligand exchange is also a major adsorption reaction for HA; however, other reactions contribute to adsorption for some solution compositions. At high pH, cation and water bridging become increasingly important for HA adsorption with increasing amounts of Na + and Ca 2+, respectively. At low to neutral pH values, increases in these same two cations make hydrophobic bonding more effective. Calculations of HS carboxyl group densities in the adsorbed layer support the proposed adsorption reactions. From the adsorption data it appears that fewer than 3.3 HS-COO - groups per nm 2 can be bound directly as inner-sphere complexes by the alumina surface. We propose that the influence of aqueous chemistry on HS adsorption reactions, and therefore on the types of HS surface complexes formed, affects the formation and nature of organic coatings on mineral surfaces.

Chemistry of Hot Spring Pool Waters in Calamba and Los Banos and Potential Effect on the Water Quality of Laguna De Bay

NASA Astrophysics Data System (ADS)

Balangue, M. I. R. D.; Pena, M. A. Z.; Siringan, F. P.; Jago-on, K. A. B.; Lloren, R. B.; Taniguchi, M.

2014-12-01

Since the Spanish Period (1600s), natural hot spring waters have been harnessed for balneological purposes in the municipalities of Calamba and Los Banos, Laguna, south of Metro Manila. There are at more than a hundred hot spring resorts in Brgy. Pansol, Calamba and Tadlac, Los Banos. These two areas are found at the northern flanks of Mt. Makiling facing Laguna de Bay. This study aims to provide some insights on the physical and chemical characteristics of hot spring resorts and the possible impact on the lake water quality resulting from the disposal of used water. Initial ocular survey of the resorts showed that temperature of the pool water ranges from ambient (>300C) to as high as 500C with an average pool size of 80m3. Water samples were collected from a natural hot spring and pumped well in Los Banos and another pumped well in Pansol to determine the chemistry. The field pH ranges from 6.65 to 6.87 (Pansol springs). Cation analysis revealed that the thermal waters belonged to the Na-K-Cl-HCO3 type with some trace amount of heavy metals. Methods for waste water disposal are either by direct discharge down the drain of the pool or by discharge in the public road canal. Both methods will dump the waste water directly into Laguna de Bay. Taking in consideration the large volume of waste water used especially during the peak season, the effect on the lake water quality would be significant. It is therefore imperative for the environmental authorities in Laguna to regulate and monitor the chemistry of discharges from the pool to protect both the lake water as well as groundwater quality.

Monitoring and assessment of ocean acidification in the Arctic Ocean-A scoping paper

USGS Publications Warehouse

Robbins, Lisa L.; Yates, Kimberly K.; Feely, Richard; Fabry, Victoria

2010-01-01

Carbon dioxide (CO2) in the atmosphere is absorbed at the ocean surface by reacting with seawater to form a weak, naturally occurring acid called carbonic acid. As atmospheric carbon dioxide increases, the concentration of carbonic acid in seawater also increases, causing a decrease in ocean pH and carbonate mineral saturation states, a process known as ocean acidification. The oceans have absorbed approximately 525 billion tons of carbon dioxide from the atmosphere, or about one-quarter to one-third of the anthropogenic carbon emissions released since the beginning of the Industrial Revolution. Global surveys of ocean chemistry have revealed that seawater pH has decreased by about 0.1 units (from a pH of 8.2 to 8.1) since the 1700s due to absorption of carbon dioxide (Raven and others, 2005). Modeling studies, based on Intergovernmental Panel on Climate Change (IPCC) CO2 emission scenarios, predict that atmospheric carbon dioxide levels could reach more than 500 parts per million (ppm) by the middle of this century and 800 ppm by the year 2100, causing an additional decrease in surface water pH of 0.3 pH units. Ocean acidification is a global threat and is already having profound and deleterious effects on the geology, biology, chemistry, and socioeconomic resources of coastal and marine habitats. The polar and sub-polar seas have been identified as the bellwethers for global ocean acidification.

[Dissolved aluminum and organic carbon in soil solution under six tree stands in Lushan forest ecosystems].

PubMed

Wang, Lianfeng; Pan, Genxing; Shi, Shengli; Zhang, Lehua; Huang, Mingxing

2003-10-01

Different depths of soils under 6 tree stands in Lushan Botany Garden were sampled and water-digested at room temperature. The dissolved aluminum and organic carbon were then determined by colorimetry, using 8-hydroxylquilin and TOC Analyzer, respectively. The results indicated that even derived from a naturally identical soil type, the test soils exhibited a diverse solution chemistry, regarding with the Al speciation. The soil solutions under Japanese cedar, giant arborvitae and tea had lower pH values and higher contents of soluble aluminum than those under Giant dogwood, azalea and bamboo. Under giant arborvitae, the lowest pH and the highest content of total soluble aluminum and monomeric aluminum were found in soil solution. There was a significant correlation between soluble aluminum and DOC, which tended to depress the accumulation of toxic monomeric aluminum. The 6 tree stands could be grouped into 2 categories of solution chemistry, according to aluminum mobilization.

Hydrogeochemical analysis and evaluation of surface water quality of Pratapgarh district, Uttar Pradesh, India

NASA Astrophysics Data System (ADS)

Tiwari, Ashwani Kumar; Singh, Abhay Kumar; Singh, Amit Kumar; Singh, M. P.

2017-07-01

The hydrogeochemical study of surface water in Pratapgarh district has been carried out to assess the major ion chemistry and water quality for drinking and domestic purposes. For this purpose, twenty-five surface water samples were collected from river, ponds and canals and analysed for pH, electrical conductivity, total dissolved solids (TDS), turbidity, hardness, major cations (Ca2+, Mg2+, Na+ and K+), major anions (HCO3 -, F-, Cl-, NO3 -, SO4 2-) and dissolved silica concentration. The analytical results show mildly acidic to alkaline nature of surface water resources of Pratapgarh district. HCO3 - and Cl- are the dominant anions, while cation chemistry is dominated by Na+ and Ca2+. The statistical analysis and data plotted on the Piper diagram reveals that the surface water chemistry is mainly controlled by rock weathering with secondary contributions from agriculture and anthropogenic sources. Ca2+-Mg2+-HCO3 -, Ca2+-Mg2+-Cl- and Na+-HCO3 --Cl- are the dominant hydrogeochemical facies in the surface water of the area. For quality assessment, values of analysed parameters were compared with Indian and WHO water quality standards, which shows that the concentrations of TDS, F-, NO3 -, Na+, Mg2+ and total hardness are exceeding the desirable limits in some water samples. Water Quality Index (WQI) is one of the most effective tools to communicate information on the quality of any water body. The computed WQI values of Pratapgarh district surface water range from 28 to 198 with an average value of 82, and more than half of the study area is under excellent to good category.

Chemistry of silica scale mitigation for RO desalination with particular reference to remote operations.

PubMed

Milne, Nicholas A; O'Reilly, Tom; Sanciolo, Peter; Ostarcevic, Eddy; Beighton, Mark; Taylor, Kelvin; Mullett, Mark; Tarquin, Anthony J; Gray, Stephen R

2014-11-15

Silica scaling in reverse osmosis of groundwater is a significant issue in water stressed areas due to the limitations that scaling imposes on water recovery. While calcium and magnesium scaling potential can be significantly reduced by the use of ion exchange or other softening processes, the silica scaling potential typically remains. Improving the recovery of reverse osmosis by limiting the potential for silica scale is important in ensuring maximum water recovery. This is particularly important for mining and natural gas industries that are located in remote regions. The remote nature of these sites imposes three major restrictions on the silica scale mitigation process. Firstly, the generation of poorly dewaterable sludges must be avoided. Also, the quality of any reverse osmosis (RO) permeate must be able to meet the end use requirements, particularly for boilers. Finally, silica removal should not impact upon other potentially useful or valuable components within the brine, and should not make the disposal of the unusable waste brine components more difficult. Reduction of scaling potential can be achieved in three main ways: operating RO at high pH after hardness has been removed, operating at low pH, and reducing the silica concentration either in pretreatment or by using an interstage technique. Operating at high pH has the initial requirement of hardness removal to prevent scaling and this could be an issue on some sites. Hardness removal operations that use ion exchange resins may be challenged by water chemistry and the operational costs associated with high chemical regeneration costs. Operating at low pH may be more desirable than high pH operation as this can help to reduce the risk of scale formation from calcium or magnesium salts. The drawback comes from the cost of acid, particularly for high-alkalinity waters. There are numerous silica removal techniques including chemical dosing of lime, or aluminium or iron salts, electrocoagulation, adsorption, ion exchange and seeded precipitation. Of these, adsorption onto aluminium compounds appears to give the best results and have received the most attention where restrictions on sludge production and brine disposal common to operations in remote locations are in place. Adsorption onto iron compounds appears to occur more quickly, but leads to the formation of a hard, glass-like scale that may be more difficult to remove, making this process unattractive from the point of view of sorbent regeneration. Crown Copyright © 2014. Published by Elsevier Ltd. All rights reserved.

Comparison of Hydrazone Heterobifunctional Crosslinking Agents for Reversible Conjugation of Thiol-Containing Chemistry

PubMed Central

Christie, R. James; Anderson, Diana J.; Grainger, David W.

2010-01-01

Reversible covalent conjugation chemistries that allow site- and condition-specific coupling and uncoupling reactions are attractive components in nanotechnologies, bioconjugation methods, imaging and drug delivery systems. Here, we compare three heterobifunctional crosslinkers, containing both thiol- and amine- reactive chemistry, to form pH-labile hydrazones with hydrazide derivatives of the known and often published water-soluble polymer, poly[N-(2-hydroxypropyl methacrylamide)] (pHPMA), while subsequently coupling thiol-containing molecules to the crosslinker via maleimide addition. Two novel crosslinkers were prepared from the popular heterobifunctional crosslinking agent, succinimidyl-4-(N-maleimidomethyl) cyclohexane-1-carboxylate (SMCC), modified to contain either terminal aldehyde groups (i.e., 1-(N-3-propanal)-4-(N-maleimidomethyl) cyclohexane carboxamide, PMCA) or methylketone groups (i.e., 1-(N-3-butanone)-4-(N-maleimidomethyl) cyclohexane carboxamide, BMCA). A third crosslinking agent was the commercially available N-4-acetylphenyl maleimide (APM). PMCA and BMCA exhibited excellent reactivity towards hydrazide-derivatized pHPMA with essentially complete hydrazone conjugation to polymer reactive sites, while APM coupled only ~ 60% of available reactive sites on the polymer despite a 3-fold molar excess relative to polymer hydrazide groups. All polymer hydrazone conjugates bearing these bifunctional agents were then further reacted with thiol-modified tetramethylrhodamine dye, confirming crosslinker maleimide reactivity after initial hydrazone polymer conjugation. Incubation of dye-labeled polymer conjugates in phosphate buffered saline at 37°C showed that hydrazone coupling resulting from APM exhibited the greatest difference in stability between pH 7.4 and 5.0, with hydrolysis and dye release increased at pH 5.0 over a 24hr incubation period. Polymer conjugates bearing hydrazones formed from crosslinker BMCA exhibited intermediate stability with hydrolysis much greater at pH 5.0 at early time points, but hydrolysis at pH 7.4 was significant after 5 hrs. Hydrazones formed with the PMCA crosslinker showed no difference in release rates at pH 7.4 and 5.0. PMID:20695431

Water chemistry of tundra lakes in the periglacial zone of the Bellsund Fiord (Svalbard) in the summer of 2013.

PubMed

Szumińska, Danuta; Szopińska, Małgorzata; Lehmann-Konera, Sara; Franczak, Łukasz; Kociuba, Waldemar; Chmiel, Stanisław; Kalinowski, Paweł; Polkowska, Żaneta

2018-05-15

Climate changes observed in the Arctic (e.g. permafrost degradation, glacier retreat) may have significant influence on sensitive polar wetlands. The main objectives of this paper are defining chemical features of water within six small arctic lakes located in Bellsund (Svalbard) in the area of continuous permafrost occurrence. The unique environmental conditions of the study area offer an opportunity to observe phenomena influencing water chemistry, such as: chemical weathering, permafrost thawing, marine aerosols, atmospheric deposition and biological inputs. In the water samples collected during the summer 2013, detailed tundra lake water chemistry characteristics regarding ions, trace elements, pH and specific electrolytic conductivity (SEC 25 ) analysis were determined. Moreover, water chemistry of the studied lakes was compared to the water samples from the Tyvjobekken Creek and precipitation water samples. As a final step of data analysis, Principal Component Analysis (PCA) was performed. Detailed chemical analysis allowed us to conclude what follows: (1) Ca 2+ , Mg 2+ , SO 4 2- , Sr are of geogenic origin, (2) NO 3 - present in tundra lakes and the Tyvjobekken Creek water samples (ranging from 0.31 to 1.69mgL - 1 and from 0.25 to 1.58mgL - 1 respectively) may be of mixed origin, i.e. from biological processes and permafrost thawing, (3) high contribution of non-sea-salt SO 4 2- >80% in majority of studied samples indicate considerable inflow of sulphate-rich air to the study area, (4) high content of chlorides in tundra lakes (range: 25.6-32.0% meqL - 1 ) indicates marine aerosol influence, (5) PCA result shows that atmospheric transport may constitute a source of Mn, Co, Ni, Cu, Ga, Ba and Cd. However, further detailed inter-season and multi-seasonal study of tundra lakes in the Arctic are recommended. Especially in terms of detailed differentiation of sources influence (atmospheric transport vs. permafrost degradation). Copyright © 2017 Elsevier B.V. All rights reserved.

Green Synthesis of Novel Polyaniline Nanofibers: Application in pH Sensing.

PubMed

Tanwar, Shivani; Ho, Ja-an Annie

2015-10-13

An optically active polyaniline nanomaterial (PANI-Nap), doped with (S)-naproxen, was developed and evaluated as a potent pH sensor. We synthesized the material in one pot by the addition of the dopant, (S)-naproxen, prior to polymerization, followed by the addition of the oxidizing agent (ammonium persulfate) that causes polymerization of the aniline. This green chemistry approach allowed us to take only 1 h to produce a water-soluble and stable nanomaterial. UV-visible spectroscopy, fluorescence spectroscopy, FT-IR spectroscopy, Raman spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS) were used to characterize the designed nanomaterial. This nanomaterial exhibited excellent pH sensing properties and showed long term stability (up to one month) without loss of sensor performance.

Water chemistry in the rives of the permafrost regions on the eastern Qinghai-Tibetan Plateau

NASA Astrophysics Data System (ADS)

Wu, X.; Ma, X.; Ye, L.; Liu, G.

2017-12-01

Qinghai-Tibetan is the largest middle-low latitude permafrost areas on the world. There are several large rivers in the plateau, and the changes of the water resources of these rivers are associated with the water resource security of more than 1.35 billion people. Due to the high gradients, these rivers have a tremendous amount of potential energy for electricity output. To promote economic and social development and provide clean energy, hydropower development has taken place on several rivers which originate on the Qinghai-Tibetan Plateau. Since dam construction affect the flow velocity, water temperature, sediments delivery as well as organic matter and nitrogen, it is important to investigate the river chemistry in the head rivers of the reservoirs. We examined the water physio-chemical characteristics in the rivers under the typical vegetation types in the eastern Qinghai-Tibetan Plateau, and further analyzed their relationship to vegetation. The results showed that the total suspended sediment in the rivers were higher within the catchment of alpine steppe, with the lowest dissolved organic carbon content. In contrast, the rivers within the meadow had the highest dissolved organic carbon and lowest total suspension sediment. The dissolved organic carbon significantly positively correlated with the proportions of the meadow and wet meadow in the catchment. The pH, turbidity, and SUVA254 and dissolved organic carbon also correlated with each other. The results suggest that the vegetation type strongly affect the water chemistry in the permafrost regions on the Qinghai-Tibetan Plateau.

Experiments on the Multiphase Chemistry of Isocyanic Acid, HNCO.

NASA Astrophysics Data System (ADS)

Roberts, J. M.; Liu, Y.

2015-12-01

Isocyanic acid, HNCO, has emerged as a potentially important reduced nitrogen compound that is emitted in wildfires, and may have health effect implications. The extent of the health effects depends on the solubility of HNCO in aqueous and non-aqueous solutions and the relative rates of hydrolysis versus carbamylation reactions (for example: HNCO + ROH => H2NC(O)OR). We report here results of studies of HNCO solubility and its reaction in buffered aqueous solutions (pH3), tridecane, and n-octanol at temperatures over the range 5 to 37°C. From these data, the heats of solution and activation energy of hydrolysis are estimated, and a partition coefficient between n-octanol and water at 25°C is greater than 1 for low pH solutions, indicating appreciable portioning to a non-polar phase, but HNCO will be distributed mostly in the aqueous phase at neutral pH. In addition, it was found that the rate of reaction of HNCO with n-octanol was competitive with hydrolysis under physiologically relevant conditions (pH7.4, 37°C), indicating that carbamylation of ROH groups could be significant. Based on these results, research on the carbamylation of other functional groups, and solubility and reaction studies of other isocyanates (e.g. CH3NCO) are warranted. The implications of this multi-phase chemistry for global exposures to wildfire emissions will be discussed.

Aspects of Solvent Chemistry for Calcium Hydroxide Medicaments

PubMed Central

Athanassiadis, Basil

2017-01-01

Calcium hydroxide pastes have been used in endodontics since 1947. Most current calcium hydroxide endodontic pastes use water as the vehicle, which limits the dissolution of calcium hydroxide that can be achieved and, thereby, the maximum pH that can be achieved within the root canal system. Using polyethylene glycol as a solvent, rather than water, can achieve an increase in hydroxyl ions release compared to water or saline. By adopting non-aqueous solvents such as the polyethylene glycols (PEG), greater dissolution and faster hydroxyl ion release can be achieved, leading to enhanced antimicrobial actions, and other improvements in performance and biocompatibility. PMID:29065542

Coral records of reef-water pH across the central Great Barrier Reef, Australia: assessing the influence of river runoff on inshore reefs

NASA Astrophysics Data System (ADS)

D'Olivo, J. P.; McCulloch, M. T.; Eggins, S. M.; Trotter, J.

2015-02-01

The boron isotopic (δ11Bcarb) compositions of long-lived Porites coral are used to reconstruct reef-water pH across the central Great Barrier Reef (GBR) and assess the impact of river runoff on inshore reefs. For the period from 1940 to 2009, corals from both inner- and mid-shelf sites exhibit the same overall decrease in δ11Bcarb of 0.086 ± 0.033‰ per decade, equivalent to a decline in seawater pH (pHsw) of ~0.017 ± 0.007 pH units per decade. This decline is consistent with the long-term effects of ocean acidification based on estimates of CO2 uptake by surface waters due to rising atmospheric levels. We also find that, compared to the mid-shelf corals, the δ11Bcarb compositions of inner-shelf corals subject to river discharge events have higher and more variable values, and hence higher inferred pHsw values. These higher δ11Bcarb values of inner-shelf corals are particularly evident during wet years, despite river waters having lower pH. The main effect of river discharge on reef-water carbonate chemistry thus appears to be from reduced aragonite saturation state and higher nutrients driving increased phytoplankton productivity, resulting in the drawdown of pCO2 and increase in pHsw. Increased primary production therefore has the potential to counter the more transient effects of low-pH river water (pHrw) discharged into near-shore environments. Importantly, however, inshore reefs also show a consistent pattern of sharply declining coral growth that coincides with periods of high river discharge. This occurs despite these reefs having higher pHsw, demonstrating the overriding importance of local reef-water quality and reduced aragonite saturation state on coral reef health.

Major Cation, Carbon System and Trace Element Chemistry in Pore Waters from a Depth Transect of Cores on the Iberian Margin: Implications for Paleoproxies.

NASA Astrophysics Data System (ADS)

Greaves, M.; Elderfield, H.; Hodell, D. A.; Skinner, L. C.; Sevilgen, D.; Grauel, A. L.; de la Fuente, M.; Misra, S.

2014-12-01

A significant body of work exists on the chemistry of pore waters from DSDP and ODP drilling cores (e.g. Gieskes 1975; Sayles 1981) showing large gradients in sea salt cations and anions interpreted in terms of diagenetic reactions such as the formation of Mg-rich clays and dolomite formation (Higgins and Schrag, 2010). Another class of diagenetic reactions involves the breakdown of organic matter and trace element behaviour (Froelich et al., 1979). The translation of chemical gradients into fluxes requires estimates of pore water chemistry across the sea water - sediment surface boundary. Additionally, the use of the chemistry of benthic foraminiferal calcite for seawater paleochemistry requires estimation of the chemistry of pore waters which may differ from that of bottom seawater because of diagenetic reactions. In this work we have collected multi core samples from 10 core sites on cruise RRS James Cook JC089 on the southwest Iberian continental margin. Pore waters were extracted from the core surface and at 1 cm depth intervals down core (typically to ~40 cm depth) using Rhizon samplers and analysed for Alkalinity, DIC, ∂13C and Na, K, Mg, Ca, Li, Mn, Fe, Ba, B, Sr by atomic emission spectrophotometry as well as O2 penetration and pH by microelectrodes. This has allowed us to inspect chemical behavior at the bottom water - sediment interface. Some examples of results are a large gradient in ∂13C of DIC, the similarity of zero O2 penetration followed by an increase in Mn concentration and then decrease to zero, the similarity of Li to Mn and, in contrast to much DSDP/ODP work, Ca2+ and Mg2+both decrease with depth in pore waters near the sediment surface. References: Gieskes J.M. Annu. Rev. Earth Planet. Sci. 3, 433 (1975). Sayles F. L. Geochim. Cosmochim. Acta45, 1061 (1981). Higgins J.A. and D.P. Schrag. Geochim. Cosmochim. Acta.74, 5039 (2010). Froelich, P.N., et al., Geochim. Cosmochim. Acta. 43, 1075 (1979).

Contained radiological analytical chemistry module

DOEpatents

Barney, David M.

1989-01-01

A system which provides analytical determination of a plurality of water chemistry parameters with respect to water samples subject to radiological contamination. The system includes a water sample analyzer disposed within a containment and comprising a sampling section for providing predetermined volumes of samples for analysis; a flow control section for controlling the flow through the system; and a gas analysis section for analyzing samples provided by the sampling system. The sampling section includes a controllable multiple port valve for, in one position, metering out sample of a predetermined volume and for, in a second position, delivering the material sample for analysis. The flow control section includes a regulator valve for reducing the pressure in a portion of the system to provide a low pressure region, and measurement devices located in the low pressure region for measuring sample parameters such as pH and conductivity, at low pressure. The gas analysis section which is of independent utility provides for isolating a small water sample and extracting the dissolved gases therefrom into a small expansion volume wherein the gas pressure and thermoconductivity of the extracted gas are measured.

Contained radiological analytical chemistry module

DOEpatents

Barney, David M.

1990-01-01

A system which provides analytical determination of a plurality of water chemistry parameters with respect to water samples subject to radiological contamination. The system includes a water sample analyzer disposed within a containment and comprising a sampling section for providing predetermined volumes of samples for analysis; a flow control section for controlling the flow through the system; and a gas analysis section for analyzing samples provided by the sampling system. The sampling section includes a controllable multiple port valve for, in one position, metering out sample of a predetermined volume and for, in a second position, delivering the material sample for analysis. The flow control section includes a regulator valve for reducing the pressure in a portion of the system to provide a low pressure region, and measurement devices located in the low pressure region for measuring sample parameters such as pH and conductivity, at low pressure. The gas analysis section which is of independent utility provides for isolating a small water sample and extracting the dissolved gases therefrom into a small expansion volume wherein the gas pressure and thermoconductivity of the extracted gas are measured.

Differential natural organic matter fouling of ceramic versus polymeric ultrafiltration membranes.

PubMed

Lee, Seung-Jin; Kim, Jae-Hong

2014-01-01

Ceramic ultrafiltration membranes has drawn increasing attention in drinking water treatment sectors as an alternative to traditional polymeric counterparts, yet only limited information has been made available about the characteristics of ceramic membrane fouling by natural organic matter. The effects of solution chemistry including ionic strength, divalent ion concentration and pH on the flux behavior were comparatively evaluated for ceramic and polymeric ultrafiltration of synthetic water containing model natural organic matter. Filtration characteristics were further probed via resistance-in-series model analysis, fouling visualization using quantum dots, batch adsorption test, contact angle measurement, solute-membrane surface adhesion force measurement, and quantitative comparison of fouling characteristics between ceramic and polymeric membranes. The results collectively suggested that the effects of solution chemistry on fouling behavior of ceramic membranes were generally similar to polymeric counterparts in terms of trends, while the extent varied significantly depending on water quality parameters. Lower fouling tendency and enhanced cleaning efficiency were observed with the ceramic membrane, further promoting the potential for ceramic membrane application to surface water treatment. Copyright © 2013 Elsevier Ltd. All rights reserved.

Forces of interactions between bare and polymer-coated iron and silica: effect of pH, ionic strength, and humic acids.

PubMed

Pensini, Erica; Sleep, Brent E; Yip, Christopher M; O'Carroll, Denis

2012-12-18

The interactions between a silica substrate and iron particles were investigated using atomic force microscopy-based force spectroscopy (AFM). The micrometer- and nanosized iron particles employed were either bare or coated with carboxymethyl cellulose (CMC), a polymer utilized to stabilize iron particle suspensions. The effect of water chemistry on the forces of interaction was probed by varying ionic strength (with 100 mM NaCl and 100 mM CaCl₂) or pH (4, 5.5, and 8) or by introducing 10 mg/L of humic acids (HA). When particles were uncoated, the forces upon approach between silica and iron were attractive at pH 4 and 5.5 and in 100 mM CaCl₂ at pH 8, but they were negligible in 100 mM NaCl buffered to pH 8 and repulsive in water buffered to pH 8 and in HA solutions. HA produced electrosteric repulsion between iron particles and silica, likely due to its sorption to iron particles. HA sorption to silica was excluded on the basis of experiments conducted with a quartz-crystal microbalance with dissipation monitoring. Repulsion with CMC-coated iron was attributed to electrosteric forces, which were damped at high ionic strength. An extended DLVO model and a modified version of Ohshima's theory were successfully utilized to model AFM data.

Locally driven interannual variability of near-surface pH and ΩA in the Strait of Georgia

NASA Astrophysics Data System (ADS)

Moore-Maley, Ben L.; Allen, Susan E.; Ianson, Debby

2016-03-01

Declines in mean ocean pH and aragonite saturation state (ΩA) driven by anthropogenic CO2 emissions have raised concerns regarding the trends of pH and ΩA in estuaries. Low pH and ΩA can be harmful to a variety of marine organisms, especially those with calcium carbonate shells, and so may threaten the productive ecosystems and commercial fisheries found in many estuarine environments. The Strait of Georgia is a large, temperate, productive estuarine system with numerous wild and aquaculture shellfish and finfish populations. We determine the seasonality and variability of near-surface pH and ΩA in the Strait using a one-dimensional, biophysical, mixing layer model. We further evaluate the sensitivity of these quantities to local wind, freshwater, and cloud forcing by running the model over a wide range of scenarios using 12 years of observations. Near-surface pH and ΩA demonstrate strong seasonal cycles characterized by low pH, aragonite-undersaturated waters in winter and high pH, aragonite-supersaturated waters in summer. The aragonite saturation horizon generally lies at ˜20 m depth except in winter and during strong Fraser River freshets when it shoals to the surface. Periods of strong interannual variability in pH and aragonite saturation horizon depth arise in spring and summer. We determine that at different times of year, each of wind speed, freshwater flux, and cloud fraction are the dominant drivers of this variability. These results establish the mechanisms behind the emerging observations of highly variable near-surface carbonate chemistry in the Strait.

Ambarish Nag | NREL

Science.gov Websites

|Mathematical biology Education Ph.D., Computational Chemistry, University of Chicago M.S., Chemistry , University of Chicago M.S., (2-Year) Chemistry, Indian Institute of Technology, Kanpur, India B.S., Chemistry

Studies of the phytoplankton and soil algae of two strip-mine impoundments in Tuscarawas County, Ohio

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

Richards, J.N.

1973-01-01

The process of strip-mining leaves vast areas that are denuded of vegetation and are open to primary succession by organisms such as algae. Acid strip-mine impoundments are either formed by man-made or natural processes. These impoundments are remnants of old strip-mine pits that have been filled with runoff water. The water chemistry of these ponds reflects the chemistry of the earth strata above the coal seam that was mined. These young impoundments or ponds are extremely low in pH and quite acidic due to the presence of great amounts of sulfuric acid. Algae that are found in these types ofmore » habitats exhibit a tolerance to acid conditions and are considered to be acidophilic. Few species of algae are known to be common componenets of these habitats.« less

A molecular molybdenum-oxo catalyst for generating hydrogen from water.

PubMed

Karunadasa, Hemamala I; Chang, Christopher J; Long, Jeffrey R

2010-04-29

A growing awareness of issues related to anthropogenic climate change and an increase in global energy demand have made the search for viable carbon-neutral sources of renewable energy one of the most important challenges in science today. The chemical community is therefore seeking efficient and inexpensive catalysts that can produce large quantities of hydrogen gas from water. Here we identify a molybdenum-oxo complex that can catalytically generate gaseous hydrogen either from water at neutral pH or from sea water. This work shows that high-valency metal-oxo species can be used to create reduction catalysts that are robust and functional in water, a concept that has broad implications for the design of 'green' and sustainable chemistry cycles.

Aluminum toxicity risk reduction as a result of reduced acid deposition in Adirondack lakes and ponds.

PubMed

Michelena, Toby M; Farrell, Jeremy L; Winkler, David A; Goodrich, Christine A; Boylen, Charles W; Sutherland, James W; Nierzwicki-Bauer, Sandra A

2016-11-01

In 1990, the US Congress amended the Clean Air Act (CAA) to reduce regional-scale ecosystem degradation from SO x and NO x emissions which have been responsible for acid deposition in regions such as the Adirondack Mountains of New York State. An ecosystem assessment project was conducted from 1994 to 2012 by the Darrin Fresh Water Institute to determine the effect of these emission reduction policies on aquatic systems. The project investigated water chemistry and biota in 30 Adirondack lakes and ponded waters. Although regulatory changes made in response to the 1990 CAA amendments resulted in a reduction of acid deposition within the Adirondacks, the ecosystem response to these reductions is complicated. A statistical analysis of SO 4 , pH, Al, and DOC data collected during this project demonstrates positive change in response to decreased deposition. The changes in water chemistry also have lowered the risk of Al toxicity to brook trout (Salvelinus fontinalis [Mitchill]), which allowed the re-introduction of this species to Brooktrout Lake from which it had been extirpated. However, pH and labile aluminum (Al im ) fluctuate and are not strongly correlated to changes in acid deposition. As such, toxicity to S. fontinalis also is cyclic and provides rationale for the difficulties inherent in re-establishing resident populations in impacted aquatic environments. Overall, aquatic ecosystems of the Adirondacks show a positive response to reduced deposition driven by changes in environmental policy, but the response is more complex and indicates an ecosystem-wide interaction between aquatic and watershed components of the ecosystem.

Trends in Ph.D. Productivity and Diversity in Top-50 U.S. Chemistry Departments: An Institutional Analysis

ERIC Educational Resources Information Center

Laursen, Sandra L.; Weston, Timothy J.

2014-01-01

The education of doctoral chemists contributes to the chemical research enterprise and thus to innovation as an engine of the economy. This quantitative analysis describes trends in the production and diversity of chemistry Ph.D. degrees in the top-50 U.S. Ph.D.-granting departments in the past two decades. Time series data for individual…

Particle water and pH in the eastern Mediterranean: source variability and implications for nutrient availability

NASA Astrophysics Data System (ADS)

Bougiatioti, Aikaterini; Nikolaou, Panayiota; Stavroulas, Iasonas; Kouvarakis, Giorgos; Weber, Rodney; Nenes, Athanasios; Kanakidou, Maria; Mihalopoulos, Nikolaos

2016-04-01

Particle water (liquid water content, LWC) and aerosol pH are important parameters of the aerosol phase, affecting heterogeneous chemistry and bioavailability of nutrients that profoundly impact cloud formation, atmospheric composition, and atmospheric fluxes of nutrients to ecosystems. Few measurements of in situ LWC and pH, however, exist in the published literature. Using concurrent measurements of aerosol chemical composition, cloud condensation nuclei activity, and tandem light scattering coefficients, the particle water mass concentrations associated with the aerosol inorganic (Winorg) and organic (Worg) components are determined for measurements conducted at the Finokalia atmospheric observation station in the eastern Mediterranean between June and November 2012. These data are interpreted using the ISORROPIA-II thermodynamic model to predict the pH of aerosols originating from the various sources that influence air quality in the region. On average, closure between predicted aerosol water and that determined by comparison of ambient with dry light scattering coefficients was achieved to within 8 % (slope = 0.92, R2 = 0.8, n = 5201 points). Based on the scattering measurements, a parameterization is also derived, capable of reproducing the hygroscopic growth factor (f(RH)) within 15 % of the measured values. The highest aerosol water concentrations are observed during nighttime, when relative humidity is highest and the collapse of the boundary layer increases the aerosol concentration. A significant diurnal variability is found for Worg with morning and afternoon average mass concentrations being 10-15 times lower than nighttime concentrations, thus rendering Winorg the main form of particle water during daytime. The average value of total aerosol water was 2.19 ± 1.75 µg m-3, contributing on average up to 33 % of the total submicron mass concentration. Average aerosol water associated with organics, Worg, was equal to 0.56 ± 0.37 µg m-3; thus, organics contributed about 27.5 % to the total aerosol water, mostly during early morning, late evening, and nighttime hours.

The aerosol was found to be highly acidic with calculated aerosol pH varying from 0.5 to 2.8 throughout the study period. Biomass burning aerosol presented the highest values of pH in the submicron fraction and the lowest values in total water mass concentration. The low pH values observed in the submicron mode and independently of air mass origin could increase nutrient availability and especially P solubility, which is the nutrient limiting sea water productivity of the eastern Mediterranean.

Cations and microbial indicators: strong relationships in waters of urban/mixed land use watersheds of Southwest, VA

NASA Astrophysics Data System (ADS)

Steele, M.; Badgley, B.

2016-12-01

Background The salinity and composition of salts in freshwater streams, rivers, and waterbodies varies substantially, often impacted by human urban, agricultural, and mining land uses. While extreme fluctuations in salinity have been shown to influence both microbial communities and biogeochemical cycles, the differential effects of specific ion species at low salinity levels is poorly understood. The objective of this study was to examine the relationship between water chemistry and microbial water quality indicators. We collected weekly grab samples from nine sub-watersheds in Southwest Virginia. Samples were measured for standard physical and chemical properties: dissolved oxygen, temperature, specific conductance, pH, calcium, magnesium, potassium, chloride, fluoride, sulfate, nitrogen species, phosphorus, and dissolved organic carbon. In addition, three types of microbial fecal indicators were measured: total coliforms, E. coli, and HF183 (a human specific genomic marker). Results The relationships within and between water chemistry and water quality indicators are complex and frequently co-correlated. Concentrations of traditional biogeochemical elements (N, P, C) were less strongly related to water quality indicators than were Ca, Mg, Na in watersheds. Ca and Mg were strongly correlated with total coliforms, r2 = 0.88 and r2 = 0.86 respectively. While potassium is very strongly related to E. coli (r2 = 0.96). Currently, we cannot reasonably explain these relationships by the land use composition or common sources within the landscape. The human specific fecal indicator was not well correlated with other microbial water quality indicators, and yet found ubiquitously across the developed watersheds and most strongly correlated with sodium concentrations (r2 = 0.84). The results suggest that 1) wastewater via subsurface flowpaths may more broadly impact surface water chemistry and quality than expected, and 2) that cation chemistry may influence the microbial community and serve as a mediator of watershed biogeochemical cycling.

Synoptic sampling and principal components analysis to identify sources of water and metals to an acid mine drainage stream.

PubMed

Byrne, Patrick; Runkel, Robert L; Walton-Day, Katherine

2017-07-01

Combining the synoptic mass balance approach with principal components analysis (PCA) can be an effective method for discretising the chemistry of inflows and source areas in watersheds where contamination is diffuse in nature and/or complicated by groundwater interactions. This paper presents a field-scale study in which synoptic sampling and PCA are employed in a mineralized watershed (Lion Creek, Colorado, USA) under low flow conditions to (i) quantify the impacts of mining activity on stream water quality; (ii) quantify the spatial pattern of constituent loading; and (iii) identify inflow sources most responsible for observed changes in stream chemistry and constituent loading. Several of the constituents investigated (Al, Cd, Cu, Fe, Mn, Zn) fail to meet chronic aquatic life standards along most of the study reach. The spatial pattern of constituent loading suggests four primary sources of contamination under low flow conditions. Three of these sources are associated with acidic (pH <3.1) seeps that enter along the left bank of Lion Creek. Investigation of inflow water (trace metal and major ion) chemistry using PCA suggests a hydraulic connection between many of the left bank inflows and mine water in the Minnesota Mine shaft located to the north-east of the river channel. In addition, water chemistry data during a rainfall-runoff event suggests the spatial pattern of constituent loading may be modified during rainfall due to dissolution of efflorescent salts or erosion of streamside tailings. These data point to the complexity of contaminant mobilisation processes and constituent loading in mining-affected watersheds but the combined synoptic sampling and PCA approach enables a conceptual model of contaminant dynamics to be developed to inform remediation.

Synoptic sampling and principal components analysis to identify sources of water and metals to an acid mine drainage stream

USGS Publications Warehouse

Byrne, Patrick; Runkel, Robert L.; Walton-Day, Katie

2017-01-01

Combining the synoptic mass balance approach with principal components analysis (PCA) can be an effective method for discretising the chemistry of inflows and source areas in watersheds where contamination is diffuse in nature and/or complicated by groundwater interactions. This paper presents a field-scale study in which synoptic sampling and PCA are employed in a mineralized watershed (Lion Creek, Colorado, USA) under low flow conditions to (i) quantify the impacts of mining activity on stream water quality; (ii) quantify the spatial pattern of constituent loading; and (iii) identify inflow sources most responsible for observed changes in stream chemistry and constituent loading. Several of the constituents investigated (Al, Cd, Cu, Fe, Mn, Zn) fail to meet chronic aquatic life standards along most of the study reach. The spatial pattern of constituent loading suggests four primary sources of contamination under low flow conditions. Three of these sources are associated with acidic (pH <3.1) seeps that enter along the left bank of Lion Creek. Investigation of inflow water (trace metal and major ion) chemistry using PCA suggests a hydraulic connection between many of the left bank inflows and mine water in the Minnesota Mine shaft located to the north-east of the river channel. In addition, water chemistry data during a rainfall-runoff event suggests the spatial pattern of constituent loading may be modified during rainfall due to dissolution of efflorescent salts or erosion of streamside tailings. These data point to the complexity of contaminant mobilisation processes and constituent loading in mining-affected watersheds but the combined synoptic sampling and PCA approach enables a conceptual model of contaminant dynamics to be developed to inform remediation.

Effects of Submarine Groundwater Discharge (SGD) on the Growth of the Lobe Coral Porites lobata in Maunalua Bay, Hawaii.

NASA Astrophysics Data System (ADS)

Lubarsky, K.

2016-02-01

Submarine groundwater discharge (SGD) constitutes a large percentage of the freshwater inputs onto coastal coral reefs on high islands such as the Hawaiian Islands, although the impact of SGD on coral reef health is currently understudied. In Maunalua Bay, on Oahu, Hawaii, SGD is discharged onto shallow reef flats from discrete seeps, creating natural gradients of water chemistry across the reef flat. We used this system to investigate rates of growth of the lobe coral Porites lobata across a gradient of SGD influence at two study sites within the bay, and to characterize the variation in water chemistry gradient over space and time due to SGD. SGD input at these sites is tidally modulated, and the groundwater itself is brackish and extremely nutrient-rich (mean=190 μM NO3- at the Black Point study site, mean=40 μM NO3- at Wailupe Beach Park), with distinct carbonate signatures at both study sites. Coral nubbins were placed across the gradient for 6 months, and growth was measured using three metrics: surface area (photo analysis), buoyant weight, and linear extension. Various chemical parameters, including pH, salinity, total alkalinity, nutrients, and chlorphyll were sampled at the same locations across the gradient over 24 hour periods in the spring and fall in order to capture spatial and temporal variation in water chemistry due to the SGD plume. Spatial patterns and temporal variation in water chemistry were correlated with the observed spatial patterns in coral growth across the SGD gradient.

Diverse strategies for ion regulation in fish collected from the ion-poor, acidic Rio Negro.

PubMed

Gonzalez, R J; Wilson, R W; Wood, C M; Patrick, M L; Val, A L

2002-01-01

We measured unidirectional ion fluxes of fish collected directly from the Rio Negro, an extremely dilute, acidic blackwater tributary of the Amazon. Kinetic analysis of Na(+) uptake revealed that most species had fairly similar J(max) values, ranging from 1,150 to 1,750 nmol g(-1) h(-1), while K(m) values varied to a greater extent. Three species had K(m) values <33 micromol L(-1), while the rest had K(m) values >or=110 micromol L(-1). Because of the extremely low Na(+) concentration of Rio Negro water, the differences in K(m) values yield very different rates of Na(+) uptake. However, regardless of the rate of Na(+) uptake, measurements of Na(+) efflux show that Na(+) balance was maintained at very low Na(+) levels (<50 micromol L(-1)) by most species. Unlike other species with high K(m) values, the catfish Corydoras julii maintained high rates of Na(+) uptake in dilute waters by having a J(max) value at least 100% higher than the other species. Corydoras julii also demonstrated the ability to modulate kinetic parameters in response to changes in water chemistry. After 2 wk in 2 mmol L(-1) NaCl, J(max) fell >50%, and K(m) dropped about 70%. The unusual acclimatory drop in K(m) may represent a mechanism to ensure high rates of Na(+) uptake on return to dilute water. As well as being tolerant of extremely dilute waters, Rio Negro fish generally were fairly tolerant of low pH. Still, there were significant differences in sensitivity to pH among the species on the basis of degree of stimulation of Na(+) efflux at low pH. There were also differences in sensitivity to low pH of Na(+) uptake, and two species maintained significant rates of uptake even at pH 3.5. When fish were exposed to low pH in Rio Negro water instead of deionized water (with the same concentrations of major ions), the effects of low pH were reduced. This suggests that high concentrations of dissolved organic molecules in the water, which give it its dark tea color, may interact with the branchial epithelium in some protective manner.

Effect of deforestation on stream water chemistry in the Skrzyczne massif (the Beskid Śląski Mountains in southern Poland).

PubMed

Kosmowska, Amanda; Żelazny, Mirosław; Małek, Stanisław; Siwek, Joanna Paulina; Jelonkiewicz, Łukasz

2016-10-15

The purpose of the study was to identify the factors affecting stream water chemistry in the small mountain catchments deforested to varying degrees, from 98.7 to 14.1%, due to long-term acid deposition. Water samples were collected monthly in 2013 and 2014 from 17 streams flowing across three distinct elevation zones in the Skrzyczne massif (Poland): Upper, Middle and Lower Forest Zone. Chemical and physical analyses, including the pH, electrical conductivity (EC), total mineral content (Mt), water temperature, and the concentrations of Ca(2+), Mg(2+), Na(+), K(+), HCO3(-), SO4(2-), Cl(-), and NO3(-), were conducted. Based on Principal Component Analysis (PCA), the most important factor affecting water chemistry was human impact associated with changes in pH, SO4(2-) concentration, and the concentration of most of the main ions. The substantial acidity of the studied environment contributed to the exclusion of natural factors, associated with changes in discharge, from the list of major factors revealed by PCA. All of the streams were characterized by very low EC, Mt, and low concentrations of the main ions such as Ca(2+) and HCO3(-). This is the effect of continuous leaching of solutes from the soils by acidic precipitation. The lowest parameter values were measured for the streams situated in the Upper Forest Zone, which is associated with greater acid deposition at the higher elevations. In the streams located in the Upper Forest Zone, a higher percentage of SO4(2-) occurred than in the streams situated in the Middle and Lower Forest Zones. However, the largest share of SO4(2-) was measured in the most deforested catchment. The saturation of the studied deforested catchment with sulfur compounds is reflected by a positive correlation between SO4(2-) and discharge. Hence, a forest acts as a natural buffer that limits the level of acidity in the natural environment caused by acidic atmospheric deposition. Copyright © 2016 Elsevier B.V. All rights reserved.

Hydrothermal activity in the Lau back-arc basin: Sulfides and water chemistry

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

Fouquet, Y.; Charlou, J.L.; Donval, J.P.

1991-04-01

The submersible Nautile completed 22 dives during the Nautilau cruise (R/V Nadir, April 17-May 10, 1989) for a detailed investigation of the southern Lau basin near Tonga. The objective of the scientific team from France, Germany, and Tonga was to understand the process of sea-floor ore formation associated with hydrothermal circulation along the Valu Fa back-arc ridge behind the Tonga-Kermadec trench. The four diving areas, between lat21{degree}25'S and 22{degree}40'S in water{approximately}2000 m deep, were selected on the basis of results from cruises of the R/V Jean Charcot and R/V Sonne. The Nadir cruise provided proof of hydrothermal activity-in all formore » areas, over more than 100 km-as indicated by the widespread occurence of hydrothermal deposits and by heat flow, conductivity, and temperature measurements near the sea bottom. The most spectacular findings were high-temperature white and black smokers and associated fauna and ore deposits. Hydrothermal water chemistry and sulfide composition data presented here indicate that this hydrothermal field is very different from the hydrothermal fields in oceanic ridges. This difference is seen in water chemistry of the hydrothermal fluid (pH=2 and high metal content) and the chemical composition of sulfides (enrichment in Ba, As, and Pb).« less

Groundwater quality around Tummalapalle area, Cuddapah District, Andhra Pradesh, India

NASA Astrophysics Data System (ADS)

Sreedhar, Y.; Nagaraju, A.

2017-11-01

The suitability of groundwater for drinking and irrigation was assessed in Tummalapalle area. Forty groundwater samples were analysed for major cations, anions and other parameters such as pH, electrical conductivity, total dissolved solids (TDS), total alkalinity and total hardness (TH). The parameters such as sodium adsorption ratio, adjusted sodium adsorption ratio (adj.SAR), per cent sodium, potential salinity, residual sodium carbonate, non-carbonate hardness, Kelly's ratio and permeability index were calculated for the evaluation of irrigation water quality. Groundwater chemistry was also analysed by statistical analysis, USSL, Wilcox, Doneen, Piper and Chadhas diagrams, to find out their suitability for irrigation. TDS and TH were used as main parameters to interpret the suitability of groundwater for drinking purpose. The correlation coefficient matrix between the hydrochemical parameters was carried out using Pearson's correlation to infer the possible water-rock interactions responsible for the variation of groundwater chemistry and this has been supported by Gibbs diagram. The results indicate that the groundwater in Tummalapalle area is alkaline in nature. Ca-Mg-HCO3 is the dominant hydrogeochemical facies. Water chemistry of the study area strongly reflects the dominance of weathering of rock-forming minerals such as bicarbonates and silicates. All parameters and diagrams suggest that the water samples of the study are good for irrigation, and the plots of TDS and TH suggest that 12.5% of the samples are good for human consumption.

[(H2O)(terpy)Mn(μ-O)2Mn(terpy)(OH2)](NO3)3 (terpy = 2,2′:6,2″-terpyridine) and its relevance to the oxygen-evolving complex of photosystem II examined through pH dependent cyclic voltametry

PubMed Central

Cady, Clyde W.; Shinopoulos, Katherine E.; Crabtree, Robert H.; Brudvig, Gary W.

2010-01-01

Photosynthetic water oxidation occurs naturally at a tetranuclear manganese center in the photosystem II protein complex. Synthetically mimicking this tetramanganese center, known as the oxygen-evolving complex (OEC), has been an ongoing challenge of bioinorganic chemistry. Most past efforts have centered on water-oxidation catalysis using chemical oxidants. However, solar energy applications have drawn attention to electrochemical methods. In this paper, we examine the electrochemical behavior of the biomimetic water-oxidation catalyst [(H2O)(terpy)Mn(μ-O)2Mn(terpy)(H2O)](NO3)3 [terpy = 2,2′:6′,2″-terpyridine] (1) in water under a variety of pH and buffered conditions and in the presence of acetate that binds to 1 in place of one of the terminal water ligands. These experiments will show that 1 not only exhibits proton-coupled electron-transfer reactivity analogous to the OEC, but also may be capable of electrochemical oxidation of water to oxygen. PMID:20372724

Interactions between hydrology and water chemistry shape bacterioplankton biogeography across boreal freshwater networks

PubMed Central

Niño-García, Juan Pablo; Ruiz-González, Clara; del Giorgio, Paul A

2016-01-01

Disentangling the mechanisms shaping bacterioplankton communities across freshwater ecosystems requires considering a hydrologic dimension that can influence both dispersal and local sorting, but how the environment and hydrology interact to shape the biogeography of freshwater bacterioplankton over large spatial scales remains unexplored. Using Illumina sequencing of the 16S ribosomal RNA gene, we investigate the large-scale spatial patterns of bacterioplankton across 386 freshwater systems from seven distinct regions in boreal Québec. We show that both hydrology and local water chemistry (mostly pH) interact to shape a sequential structuring of communities from highly diverse assemblages in headwater streams toward larger rivers and lakes dominated by fewer taxa. Increases in water residence time along the hydrologic continuum were accompanied by major losses of bacterial richness and by an increased differentiation of communities driven by local conditions (pH and other related variables). This suggests that hydrology and network position modulate the relative role of environmental sorting and mass effects on community assembly by determining both the time frame for bacterial growth and the composition of the immigrant pool. The apparent low dispersal limitation (that is, the lack of influence of geographic distance on the spatial patterns observed at the taxonomic resolution used) suggests that these boreal bacterioplankton communities derive from a shared bacterial pool that enters the networks through the smallest streams, largely dominated by mass effects, and that is increasingly subjected to local sorting of species during transit along the hydrologic continuum. PMID:26849312

Interactions between hydrology and water chemistry shape bacterioplankton biogeography across boreal freshwater networks.

PubMed

Niño-García, Juan Pablo; Ruiz-González, Clara; Del Giorgio, Paul A

2016-07-01

Disentangling the mechanisms shaping bacterioplankton communities across freshwater ecosystems requires considering a hydrologic dimension that can influence both dispersal and local sorting, but how the environment and hydrology interact to shape the biogeography of freshwater bacterioplankton over large spatial scales remains unexplored. Using Illumina sequencing of the 16S ribosomal RNA gene, we investigate the large-scale spatial patterns of bacterioplankton across 386 freshwater systems from seven distinct regions in boreal Québec. We show that both hydrology and local water chemistry (mostly pH) interact to shape a sequential structuring of communities from highly diverse assemblages in headwater streams toward larger rivers and lakes dominated by fewer taxa. Increases in water residence time along the hydrologic continuum were accompanied by major losses of bacterial richness and by an increased differentiation of communities driven by local conditions (pH and other related variables). This suggests that hydrology and network position modulate the relative role of environmental sorting and mass effects on community assembly by determining both the time frame for bacterial growth and the composition of the immigrant pool. The apparent low dispersal limitation (that is, the lack of influence of geographic distance on the spatial patterns observed at the taxonomic resolution used) suggests that these boreal bacterioplankton communities derive from a shared bacterial pool that enters the networks through the smallest streams, largely dominated by mass effects, and that is increasingly subjected to local sorting of species during transit along the hydrologic continuum.

Synthesis of the Plasma Chemistry Occurring in High Power CO2 Lasers

DTIC Science & Technology

1978-12-01

AFIT/GEP/PH/78D-13 44 SYNTHESIS OF THE PLASMA CHEMISTRY D D C OCCURRING IN HIGH POWER CO 2 LASERS ’Una CTHESIS David E. Toodle AFIT/GEP/PH/78D-13 2nd...inves- tivation is the plasma chemistry occurring in the laser discharge. These studies are ultimately related to the development of flowing and...aids in the understanding of plasma chemistry pro- cesses in the CO2 laser discharge. I would like to thank the whole staff of the Advanced Concepts

Imidazole as a pH Probe: An NMR Experiment for the General Chemistry Laboratory

ERIC Educational Resources Information Center

Hagan, William J., Jr.; Edie, Dennis L.; Cooley, Linda B.

2007-01-01

The analysis describes an NMR experiment for the general chemistry laboratory, which employs an unknown imidazole solution to measure the pH values. The described mechanism can also be used for measuring the acidity within the isolated cells.

A Profile of Chemistry Degree Holders in Academic Jobs

ERIC Educational Resources Information Center

Robinson, G. W.

1973-01-01

Presents statistical data on the distribution of institutions' Bachelor and Ph.D. chemistry graduates in faculty positions at research oriented schools with a comparison between the institutions' Ph.D. degree rankings and the rankings given by the American Council on Education included. (CC)

Particle water and pH in the Eastern Mediterranean: sources variability and implications for nutrients availability

NASA Astrophysics Data System (ADS)

Nikolaou, P.; Bougiatioti, A.; Stavroulas, I.; Kouvarakis, G.; Nenes, A.; Weber, R.; Kanakidou, M.; Mihalopoulos, N.

2015-10-01

Particle water (LWC) and aerosol pH drive the aerosol phase, heterogeneous chemistry and bioavailability of nutrients that profoundly impact cloud formation, atmospheric composition and atmospheric fluxes of nutrients to ecosystems. Few measurements of in-situ LWC and pH however exist in the published literature. Using concurrent measurements of aerosol chemical composition, cloud condensation nuclei activity and tandem light scattering coefficients, the particle water mass concentrations associated with the aerosol inorganic (Winorg) and organic (Worg) components are determined for measurements conducted at the Finokalia atmospheric observation station in the eastern Mediterranean between August and November 2012. These data are interpreted using the ISORROPIA-II thermodynamic model to predict pH of aerosols originating from the various sources that influence air quality in the region. On average, closure between predicted aerosol water and that determined by comparison of ambient with dry light scattering coefficients was achieved to within 8 % (slope = 0.92, R2 = 0.8, n = 5201 points). Based on the scattering measurements a parameterization is also derived, capable of reproducing the hygroscopic growth factor (f(RH)) within 15 % of the measured values. The highest aerosol water concentrations are observed during nighttime, when relative humidity is highest and the collapse of the boundary layer increases the aerosol concentration. A significant diurnal variability is found for Worg with morning and afternoon average mass concentrations being 10-15 times lower than nighttime concentrations, thus rendering Winorg the main form of particle water during daytime. The average value of total aerosol water was 2.19 ± 1.75 μg m-3, contributing on average up to 33 % of the total submicron mass concentration. Average aerosol water associated with organics, Worg, was equal to 0.56 ± 0.37 μg m-3, thus organics contributed about 27.5 % to the total aerosol water, mostly during early morning, late evening and nighttime hours. The aerosol was found to be highly acidic with calculated aerosol pH varying from 0.5 to 2.8 throughout the study period. Biomass burning aerosol presented the highest values of pH in the submicron fraction and the lowest values in total water mass concentration. The low pH values observed in the submicron mode and independently of air masses origin could increase nutrient availability and especially P solubility, which is the nutrient limiting sea water productivity of the eastern Mediterranean.

General Procedure for the Easy Calculation of pH in an Introductory Course of General or Analytical Chemistry

ERIC Educational Resources Information Center

Cepriá, Gemma; Salvatella, Luis

2014-01-01

All pH calculations for simple acid-base systems used in introductory courses on general or analytical chemistry can be carried out by using a general procedure requiring the use of predominance diagrams. In particular, the pH is calculated as the sum of an independent term equaling the average pK[subscript a] values of the acids involved in the…

Rising CO2 Levels Will Intensify Phytoplankton Blooms in Eutrophic and Hypertrophic Lakes

PubMed Central

Verspagen, Jolanda M. H.; Van de Waal, Dedmer B.; Finke, Jan F.; Visser, Petra M.; Van Donk, Ellen; Huisman, Jef

2014-01-01

Harmful algal blooms threaten the water quality of many eutrophic and hypertrophic lakes and cause severe ecological and economic damage worldwide. Dense blooms often deplete the dissolved CO2 concentration and raise pH. Yet, quantitative prediction of the feedbacks between phytoplankton growth, CO2 drawdown and the inorganic carbon chemistry of aquatic ecosystems has received surprisingly little attention. Here, we develop a mathematical model to predict dynamic changes in dissolved inorganic carbon (DIC), pH and alkalinity during phytoplankton bloom development. We tested the model in chemostat experiments with the freshwater cyanobacterium Microcystis aeruginosa at different CO2 levels. The experiments showed that dense blooms sequestered large amounts of atmospheric CO2, not only by their own biomass production but also by inducing a high pH and alkalinity that enhanced the capacity for DIC storage in the system. We used the model to explore how phytoplankton blooms of eutrophic waters will respond to rising CO2 levels. The model predicts that (1) dense phytoplankton blooms in low- and moderately alkaline waters can deplete the dissolved CO2 concentration to limiting levels and raise the pH over a relatively wide range of atmospheric CO2 conditions, (2) rising atmospheric CO2 levels will enhance phytoplankton blooms in low- and moderately alkaline waters with high nutrient loads, and (3) above some threshold, rising atmospheric CO2 will alleviate phytoplankton blooms from carbon limitation, resulting in less intense CO2 depletion and a lesser increase in pH. Sensitivity analysis indicated that the model predictions were qualitatively robust. Quantitatively, the predictions were sensitive to variation in lake depth, DIC input and CO2 gas transfer across the air-water interface, but relatively robust to variation in the carbon uptake mechanisms of phytoplankton. In total, these findings warn that rising CO2 levels may result in a marked intensification of phytoplankton blooms in eutrophic and hypertrophic waters. PMID:25119996

Factors affecting the hydrochemistry of a mangrove tidal creek, sepetiba bay, Brazil

NASA Astrophysics Data System (ADS)

Ovalle, A. R. C.; Rezende, C. E.; Lacerda, L. D.; Silva, C. A. R.

1990-11-01

We studied the porewater chemistry, and spatial and temporal variation of mangrove creek hydrochemistry. Except for nitrate porewater, the concentrations of nutrients we analysed were higher than for creek water. Groundwater is a source of silica and phosphate, whereas total alkalinity and ammonium are related to mangrove porewater migration to the creek. Open bay waters contribute chlorine, dissolved oxygen and elevated pH. The results also suggest that nitrate is related to nitrification inside the creek. During flood tides, salinity, chlorine, dissolved oxygen and pH increase, whereas total alkalinity decreases. This pattern is reversed at ebb tides. Silica, phosphate, nitrate and ammonium show an erratic behaviour during the tidal cycle. Tidal dynamics, precipitation events and nitrification inside the creek were identified as major control factors and an estimate of tidal exchanges indicate that the system is in an equilibrium state.

Environmental policy constraints for acidic exhaust gas scrubber discharges from ships.

PubMed

Ülpre, H; Eames, I

2014-11-15

Increasingly stringent environmental legislation on sulphur oxide emissions from the combustion of fossil fuels onboard ships (International Maritime Organization (IMO) Regulation 14) can be met by either refining the fuel to reduce sulphur content or by scrubbing the exhaust gases. Commonly used open loop marine scrubbers discharge warm acidic exhaust gas wash water into the sea, depressing its pH. The focus on this paper is on the physics and chemistry behind the disposal of acidic discharges in seawater. The IMO Marine Environment Protection Committee (MEPC 59/24/Add.1 Annex 9) requires the wash water to reach a pH greater than 6.5 at a distance of 4m from the point of discharge. We examine the engineering constraints, specifically size and number of ports, to identify the challenges of meeting regulatory compliance. Copyright © 2014. Published by Elsevier Ltd.

USGS Arctic Ocean carbon cruise 2010: field activity H-03-10-AR to collect carbon data in the Arctic Ocean, August - September 2010

USGS Publications Warehouse

Robbins, Lisa L.; Yates, Kimberly K.; Gove, Matthew D.; Knorr, Paul O.; Wynn, Jonathan; Byrne, Robert H.; Liu, Xuewu

2013-01-01

Carbon dioxide (CO2) in the atmosphere is absorbed at the surface of the ocean by reacting with seawater to form carbonic acid, a weak, naturally occurring acid. As atmospheric carbon dioxide increases, the concentration of carbonic acid in seawater also increases, causing a decrease in ocean pH and carbonate mineral saturation states, a process known as ocean acidification. The oceans have absorbed approximately 525 billion tons of carbon dioxide from the atmosphere, or about one-quarter to one-third of the anthropogenic carbon emissions released since the beginning of the Industrial Revolution (Sabine and others, 2004). Global surveys of ocean chemistry have revealed that seawater pH has decreased by about 0.1 units (from a pH of 8.2 to 8.1) since the 1700s due to absorption of carbon dioxide (Caldeira and Wickett, 2003; Orr and others, 2005; Raven and others, 2005). Modeling studies, based on Intergovernmental Panel on Climate Change (IPCC) CO2 emission scenarios, predict that atmospheric carbon dioxide levels could reach more than 500 parts per million (ppm) by the middle of this century and 800 ppm by the year 2100, causing an additional decrease in surface water pH of 0.3 pH units. Ocean acidification is a global threat and is already having profound and deleterious effects on the geology, biology, chemistry, and socioeconomic resources of coastal and marine habitats (Raven and others, 2005; Ruttiman, 2006). The polar and sub-polar seas have been identified as the bellwethers for global ocean acidification.

USGS Arctic Ocean carbon cruise 2011: field activity H-01-11-AR to collect carbon data in the Arctic Ocean, August - September 2011

USGS Publications Warehouse

Robbins, Lisa L.; Yates, Kimberly K.; Knorr, Paul O.; Wynn, Jonathan; Lisle, John; Buczkowski, Brian J.; Moore, Barbara; Mayer, Larry; Armstrong, Andrew; Byrne, Robert H.; Liu, Xuewu

2013-01-01

Carbon dioxide (CO2) in the atmosphere is absorbed at the surface of the ocean by reacting with seawater to form a weak, naturally occurring acid called carbonic acid. As atmospheric carbon dioxide increases, the concentration of carbonic acid in seawater also increases, causing a decrease in ocean pH and carbonate mineral saturation states, a process known as ocean acidification. The oceans have absorbed approximately 525 billion tons of carbon dioxide from the atmosphere, or about one-quarter to one-third of the anthropogenic carbon emissions released since the beginning of the Industrial Revolution (Sabine and others, 2004). Global surveys of ocean chemistry have revealed that seawater pH has decreased by about 0.1 units (from a pH of 8.2 to 8.1) since the 1700s due to absorption of carbon dioxide (Caldeira and Wickett, 2003; Orr and others, 2005; Raven and others, 2005). Modeling studies, based on Intergovernmental Panel on Climate Change (IPCC) CO2 emission scenarios, predict that atmospheric carbon dioxide levels could reach more than 500 parts per million (ppm) by the middle of this century and 800 ppm by the year 2100, causing an additional decrease in surface water pH of 0.3 pH units. Ocean acidification is a global threat and is already having profound and deleterious effects on the geology, biology, chemistry, and socioeconomic resources of coastal and marine habitats (Raven and others, 2005; Ruttiman, 2006). The polar and sub-polar seas have been identified as the bellwethers for global ocean acidification.

Inorganic carbon speciation and fluxes in the Congo River

NASA Astrophysics Data System (ADS)

Wang, Zhaohui Aleck; Bienvenu, Dinga Jean; Mann, Paul J.; Hoering, Katherine A.; Poulsen, John R.; Spencer, Robert G. M.; Holmes, Robert M.

2013-02-01

Seasonal variations in inorganic carbon chemistry and associated fluxes from the Congo River were investigated at Brazzaville-Kinshasa. Small seasonal variation in dissolved inorganic carbon (DIC) was found in contrast with discharge-correlated changes in pH, total alkalinity (TA), carbonate species, and dissolved organic carbon (DOC). DIC was almost always greater than TA due to the importance of CO2*, the sum of dissolved CO2 and carbonic acid, as a result of low pH. Organic acids in DOC contributed 11-61% of TA and had a strong titration effect on water pH and carbonate speciation. The CO2* and bicarbonate fluxes accounted for ~57% and 43% of the DIC flux, respectively. Congo River surface water released CO2 at a rate of ~109 mol m-2 yr-1. The basin-wide DIC yield was ~8.84 × 104 mol km-2 yr-1. The discharge normalized DIC flux to the ocean amounted to 3.11 × 1011 mol yr-1. The DOC titration effect on the inorganic carbon system may also be important on a global scale for regulating carbon fluxes in rivers.

Hydraulic and field water-chemistry characteristics of piedmont alluvial deposits in the Middle Tyger River near Lyman, Spartanburg County, South Carolina, 2005

USGS Publications Warehouse

Harrelson, Larry G.; Addison, Adrian D.

2006-01-01

This study explores the possibility of developing a bank-filtration process to improve water quality in which alluvial deposits serve as a natural sand filter to pretreat water to be used as a secondary drinking-water source in a small piedmont reservoir along the Middle Tyger River near Lyman in Spartanburg County, South Carolina. From January 2004 to September 2005, data from 10 auger borings, 2 sediment cores, 29 ground-penetrating radar transects, and 3 temporary observation wells, and field water-chemistry data were collected and analyzed. These data were collected and used to characterize the lithology, geometry, hydraulic properties, yield potential, and water-chemistry characteristics of the alluvial deposits in the channel and on the right bank of the reservoir. The assessment was undertaken to determine if an adequate amount of water could be withdrawn from the alluvial deposits to sustain a bank-filtration process and to characterize the water chemistry of the surface water and pore water. The heterogeneous alluvial and fill material at the study site--clay, silty clay, clayey sand, fine- to coarse-grained sand, and mica--on the right bank of the Middle Tyger River ranges in thickness from 0.6 to 7 meters, has a calculated horizontal hydraulic conductivity of 1 meter per day, and yields approximately 0.07 liter per second of water. The small calculated horizontal hydraulic conductivity and water yield for these deposits restrict the use of the right bank as a potential bank-filtration site. The coarse-grained alluvial sand deposit in the channel of the Middle Tyger River, however, may be used for a limited bank-filtration process. The discharge during pumping of the channel deposit yielded water at the rate of 1.9 liters per second. The coarse-grained channel deposit is approximately 49 meters wide and 3 meters thick near the dam. At approximately 183 meters upstream from the dam, the channel narrows to roughly 9 meters and the channel deposits thin to approximately 0.1 meter. Slug tests conducted in the channel deposits near the dam produced a calculated horizontal hydraulic conductivity of 60 meters per day. The limited thickness and aerial extent of the coarse-grained channel deposits coupled with large horizontal hydraulic conductivity likely would allow rapid transmission of water and may degrade the effectiveness of some water-chemistry improvements typical of a bank-filtration process. Field water-chemistry data were collected for approximately 1 hour and 45 minutes at 10 to 15 minute intervals to compare the surface-water and pore-water quality in and beneath the channel of the Middle Tyger River. The waterchemistry data indicate that (1) the mean water temperature was higher in surface water (22.5 degrees Celsius) than in pore water (18.5 degrees Celsius), (2) the mean specific conductance was less in surface water (56.9 microsiemens per centimeter at 25 degrees Celsius) than in pore water (125.7 microsiemens per centimeter at 25 degrees Celsius), (3) alkalinity was lower in surface water (22.5 milligrams per liter) than in pore water (44.6 milligrams per liter), and (4) recorded pH values ranged between 6.2 and 6.3 in the surface water and pore water during the sampling period. The flow velocity was orders of magnitude slower in the pore water than in the surface water; therefore, the pore water interacts with the alluvial sediment for a longer period of time producing the variation in water-chemistry data between the two waters.

Toward selective, sensitive, and discriminative detection of Hg(2+) and Cd(2+)via pH-modulated surface chemistry of glutathione-capped gold nanoclusters.

PubMed

Huang, Pengcheng; Li, Sha; Gao, Nan; Wu, Fangying

2015-11-07

Heavy metal pollution can exert severe effects on the environment and human health. Simple, selective, and sensitive detection of heavy metal ions, especially two or more, using a single probe, is thereby of great importance. In this study, we report a new and facile strategy for discriminative detection of Hg(2+) and Cd(2+) with high selectivity and sensitivity via pH-modulated surface chemistry of the glutathione-capped gold NCs (GSH-Au NCs). By simply adjusting pH values of the colloidal solution of the NCs, Hg(2+) could specifically turn off the fluorescence under acidic pH, however, Cd(2+) could exclusively turn on the fluorescence under alkaline pH. This enables the NCs to serve as a dual fluorescent sensor for Hg(2+) and Cd(2+). We demonstrate that these two opposing sensing modes are presumably due to different interaction mechanisms: Hg(2+) induces aggregation by dissociating GSH from the Au surface via robust coordination and, Cd(2+) could passivate the Au surface by forming a Cd-GSH complex with a compact structure. Finally, the present strategy is successfully exploited to separately determine Hg(2+) and Cd(2+) in environmental water samples.

Effects of simulated acid rain on soil and soil solution chemistry in a monsoon evergreen broad-leaved forest in southern China.

PubMed

Qiu, Qingyan; Wu, Jianping; Liang, Guohua; Liu, Juxiu; Chu, Guowei; Zhou, Guoyi; Zhang, Deqiang

2015-05-01

Acid rain is an environmental problem of increasing concern in China. In this study, a laboratory leaching column experiment with acid forest soil was set up to investigate the responses of soil and soil solution chemistry to simulated acid rain (SAR). Five pH levels of SAR were set: 2.5, 3.0, 3.5, 4.0, and 4.5 (as a control, CK). The results showed that soil acidification would occur when the pH of SAR was ≤3.5. The concentrations of NO₃(-)and Ca(2+) in the soil increased significantly when the pH of SAR fell 3.5. The concentration of SO₄(2-) in the soil increased significantly when the pH of SAR was <4.0. The effects of SAR on soil solution chemistry became increasingly apparent as the experiment proceeded (except for Na(+) and dissolved organic carbon (DOC)). The net exports of NO₃(-), SO₄(2-), Mg(2+), and Ca(2+) increased about 42-86% under pH 2.5 treatment as compared to CK. The Ca(2+) was sensitive to SAR, and the soil could release Ca(2+) through mineral weathering to mitigate soil acidification. The concentration of exchangeable Al(3+) in the soil increased with increasing the acidity of SAR. The releases of soluble Al and Fe were SAR pH dependent, and their net exports under pH 2.5 treatment were 19.6 and 5.5 times, respectively, higher than that under CK. The net export of DOC was reduced by 12-29% under SAR treatments as compared to CK. Our results indicate the chemical constituents in the soil are more sensitive to SAR than those in the soil solution, and the effects of SAR on soil solution chemistry depend not only on the intensity of SAR but also on the duration of SAR addition. The soil and soil solution chemistry in this region may not be affected by current precipitation (pH≈4.5) in short term, but the soil and soil leachate chemistry may change dramatically if the pH of precipitation were below 3.5 and 3.0, respectively.

21 CFR 862.1550 - Urinary pH (nonquantitative) test system.

Code of Federal Regulations, 2014 CFR

2014-04-01

... 21 Food and Drugs 8 2014-04-01 2014-04-01 false Urinary pH (nonquantitative) test system. 862.1550 Section 862.1550 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) MEDICAL DEVICES CLINICAL CHEMISTRY AND CLINICAL TOXICOLOGY DEVICES Clinical Chemistry Test...

Characterization of submicrometer aqueous iron(III) colloids formed in the presence of phosphate by sedimentation field flow fractionation with multiangle laser light scattering detection.

PubMed

Magnuson, M L; Lytle, D A; Frietch, C M; Kelty, C A

2001-10-15

Iron colloids play a major role in the water chemistry of natural watersheds and of engineered drinking water distribution systems. Phosphate is frequently added to distribution systems to control corrosion problems, so iron-phosphate colloids may form through reaction of iron in water pipes. In this study, sedimentation field flow fractionation (SdFFF) is coupled on-line with multiangle laser light scattering (MALLS) detection to characterize these iron colloids formed following the oxygenation of iron(II) in the presence of phosphate. The SdFFF-MALLS data were used to calculate the hydrodynamic diameter, density, and particle size distribution of these submicrometer colloids. The system was first verified with standard polystyrene beads, and the results compared well with certified values. Iron(III) colloids were formed in the presence of phosphate at a variety of pH conditions. The colloids' hydrodynamic diameters, which ranged from 218 +/- 3 (pH 7) to 208 +/- 4 nm (pH 10), did not change significantly within the 95% confidence limit. Colloid density did increase significantly from 1.12 +/- 0.01 (pH 7) to 1.36 +/- 0.02 g/mL (pH 10). Iron(III) colloids formed at pH 10 in the presence of phosphate were compared to iron(III) colloids formed without phosphate and also to iron(III) colloids formed with silicate. The iron(III) colloids formed without phosphate or silicate were 0.46 g/mL more dense than any other colloids and were >6 times more narrowly distributed than the other colloids. The data suggest competitive incorporation of respective anions into the colloid during formation.

Fluoride geochemistry of thermal waters in Yellowstone National Park: I. Aqueous fluoride speciation

USGS Publications Warehouse

Deng, Y.; Nordstrom, D. Kirk; McCleskey, R. Blaine

2011-01-01

Thermal water samples from Yellowstone National Park (YNP) have a wide range of pH (1–10), temperature, and high concentrations of fluoride (up to 50 mg/l). High fluoride concentrations are found in waters with field pH higher than 6 (except those in Crater Hills) and temperatures higher than 50 °C based on data from more than 750 water samples covering most thermal areas in YNP from 1975 to 2008. In this study, more than 140 water samples from YNP collected in 2006–2009 were analyzed for free-fluoride activity by ion-selective electrode (ISE) method as an independent check on the reliability of fluoride speciation calculations. The free to total fluoride concentration ratio ranged from <1% at low pH values to >99% at high pH. The wide range in fluoride activity can be explained by strong complexing with H+ and Al3+ under acidic conditions and lack of complexing under basic conditions. Differences between the free-fluoride activities calculated with the WATEQ4F code and those measured by ISE were within 0.3–30% for more than 90% of samples at or above 10−6 molar, providing corroboration for chemical speciation models for a wide range of pH and chemistry of YNP thermal waters. Calculated speciation results show that free fluoride, F−, and major complexes (HF(aq)0">HF(aq)0, AlF2+, AlF2+">AlF2+and AlF30">AlF30) account for more than 95% of total fluoride. Occasionally, some complex species like AlF4-">AlF4-, FeF2+, FeF2+">FeF2+, MgF+ and BF2(OH)2-">BF2(OH)2- may comprise 1–10% when the concentrations of the appropriate components are high. According to the simulation results by PHREEQC and calculated results, the ratio of main fluoride species to total fluoride varies as a function of pH and the concentrations and ratios of F and Al.

Science, Engineering, and Mathematics (SEM) at the Timbuktu Academy

DTIC Science & Technology

2005-07-31

School @ CalTech (PhD Chemistry Program) Millican , Jasmine F Su02 ONR 20 Fall `02- Grad . School @ LSU for Ph .D. in Chemistry, Baton Rouge, LA Thomas...n 22 . Joshua McKinsey Stennis Space Center - Stennis Space Center, M S 23 . Jasmine Millican Louisiana State University (LAMP Program) - Baton Rouge...OH 26. Rachel Mckinsey Fr ./Physics MIT- Boston, M A 27. Jasmine Millican Jr ./Chemistry University of Illinois - Chicago, I L 28. Symoane Mizell So

Modelling the radiolysis of RSG-GAS primary cooling water

NASA Astrophysics Data System (ADS)

Butarbutar, S. L.; Kusumastuti, R.; Subekti, M.; Sunaryo, G. R.

2018-02-01

Water chemistry control for light water coolant reactor required a reliable understanding of radiolysis effect in mitigating corrosion and degradation of reactor structure material. It is known that oxidator products can promote the corrosion, cracking and hydrogen pickup both in the core and in the associated piping components of the reactor. The objective of this work is to provide the radiolysis model of RSG GAS cooling water and further more to predict the oxidator concentration which can lead to corrosion of reactor material. Direct observations or measurements of the chemistry in and around the high-flux core region of a nuclear reactor are difficult due to the extreme conditions of high temperature, pressure, and mixed radiation fields. For this reason, chemical models and computer simulations of the radiolysis of water under these conditions are an important route of investigation. FACSIMILE were used to calculate the concentration of O2 formed at relatively long-time by the pure water γ and neutron irradiation (pH=7) at temperature between 25 and 50 °C. This simulation method is based on a complex chemical reaction kinetic. In this present work, 300 MeV-proton were used to mimic γ-rays radiolysis and 2 MeV fast neutrons. Concentration of O2 were calculated at 10-6 - 106 s time scale.

Pore Water Chemistry as Sensitive Indicators for Fluid Flow in Brazos-Trinity Basin #4 and Ursa Basin, Northeast Gulf of Mexico (IODP Expedition 308)

NASA Astrophysics Data System (ADS)

Jiang, S.; Gilhooly, W.; Takano, Y.; Flemings, P.; Behrmann, J.; John, C.

2005-12-01

Rapid sediment loading drives overpressure in marine sedimentary basins around the world. During IODP Expedition 308, two basins (Brazos-Trinity Basin #4 and Ursa Basin) with large different sedimentary loading of turbidite and hemipelagic sediments in the northeast Gulf of Mexico, were investigated to characterize in-situ spatial variations in temperature, pressure, and rock and fluid physical properties and chemistry. Pore water chemical compositions including alkalinity, salinity, pH, anions (Cl, SO4, PO4, H4SiO4), cations (Na, K, Ca, Mg), trace metals (Li, B, Sr, Ba, Fe, Mn), were analyzed in four drill holes at sites U1319, U1320, U1322, and U1324, in the Brazos-Trinity Basin #4 and Ursa Basin. At all sites, pore water chemistry shows great variability at shallow depths with maximam or miminum values corresponding well to seismic reflectors and lithostratigraphic units. The sulfate profile shows a dramatic decrease in SO4 content with a sulfate-methane interface (SMI) of 15 mbsf at Site 1319 and 22 mbsf at Site 1320 in the Brazos-Trinity Basin #4 Basin. In contrast, the sulfate- methane interfaces (SMI) are much deeper in Ursa Basin, i.e., 74 mbsf at Site 1322, and 94 mbsf at Site 2324. The deep SMI in Ursa Basin suggest relatively slow anaerobic degradation of organic matter considering the location of drilling site though we do not determine sulfate reducing rate with organic matter or methane as substrate at this leg. The downhole consumption of sulfate coincides with a concomitant increase in alkalinity and a decrease of Mn, Ca, Mg, Sr, and Li. Furthermore, initial pore water chemistry results appear to be influence by hydrogeologic fluid flow in both basins. Coincidence between pore water profile concentration maxima and parallel seismic reflectors may suggest that these seismic surfaces occur along specific stratigraphic units, which serve as channels for lateral fluid flow. Overall, the downhole variations in interstitial water chemistry may reflect a combination of processes, including anaerobic degradation of organic matter, diagenetic carbonate precipitation/dissolution, and fluid flow pathways.

Distributions and Changes of Carbonate Parameters Along the U.S. East Coast

NASA Astrophysics Data System (ADS)

Xu, Y. Y.; Cai, W. J.; Wanninkhof, R. H.; Salisbury, J., II

2017-12-01

On top of anthropogenic climate change, upwelling, eutrophication, river discharge, and interactions with the open ocean have affected carbonate chemistry in coastal waters. In this study, we present the large-scale variations of carbonate parameters along the U.S. east coast using in situ observations obtained during an East Coast Ocean Acidification (ECOA) cruise in summer 2015. Compare with previous large-scale cruises along the east coast, the ECOA cruise increases spatial coverage in the Gulf of Marine region and has more offshore stations for a better understanding of carbon dynamics in coastal waters and their interactions with open ocean waters. Our results show that the spatial distribution of water mass properties set up the large-scale advection of salt and heat and the distribution of total alkalinity (TA). However, dissolved inorganic carbon (DIC) shows a distinct pattern. Coastal water pH displays high variability in the Gulf of Maine and the Mid-Atlantic Bight (MAB). But it is relatively homogeneous in the South Atlantic Bight (SAB). In contrast, the distribution of aragonite saturation state (Ω) has an increase pattern from north to south similar to those of TA, SST, and SSS. A mechanistic discussion will be presented to understand the controls on Ω in eastern coastal waters. A comparison with previous cruises also suggests very different changes of pH and Ω in the MAB and SAB. Preliminary analysis suggests an overall increase in surface pH and Ω in the MAB. In contrast, pH and Ω in the SAB surface waters decrease over the past two decades. This work serves as a platform for the monitoring of large-scale carbon cycling in the U.S. east coast. It is also important to identify the physical and biogeochemical processes that affect these distributions and changes over time for a better understanding of carbon cycling and ocean acidification in coastal waters.

Microbial sulfate reduction and metal attenuation in pH 4 acid mine water

USGS Publications Warehouse

Church, C.D.; Wilkin, R.T.; Alpers, Charles N.; Rye, R.O.; Blaine, R.B.

2007-01-01

Sediments recovered from the flooded mine workings of the Penn Mine, a Cu-Zn mine abandoned since the early 1960s, were cultured for anaerobic bacteria over a range of pH (4.0 to 7.5). The molecular biology of sediments and cultures was studied to determine whether sulfate-reducing bacteria (SRB) were active in moderately acidic conditions present in the underground mine workings. Here we document multiple, independent analyses and show evidence that sulfate reduction and associated metal attenuation are occurring in the pH-4 mine environment. Water-chemistry analyses of the mine water reveal: (1) preferential complexation and precipitation by H2S of Cu and Cd, relative to Zn; (2) stable isotope ratios of 34S/32S and 18O/16O in dissolved SO4 that are 2-3 ??? heavier in the mine water, relative to those in surface waters; (3) reduction/oxidation conditions and dissolved gas concentrations consistent with conditions to support anaerobic processes such as sulfate reduction. Scanning electron microscope (SEM) analyses of sediment show 1.5-micrometer, spherical ZnS precipitates. Phospholipid fatty acid (PLFA) and denaturing gradient gel electrophoresis (DGGE) analyses of Penn Mine sediment show a high biomass level with a moderately diverse community structure composed primarily of iron- and sulfate-reducing bacteria. Cultures of sediment from the mine produced dissolved sulfide at pH values near 7 and near 4, forming precipitates of either iron sulfide or elemental sulfur. DGGE coupled with sequence and phylogenetic analysis of 16S rDNA gene segments showed populations of Desulfosporosinus and Desulfitobacterium in Penn Mine sediment and laboratory cultures. ?? 2007 Church et al; licensee BioMed Central Ltd.

Dark production of carbon monoxide (CO) from dissolved organic matter in the St. Lawrence estuarine system: Implication for the global coastal and blue water CO budgets

NASA Astrophysics Data System (ADS)

Zhang, Yong; Xie, Huixiang; Fichot, CéDric G.; Chen, Guohua

2008-12-01

We investigated the thermal (dark) production of carbon monoxide (CO) from dissolved organic matter (DOM) in the water column of the St. Lawrence estuarine system in spring 2007. The production rate, Qco, decreased seaward horizontally and downward vertically. Qco exhibited a positive, linear correlation with the abundance of chromophoric dissolved organic matter (CDOM). Terrestrial DOM was more efficient at producing CO than marine DOM. The temperature dependence of Qco can be characterized by the Arrhenius equation with the activation energies of freshwater samples being higher than those of salty samples. Qco remained relatively constant between pH 4-6, increased slowly between pH 6-8 and then rapidly with further rising pH. Ionic strength and iron chemistry had little influence on Qco. An empirical equation, describing Qco as a function of CDOM abundance, temperature, pH, and salinity, was established to evaluate CO dark production in the global coastal waters (depth < 200 m). The total coastal CO dark production from DOM was estimated to be from 0.46 to 1.50 Tg CO-C a-1 (Tg carbon from CO a-1). We speculated the global oceanic (coastal plus open ocean) CO dark production to be in the range from 4.87 to 15.8 Tg CO-C a-1 by extrapolating the coastal water-based results to blue waters (depth > 200 m). Both the coastal and global dark source strengths are significant compared to the corresponding photochemical CO source strengths (coastal: ˜2.9 Tg CO-C a-1; global: ˜50 Tg CO-C a-1). Steady state deepwater CO concentrations inferred from Qco and microbial CO uptake rates are <0.1 nmol L-1.

Microbial sulfate reduction and metal attenuation in pH 4 acid mine water

PubMed Central

Church, Clinton D; Wilkin, Richard T; Alpers, Charles N; Rye, Robert O; McCleskey, R Blaine

2007-01-01

Sediments recovered from the flooded mine workings of the Penn Mine, a Cu-Zn mine abandoned since the early 1960s, were cultured for anaerobic bacteria over a range of pH (4.0 to 7.5). The molecular biology of sediments and cultures was studied to determine whether sulfate-reducing bacteria (SRB) were active in moderately acidic conditions present in the underground mine workings. Here we document multiple, independent analyses and show evidence that sulfate reduction and associated metal attenuation are occurring in the pH-4 mine environment. Water-chemistry analyses of the mine water reveal: (1) preferential complexation and precipitation by H2S of Cu and Cd, relative to Zn; (2) stable isotope ratios of 34S/32S and 18O/16O in dissolved SO4 that are 2–3 ‰ heavier in the mine water, relative to those in surface waters; (3) reduction/oxidation conditions and dissolved gas concentrations consistent with conditions to support anaerobic processes such as sulfate reduction. Scanning electron microscope (SEM) analyses of sediment show 1.5-micrometer, spherical ZnS precipitates. Phospholipid fatty acid (PLFA) and denaturing gradient gel electrophoresis (DGGE) analyses of Penn Mine sediment show a high biomass level with a moderately diverse community structure composed primarily of iron- and sulfate-reducing bacteria. Cultures of sediment from the mine produced dissolved sulfide at pH values near 7 and near 4, forming precipitates of either iron sulfide or elemental sulfur. DGGE coupled with sequence and phylogenetic analysis of 16S rDNA gene segments showed populations of Desulfosporosinus and Desulfitobacterium in Penn Mine sediment and laboratory cultures. PMID:17956615

Synthesis and evaluation of functional alginate hydrogels based on click chemistry for drug delivery applications.

PubMed

García-Astrain, Clara; Avérous, Luc

2018-06-15

Environment-sensitive alginate-based hydrogels for drug delivery applications are receiving increasing attention. However, most work in this field involves traditional cross-linking strategies which led to hydrogels with poor long-term stability. Herein, a series of chemically cross-linked alginate hydrogels was synthesized via click chemistry using Diels-Alder reaction by reacting furan-modified alginate and bifunctional cross-linkers. Alginate was successfully functionalized with furfurylamine. Then, 3D architectures were synthesized with water-soluble bismaleimides. Different substitution degrees were achieved in order to study the effect of alginate modification and the cross-linking extent over the behaviour of the hydrogels. The ensuing hydrogels were analysed in terms of microstructure, swelling, structure modification and rheological behaviour. The materials response to external stimuli such as pH was also investigated, revealing a pulsatile behaviour in a large pH range (1-13) and a clear pH-dependent swelling. Finally, vanillin release studies were conducted to demonstrate the potential of these biobased materials for drug delivery applications. Copyright © 2018 Elsevier Ltd. All rights reserved.

Hydrogeochemistry of high-fluoride groundwater at Yuncheng Basin, northern China.

PubMed

Li, Chengcheng; Gao, Xubo; Wang, Yanxin

2015-03-01

Hydrogeochemical and environmental isotope methods were integrated to delineate the spatial distribution and enrichment of fluoride in groundwater at Yuncheng Basin in northern China. One hundred groundwater samples and 10 Quaternary sediment samples were collected from the Basin. Over 69% of the shallow groundwater (with a F(-) concentration of up to 14.1mg/L), 44% of groundwater samples from the intermediate and 31% from the deep aquifers had F(-) concentrations above the WHO provisional drinking water guideline of 1.5mg/L. Groundwater with high F(-) concentrations displayed a distinctive major ion chemistry: Na-rich and Ca-poor with a high pH value and high HCO3(-) content. Hydrochemical diagrams and profiles and hydrogen and oxygen isotope compositions indicate that variations in the major ion chemistry and pH are controlled by mineral dissolution, cation exchange and evaporation in the aquifer systems, which are important for F(-) mobilization as well. Leakage of shallow groundwater and/or evaporite (gypsum and mirabilite) dissolution may be the major sources for F(-) in groundwater of the intermediate and deep aquifers. Copyright © 2014 Elsevier B.V. All rights reserved.

Heterogeneous organocatalysis at work: functionalization of hollow periodic mesoporous organosilica spheres with MacMillan catalyst.

PubMed

Shi, Jiao Yi; Wang, Chang An; Li, Zhi Jun; Wang, Qiong; Zhang, Yuan; Wang, Wei

2011-05-23

We report a new method for the synthesis of hollow-structured phenylene-bridged periodic mesoporous organosilica (PMO) spheres with a uniform particle size of 100-200 nm using α-Fe(2)O(3) as a hard template. Based on this method, the hollow-structured phenylene PMO could be easily functionalized with MacMillan catalyst (H-PhPMO-Mac) by a co-condensation process and a "click chemistry" post-modification. The synthesized H-PhPMO-Mac catalyst has been found to exhibit high catalytic activity (98% yield, 81% enantiomeric excess (ee) for endo and 81% ee for exo) in asymmetric Diels-Alder reactions with water as solvent. The catalyst could be reused for at least seven runs without a significant loss of catalytic activity. Our results have also indicated that hollow-structured PMO spheres exhibit higher catalytic efficiency than solid (non-hollow) PMO spheres, and that catalysts prepared by the co-condensation process and "click chemistry" post-modification exhibit higher catalytic efficiency than those prepared by a grafting method. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Laboratory investigations on the role of sediment surface and ground water chemistry in transport of bacteria through a contaminated Sandy Aquifer

USGS Publications Warehouse

Scholl, M.A.; Harvey, R.W.

1992-01-01

The effects of pH and sediment surface characteristics on sorption of indigenous groundwater bacteria were determined using contaminated and uncontaminated aquifer material from Cape Cod, MA. Over the pH range of the aquifer (5-7), the extent of bacterial sorption onto sediment in uncontaminated groundwater was strongly pH-dependent, but relatively pH-insensitive in contaminated groundwater from the site. Bacterial sorption was also affected by the presence of oxyhydroxide coatings (iron, aluminum, and manganese). Surface coating effects were most pronounced in uncontaminated groundwater (pH 6.4 at 10??C). Desorption of attached bacteria (up to 14% of the total number of labeled cells added) occurred in both field and laboratory experiments upon adjustment of groundwater to pH 8. The dependence of bacterial sorption upon environmental conditions suggests that bacterial immobilization could change substantially over relatively short distances in contaminated, sandy aquifers and that effects caused by changes in groundwater geochemistry can be significant.

Ammonia Gas Transport and Reactions in Unsaturated Sediments: Implications for Use as an Amendment to Immobilize Inorganic Contaminants

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

Zhong, Lirong; Szecsody, James E.; Truex, Michael J.

Use of gas-phase amendments for in situ remediation of inorganic contaminants in unsaturated sediments of the vadose zone may be advantageous, but there has been limited development and testing of gas remediation technologies. Treatment with ammonia gas has been studied and has a potential for use in treating inorganic contaminants such as uranium because it induces a high pore-water pH causing mineral dissolution and subsequent formation of stable precipitates that decrease the mobility of some contaminants. For field application, knowledge of ammonia transport and the geochemical reactions induced by ammonia is needed. Laboratory studies were conducted to support calculations neededmore » for field treatment design, to quantify advective and diffusive ammonia transport in unsaturated sediments, to evaluate reactions among gas, sediment, and water, and to study reaction-induced pore-water chemistry changes as a function of ammonia delivery conditions. Ammonia gas quickly partitions into sediment pore water and increases pH up to 13.2. Injected ammonia gas front movement can be reasonably predicted by gas flow rate and equilibrium partitioning. The ammonia gas diffusion rate is a function of the water content in the sediment. Measured diffusion front movement was 0.05, 0.03, and 0.02 cm/hr. in sediments with 2.0%, 8.7%, and 13.0% water content, respectively. Sodium, aluminum, and silica pore-water concentrations increase on exposure to ammonia and then decline as aluminosilicates precipitate with declining pH. When uranium is present in the sediment and pore water, up to 85% of the water-leachable uranium was immobilized by ammonia treatment.« less

Nitroimidazoles adsorption on activated carbon cloth from aqueous solution.

PubMed

Ocampo-Pérez, R; Orellana-Garcia, F; Sánchez-Polo, M; Rivera-Utrilla, J; Velo-Gala, I; López-Ramón, M V; Alvarez-Merino, M A

2013-07-01

The objective of this study was to analyze the equilibrium and adsorption kinetics of nitroimidazoles on activated carbon cloth (ACC), determining the main interactions responsible for the adsorption process and the diffusion mechanism of these compounds on this material. The influence of the different operational variables, such as ionic strength, pH, temperature, and type of water (ultrapure, surface, and waste), was also studied. The results obtained show that the ACC has a high capacity to adsorb nitroimidazoles in aqueous solution. Electrostatic interactions play an important role at pH<3, which favors the repulsive forces between dimetridazole or metronidazole and the ACC surface. The formation of hydrogen bonds and dispersive interactions play the predominant role at higher pH values. Modifications of the ACC with NH3, K2S2O8, and O3 demonstrated that its surface chemistry plays a predominant role in nitroimidazole adsorption on this material. The adsorption capacity of ACC is considerably high in surface waters and reduced in urban wastewater, due to the levels of alkalinity and dissolved organic matter present in the different types of water. Finally, the results of applying kinetic models revealed that the global adsorption rate of dimetridazole and metronidazole is controlled by intraparticle diffusion. Copyright © 2013 Elsevier Inc. All rights reserved.

Carbonate chemistry of surface waters in a temperate karst region: the southern Yorkshire Dales, UK

NASA Astrophysics Data System (ADS)

Pentecost, Allan

1992-11-01

A detailed study of surface water chemistry is described from an important limestone region in northern England. Major ions and pH were determined for 485 sites (springs, seeps, streams, rivers and lakes) during summertime. The saturation state of the waters with respect to calcite was determined as the calcite saturation ratio (Ω). An unexpectedly large number of samples were found to be supersaturated (65.5% of the 268 km of watercourses surveyed). As a consequence, several streams entering major cave systems were incapable of further limestone solution, at least during periods of low flow. Many waters were supersaturated from their source and some deposited travertine. A significant negative correlation was found between spring discharge and both (Ω) and pH. Supersaturation was caused primarily by atmospheric degassing, with some contribution from aquatic plant photosynthesis. The median total dissolved inorganic carbon and Ca concentrations were 2.49 and 1.35 millimoles 1 -1 respectively. Calcium originated exclusively from limestone, and carbon dioxide mainly from the soil and dissolved limestone. South facing catchments provided springwaters with significantly higher levels of TDIC and Ca when compared with north facing catchments. The study suggests that acid rain made a measurable contribution to limestone dissolution. Carboniferous limestone denudation rates were estimated as 54 to 63 m 3 km -2 a -1 (54 to 63 mm 1000 years -1). About 50% of the Mg came from limestone and the remainder, together with most K, Na, SO 4 and Cl from precipitation. Concentrations of dissolved nutrients were low, medians for NO 3, NH 4, total PO 4 and SiO 3 were 24 μmol, 1.4 μmol, 0.64 μmol and 15.5 μmol 1 -1 respectively. The concentration of a further 23 trace elements was determined.

Ciprofloxacin adsorption on graphene and granular activated carbon: kinetics, isotherms, and effects of solution chemistry.

PubMed

Zhu, Xuan; Tsang, Daniel C W; Chen, Feng; Li, Shiyu; Yang, Xin

2015-01-01

Ciprofloxacin (CIP) is a commonly used antibiotic and widely detected in wastewaters and farmlands nowadays. This study evaluated the efficacy of next-generation adsorbent (graphene) and conventional adsorbent (granular activated carbon, GAC) for CIP removal. Batch experiments and characterization tests were conducted to investigate the adsorption kinetics, equilibrium isotherms, thermodynamic properties, and the influences of solution chemistry (pH, ionic strength, natural organic matter (NOM), and water sources). Compared to GAC, graphene showed significantly faster adsorption and reached equilibrium within 3 min, confirming the rapid access of CIP into the macroporous network of high surface area of graphene as revealed by the Brunner-Emmet-Teller measurements analysis. The kinetics was better described by a pseudo-second-order model, suggesting the importance of the initial CIP concentration related to surface site availability of graphene. The adsorption isotherm on graphene followed Langmuir model with a maximum adsorption capacity of 323 mg/g, which was higher than other reported carbonaceous adsorbents. The CIP adsorption was thermodynamically favourable on graphene and primarily occurred through π - π interaction, according to the FTIR spectroscopy. While the adsorption capacity of graphene decreased with increasing solution pH due to the speciation change of CIP, the adverse effects of ionic strength (0.01-0.5 mol L(-1)), presence of NOM (5 mg L⁻¹), and different water sources (river water or drinking water) were less significant on graphene than GAC. These results indicated that graphene can serve as an alternative adsorbent for CIP removal in commonly encountered field conditions, if proper separation and recovery is available in place.

Response of surface water chemistry to reduced levels of acid precipitation: Comparison of trends in two regions of New York, USA

USGS Publications Warehouse

Burns, Douglas A.; McHale, M.R.; Driscoll, C.T.; Roy, K.M.

2006-01-01

In light of recent reductions in sulphur (S) and nitrogen (N) emissions mandated by Title IV of the Clean Air Act Amendments of 1990, temporal trends and trend coherence in precipitation (1984-2001 and 1992-2001) and surface water chemistry (1992-2001) were determined in two of the most acid-sensitive regions of North America, i.e. the Catskill and Adirondack Mountains of New York. Precipitation chemistry data from six sites located near these regions showed decreasing sulphate (SO42-), nitrate (NO3-), and base cation (CB) concentrations and increasing pH during 1984-2001, but few significant trends during 1992-2001. Data from five Catskill streams and 12 Adirondack lakes showed decreasing trends in SO42- concentrations at all sites, and decreasing trends in NO3-, CB, and H+ concentrations and increasing trends in dissolved organic carbon at most sites. In contrast, acid-neutralizing capacity (ANC increased significantly at only about half the Adirondack lakes and in one of the Catskill streams. Flow correction prior to trend analysis did not change any trend directions and had little effect on SO42- trends, but it caused several significant non-flow-corrected trends in NO3- and ANC to become non-significant, suggesting that trend results for flow-sensitive constituents are affected by flow-related climate variation. SO42- concentrations showed high temporal coherence in precipitation, surface waters, and in precipitation-surface water comparisons, reflecting a strong link between S emissions, precipitation SO42- concentrations, and the processes that affect S cycling within these regions. NO3- and H+ concentrations and ANC generally showed weak coherence, especially in surface waters and in precipitation-surface water comparisons, indicating that variation in local-scale processes driven by factors such as climate are affecting trends in acid-base chemistry in these two regions. Copyright ?? 2005 John Wiley & Sons, Ltd.

Fogwater Chemistry and Air Quality in the Texas-Louisiana Gulf Coast Corridor

NASA Astrophysics Data System (ADS)

Kommalapati, R. R.; Raja, S.; Ravikrishna, R.; Murugesan, K.; Collett, J. L.; Valsaraj, K.

2007-05-01

The presence of fog water in polluted atmosphere can influence atmospheric chemistry and air quality. The study of interactions between fog water and atmospheric gases and aerosols are very important in understanding the atmospheric fate of the pollutants. In this Study several air samples and fogwater samples were collected in the heavily industrialized area of Gulf Coast corridor( Houston, TX and Baton Rouge, LA). A total of 32 fogwater samples were collected, comprising of nine fog events in Baton Rouge (Nov 2004 to Feb 2005) and two fog events in Houston (Feb, 2006), during the fog sampling campaigns. These samples were analyzed for pH, total and dissolved carbon, major inorganic ions, organic acids, and aromatics, aldehydes, VOCs, and linear alkanes organic compounds. Fogwater samples collected in Houston show clear influence of marine and anthropogenic environment, while Baton Rouge samples reveal a relatively less polluted environment. Also, a time series observation of air samples indicated that fog event at the monitoring site impacted the air concentrations of the pollutants. This is attributed to presence of surface active organic matter in fog water.

Short-term responses of soil water chemistry to nitrogen reduction in a subtropical forest ecosystem in southwest China

NASA Astrophysics Data System (ADS)

Duan, L.; Xie, D.; Zhang, T.; Huang, Y.

2017-12-01

Reactive nitrogen emission and deposition has been greatly reduced in recent years in China. To study the responses of soil water chemistry to decreasing nitrogen deposition, a field manipulating experiment was carried out in Tieshanping, a nitogen-saturated forest near Chongqing city in southwest China. After ten-year application of NH4NO3 or NaNO3 to simulate doubling nitrogen deposition with different nitrogen forms during 2005-2014, the nitrogen fertilizers were stopped applying at the end of 2014 to simulate decrease in nitrogen deposition. The continuous observing results on the changes of soil water chemistry in the next two years (2015 and 2016) showed very quick decrease in NO3- (the major form of inorganic nitrogen in soil water, because almost all NH4+ added being nitrified) concentration at the nitrogen fertilizing plots, to similar level at the reference plots without N fertilizer application. The NO3- concentrations of soil water at the NH4NO3 plots were even lower than those at the NaNO3 plots. The previous experiment on the effects of nitrogen addition had showed that NH4+ deposition, instead of NO3- deposition, increased N retention in the forest ecosystem, and led to lower NO3- concentration in soil water. The nitrogen sink seemed remained in the two years after the cease of N addition. Although the total NO3- leaching decreased after nitrogen reduction, the pH of soil water had not showed significantly increasing trend. Therefore, the recovery of Tieshanping forest ecosystem from acidification was slow, which requiring further emission abatement of reactive nitrogen in the future.

Basalt weathering rates on Earth and the duration of liquid water on the plains of Gusev Crater, Mars

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

Steefel, Carl; Hausrath, E.M.; Navarre-Sitchler, A.K.

2008-03-15

Where Martian rocks have been exposed to liquid water, chemistry versus depth profiles could elucidate both Martian climate history and potential for life. The persistence of primary minerals in weathered profiles constrains the exposure time to liquid water: on Earth, mineral persistence times range from {approx}10 ka (olivine) to {approx}250 ka (glass) to {approx}1Ma (pyroxene) to {approx}5Ma (plagioclase). Such persistence times suggest mineral persistence minima on Mars. However, Martian solutions may have been more acidic than on Earth. Relative mineral weathering rates observed for basalt in Svalbard (Norway) and Costa Rica demonstrate that laboratory pH trends can be used tomore » estimate exposure to liquid water both qualitatively (mineral absence or presence) and quantitatively (using reactive transport models). Qualitatively, if the Martian solution pH > {approx}2, glass should persist longer than olivine; therefore, persistence of glass may be a pH-indicator. With evidence for the pH of weathering, the reactive transport code CrunchFlow can quantitatively calculate the minimum duration of exposure to liquid water consistent with a chemical profile. For the profile measured on the surface of Humphrey in Gusev Crater, the minimum exposure time is 22 ka. If correct, this estimate is consistent with short-term, episodic alteration accompanied by ongoing surface erosion. More of these depth profiles should be measured to illuminate the weathering history of Mars.« less

Raising environmental awareness through applied biochemistry laboratory experiments.

PubMed

Salman Ashraf, S

2013-01-01

Our environment is under constant pressure and threat from various sources of pollution. Science students, in particular chemistry students, must not only be made aware of these issues, but also be taught that chemistry (and science) can provide solutions to such real-life issues. To this end, a newly developed biochemistry laboratory experiment is described that guides students to learn about the applicability of peroxidase enzymes to degrade organic dyes (as model pollutants) in simulated waste water. In addition to showing how enzymes can potentially be used for waste water remediation, various factors than can affect enzyme-based reactions such as pH, temperature, concentration of substrates/enzymes, and denaturants can also be tested. This "applied biotechnology" experiment was successfully implemented in an undergraduate biochemistry laboratory course to enhance students' learning of environmental issues as well important biochemistry concepts. Student survey confirmed that this laboratory experiment was successful in achieving the objectives of raising environmental awareness in students and illustrating the usefulness of chemistry in solving real-life problems. This experiment can be easily adopted in an introductory biochemistry laboratory course and taught as an inquiry-guided exercise. © 2013 by The International Union of Biochemistry and Molecular Biology.

Lithium Sorption from Simulated Geothermal Brine: Impact of pH, Temperature, and Brine Chemistry

DOE Data Explorer

Jay Renew

2016-02-06

Lithium sorption information from experiments. Data includes the effects of pH, temperature and brine chemistry on the sorption of Lithium from a simulated geothermal brine. The sorbent used in the experiments is "hydrothermally produced, Spinel-LiMn2O4". The sorbent was produced by Carus Corporation.

Molecular layer deposition of APTES on silicon nanowire biosensors: Surface characterization, stability and pH response

NASA Astrophysics Data System (ADS)

Liang, Yuchen; Huang, Jie; Zang, Pengyuan; Kim, Jiyoung; Hu, Walter

2014-12-01

We report the use of molecular layer deposition (MLD) for depositing 3-aminopropyltriethoxysilane (APTES) on a silicon dioxide surface. The APTES monolayer was characterized using spectroscopic ellipsometry, contact angle goniometry, and atomic force microscopy. Effects of reaction time of repeating pulses and simultaneous feeding of water vapor with APTES were tested. The results indicate that the synergistic effects of water vapor and reaction time are significant for the formation of a stable monolayer. Additionally, increasing the number of repeating pulses improved the APTES surface coverage but led to saturation after 10 pulses. In comparing MLD with solution-phase deposition, the APTES surface coverage and the surface quality were nearly equivalent. The hydrolytic stability of the resulting films was also studied. The results confirmed that the hydrolysis process was necessary for MLD to obtain stable surface chemistry. Furthermore, we compared the pH sensing results of Si nanowire field effect transistors (Si NWFETs) modified by both the MLD and solution methods. The highly repeatable pH sensing results reflected the stability of APTES monolayers. The results also showed an improved pH response of the sensor prepared by MLD compared to the one prepared by the solution treatment, which indicated higher surface coverage of APTES.

Marine bivalve geochemistry and shell ultrastructure from modern low pH environments

NASA Astrophysics Data System (ADS)

Hahn, S.; Rodolfo-Metalpa, R.; Griesshaber, E.; Schmahl, W. W.; Buhl, D.; Hall-Spencer, J. M.; Baggini, C.; Fehr, K. T.; Immenhauser, A.

2011-10-01

Bivalve shells can provide excellent archives of past environmental change but have not been used to interpret ocean acidification events. We investigated carbon, oxygen and trace element records from different shell layers in the mussels Mytilus galloprovincialis (from the Mediterranean) and M. edulis (from the Wadden Sea) combined with detailed investigations of the shell ultrastructure. Mussels from the harbour of Ischia (Mediterranean, Italy) were transplanted and grown in water with mean pHT 7.3 and mean pHT 8.1 near CO2 vents on the east coast of the island of Ischia. The shells of transplanted mussels were compared with M. edulis collected at pH ~8.2 from Sylt (German Wadden Sea). Most prominently, the shells recorded the shock of transplantation, both in their shell ultrastructure, textural and geochemical record. Shell calcite, precipitated subsequently under acidified seawater responded to the pH gradient by an in part disturbed ultrastructure. Geochemical data from all test sites show a strong metabolic effect that exceeds the influence of the low-pH environment. These field experiments showed that care is needed when interpreting potential ocean acidification signals because various parameters affect shell chemistry and ultrastructure. Besides metabolic processes, seawater pH, factors such as salinity, water temperature, food availability and population density all affect the biogenic carbonate shell archive.

Controlling radiation fields in siemans designed light water reactors

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

Riess, R.; Marchl, T.

1995-03-01

An essential item for the control of radiation fields is the minimization of the use of satellites in the reactor systems of Light Water Reactors (LWRs). A short description of the qualification of Co-replacement materials will be followed by an illustration of the locations where these materials were implemented in Siemens designed LWRs. Especially experiences in PWRs show the immense influence of reduction of cobalt sources on dose rate buildup. The corrosion and the fatique and wear behavior of the replacement materials has not created concern up to now. A second tool to keep occupational radiation doses at a lowmore » level in PWRs is the use of the modified B/Li-chemistry. This is practized in Siemens designed plants by keeping the Li level at a max. value of 2 ppm until it reaches a pH (at 300{degrees}C) of {approximately}7.4. This pH is kept constant until the end of the cycle. The substitution of cobalt base alloys and thus the removal of the Co-59 sources from the system had the largest impact on the radiation levels. Nonetheless, the effectiveness of the coolant chemistry should not be neglected either. Several years of successful operation of PWRs with the replacement materials resulted in an occupational radiation exposure which is below 0.5 man-Sievert/plant and year.« less

Physico-chemical changes of ZnO nanoparticles with different size and surface chemistry under physiological pH conditions.

PubMed

Gwak, Gyeong-Hyeon; Lee, Won-Jae; Paek, Seung-Min; Oh, Jae-Min

2015-03-01

We studied the physico-chemical properties of ZnO nanoparticles under physiological pH conditions (gastric, intestinal and plasma) as functions of their size (20 and 70 nm) and surface chemistry (pristine, L-serine, or citrate coating). ZnO nanoparticles were dispersed in phosphate buffered saline under physiological pH conditions and aliquots were collected at specific time points (0.5, 1, 4, 10 and 24 h) for further characterization. The pH values of the aqueous ZnO colloids at each condition were in the neutral to slightly basic range and showed different patterns depending on the original size and surface chemistry of the ZnO nanoparticles. The gastric pH condition was found to significantly dissolve ZnO nanoparticles up to 18-30 wt%, while the intestinal or plasma pH conditions resulted in much lower dissolution amounts than expected. Based on the X-ray diffraction patterns and X-ray absorption spectra, we identified partial phase transition of the ZnO nanoparticles from wurtzite to Zn(OH)2 under the intestinal and plasma pH conditions. Using scanning electron microscopy, we verified that the overall particle size and morphology of all ZnO nanoparticles were maintained regardless of the pH. Copyright © 2015 Elsevier B.V. All rights reserved.

Carbon System Dynamics within the Papahānaumokuākea Marine National Monument

NASA Astrophysics Data System (ADS)

Kealoha, A. K.; Winn, C. D.; Kahng, S.; Alin, S. R.; Mackenzie, F. T.; Kosaki, R.

2013-12-01

Continuous underway measurements of atmospheric CO2, oceanic pCO2, pH, salinity, temperature, and oxygen were collected in surface waters within Papahānaumokuākea Marine National Monument (PMNM). Transects were conducted in the summers of 2011 and 2012 and encompassed the entire length of monument waters from approximately 21° to 28°N. Discrete samples were obtained from the underway system for the determination of spectrophotometric pH and titration alkalinity. The discrete pH samples were used to assess the consistency of the underway pH electrode and indicate that the electrode generated consistent and precise data over the duration of each cruise. The underway data collected over the entire transects show considerable variability in carbon parameters and reflects mainly the intense biological activity that occurs within coral reef ecosystems in and around the atolls comprising the Northwestern Hawaiian Archipelago. The impact of organic and inorganic metabolism on the carbon system in nearshore water was based primarily on measurements taken at French Frigate Shoals (FFS), where our most intense sampling occurred. For this analysis, all of the data collected within the area encompassed by the atoll and the surrounding ocean roughly 10 km from the 50-meter depth contour were included. These data, which span an approximate 300-km2 area, clearly show that nearshore metabolic processes influence surface water chemistry out to at least 10 km away from the shallow-water environment. Our data also show that, while the spatio-temporal complexities associated with analyzing underway data can complicate the interpretation of pCO2 and pH variability, an obvious diel trend in total alkalinity (TA) was apparent. In addition, plotting temporal changes in total dissolved inorganic carbon (DIC) and TA revealed the relative contributions of organic and inorganic metabolism to net reef metabolism.

Desorption of 1,3,5-Trichlorobenzene from Multi-Walled Carbon Nanotubes: Impact of Solution Chemistry and Surface Chemistry

PubMed Central

Ma, Xingmao; Uddin, Sheikh

2013-01-01

The strong affinity of carbon nanotubes (CNTs) to environmental contaminants has raised serious concern that CNTs may function as a carrier of environmental pollutants and lead to contamination in places where the environmental pollutants are not expected. However, this concern will not be realized until the contaminants are desorbed from CNTs. It is well recognized that the desorption of environmental pollutants from pre-laden CNTs varies with the environmental conditions, such as the solution pH and ionic strength. However, comprehensive investigation on the influence of solution chemistry on the desorption process has not been carried out, even though numerous investigations have been conducted to investigate the impact of solution chemistry on the adsorption of environmental pollutants on CNTs. The main objective of this study was to determine the influence of solution chemistry (e.g., pH, ionic strength) and surface functionalization on the desorption of preloaded 1,3,5-trichlorobenzene (1,3,5-TCB) from multi-walled carbon nanotubes (MWNTs). The results suggested that higher pH, ionic strength and natural organic matter in solution generally led to higher desorption of 1,3,5-TCB from MWNTs. However, the extent of change varied at different values of the tested parameters (e.g., pH < 7 vs. pH > 7). In addition, the impact of these parameters varied with MWNTs possessing different surface functional groups, suggesting that surface functionalization could considerably alter the environmental behaviors and impact of MWNTs. PMID:28348336

Scales and sources of pH and dissolved oxygen variability in a shallow, upwelling-driven ecosystem

NASA Astrophysics Data System (ADS)

Tanner, C. A.; Martz, T.; Levin, L. A.

2011-12-01

In the coastal zone extreme variability in carbonate chemistry and oxygen is driven by fluctuations in temperature, salinity, air-sea gas exchange, mixing processes, and biology. This variability appears to be magnified in upwelling-driven ecosystems where low oxygen and low pH waters intrude into shallow depths. The oxygen and carbon chemistry signal can be further confounded by highly productive ecosystems such as kelp beds where photosynthesis and respiration consume and release significant amounts of dissolved inorganic carbon and oxygen. This variability poses a challenge for scientists assessing the impacts of climate change on nearshore ecosystems. We deployed physical & biogeochemical sensors in order to observe these processes in situ. The "SeapHOx" instruments used in this study consist of a modified Honeywell Durafet° ISFET pH sensor, an Aanderra Optode Oxygen sensor, and a SBE-37 conductivity, temperature, pressure sensor. The instruments were deployed on and around the La Jolla Kelp Forest at a variety of depths. Our goals were to (a) characterize the link between pH and oxygen and identify the magnitude of pH and oxygen variability over a range of intra-annual time scales and (b) investigate spatial patterns of pH and oxygen variability associated with depth, proximity to shore, and presence of kelp. Results thus far reveal a strong relationship between oxygen and pH. Temporal variability is greatest at the semidiurnal frequency where pH (at 7 m) can range up to 0.3 units and oxygen can change 50% over 6 h. Diurnal variability is a combination of the diurnal tidal component and diel cycles of production and respiration. Event-scale dynamics associated with upwelling can maintain pH and oxygen below 7.8 units and 200 μmol kg-1, respectively, for multiple days. Frequent current reversals drive changes in the observed oxygen and pH variability. When alongshore currents are flowing southward, driven by upwelling-favorable winds, the magnitude of semidiurnal pH variability increases 5-fold relative to the magnitude of change during northward alongshore. Applying an empirically-determined alkalinity relationship, we conclude that changes in the carbonate chemistry parameters are largely driven by changes in total carbon. On small spatial scales, cross-shore differences exist in mean oxygen and pH but differences in alongshore mean oxygen and pH at a given depth appears to be negligible. Cross-shore differences can equate to a 0.05 pH unit decrease and 25 μmol kg-1 oxygen decrease over 1 km at a given depth. Strong spatial variability in pH and oxygen conditions exist over vertical gradients in the kelp forest, with mean pH at the surface (7m) being 0.2 pH units greater than at the bottom (17m) and mean oxygen being 104 μmol kg-1 greater. The observed range of pH (7.55-8.22) observed in this shallow environment during the course of a year is greater than open ocean predictions for a global mean pH reduction of 0.2-0.3 units predicted by the year 2100. These results suggest that organisms on exposed upwelling coasts may be adapted to a range of pH conditions and highlight the need for scientists to consider biological response to varying scales of pH change in order to develop more realistic predictions of the impacts of climate change for the coastal zone.

Chemistry Notes

ERIC Educational Resources Information Center

School Science Review, 1976

1976-01-01

Described are eight chemistry experiments and demonstrations applicable to introductory chemistry courses. Activities include: measure of lattice enthalpy, Le Chatelier's principle, decarboxylation of soap, use of pocket calculators in pH measurement, and making nylon. (SL)

Copolymer Synthesis and Characterization by Post-Polymerization Modification

NASA Astrophysics Data System (ADS)

Galvin, Casey James

This PhD thesis examines the physical behavior of surface-grafted polymer assemblies (SGPAs) derived from post-polymerization modification (PPM) reactions in aqueous and vapor enriched environments, and offers an alternative method of creating SGPAs using a PPM approach. SGPAs comprise typically polymer chains grafted covalently to solid substrates. These assemblies show promise in a number of applications and technologies due to the stability imparted by the covalent graft and ability to modify interfacial properties and stability. SGPAs also offer a set of rich physics to explore in fundamental investigations as a result of confining macromolecules to a solid substrate. PPM reactions (also called polymer analogous reactions) apply small molecule organic chemistry reactions to the repeat units of polymer chains in order to generate new chemistries. By applying a PPM strategy to SGPAs, a wide variety of functional groups can be introduced into a small number of well-studied and well-behaved model polymer systems. This approach offers the advantage of holding constant other properties of the SGPA (e.g., molecular weight, MW, and grafting density, sigma) to isolate the effect of chemistry on physical behavior. Using a combination of PPM and fabrication methods that facilitate the formation of SPGAs with position-dependent gradual variation of sigma on flat impenetrable substrate, the influence of polymer chemistry and sigma is examined on the stability of weak polyelectrolyte brushes in aqueous environments at different pH levels. Degrafting of polymer chains in SGPAs exhibits a complex dependence on side chain chemistry, sigma, pH and the charge fraction (alpha) within the brush. Results of these experiments support a proposed mechanism of degrafting, wherein extension of the grafted chains away from the substrate generates tension along the polymer backbone, which activates the grafting chemistry for hydrolysis. The implications of these findings are important in developing technologies that use SGPAs in aqueous environments, and point to a need for potential alternative grafting chemistries. The behavior of SGPAs in vapor environments remains an underexplored phenomenon. By changing systematically the chemistry of SGPAs derived from a parent sample, the influence of side chain functional groups on the swelling of weak and strong polyelectrolyte brushes in the presence of water, methanol and ethanol vapors is explored. The extent of swelling and solvent uptake depends strongly on the chemistry in the polymer side chain and of the solvent. Despite bearing a permanent electrostatic charge in the side chain, the strong polyelectrolyte brushes exhibit no behavior typical of polyelectrolytes in water due to no dissociation of the counterion. Of particular interest is the behavior in humid environments of an SGPA bearing a zwitterionic group in its side chain, which results in exposure of electrostatic charges without counterions. Using substrates bearing the aforementioned sigma gradient of polymeric grafts, evidence of inter- and intramolecular complex formation is presented. Finally, a method of developing SGPAs by polymerizing bulk polymer chains through surface-grafted monomers (SGMs) is described. The SGMs are incorporated onto a solid substrate using the same PPM reaction employed in the degrafting and vapor swelling experiments, highlighting the versatility of PPM. The thickness of these SGPAs is correlated to the bulk polymer chains MW, suggesting this technique can be used in existing industrial bulk polymerization processes.

Changes in stream chemistry and biology in response to reduced levels of acid deposition during 1987-2003 in the Neversink River Basin, Catskill Mountains

USGS Publications Warehouse

Burns, Douglas A.; Riva-Murray, K.; Bode, R.W.; Passy, S.

2008-01-01

Atmospheric acid deposition has decreased in the northeastern United States since the 1970s, resulting in modest increases in pH, acid-neutralizing capacity (ANC), and decreases in inorganic monomeric aluminum (AlIM) concentrations since stream chemistry monitoring began in the 1980s in the acid-sensitive upper Neversink River basin in the Catskill Mountains of New York. Stream pH has increased by 0.01 units/year during 1987-2003 at three sites in the Neversink basin as determined by Seasonal Kendall trend analysis. In light of this observed decrease in stream acidity, we sampled 12 stream sites within the Neversink River watershed for water chemistry, macroinvertebrates, fish, and periphytic diatoms in 2003 to compare with a similar data set collected in 1987. Metrics and indices that reflect sensitivity to stream acidity were developed with these biological data to determine whether changes in stream biota over the intervening 16 years parallel those of stream chemistry. Statistical comparisons of data on stream chemistry and an acid biological assessment profile (Acid BAP) derived from invertebrate data showed no significant differences between the two years. For pH and ANC, however, values in 2003 were generally lower than those in 1987; this difference likely resulted from higher streamflow in summer 2003. Despite these likely flow-induced changes in summer 2003, an ordination and cluster analysis of macroinvertebrate taxa based on the Acid BAP indicated that the most acidic sites in the upstream half of the East Branch Neversink River form a statistically significant separate cluster consistent with less acidic stream conditions. This analysis is consistent with limited recovery of invertebrate species in the most acidic reaches of the river, but will require additional improvement in stream chemistry before a stronger conclusion can be drawn. Data on the fish and periphytic diatom communities in 2003 indicate that slimy sculpin had not extended their habitat to upstream reaches that previously were devoid of this acid-intolerant species in 1987; a diatom acid-tolerance index indicates continued high-acid impact throughout most of the East Branch and headwaters of the West Branch Neversink River. ?? 2007 Elsevier Ltd. All rights reserved.

Hydrogeochemical and mineralogical effects of sustained CO2 contamination in a shallow sandy aquifer: A field-scale controlled release experiment

NASA Astrophysics Data System (ADS)

Cahill, Aaron G.; Marker, Pernille; Jakobsen, Rasmus

2014-02-01

A shallow aquifer CO2 contamination experiment was performed to investigate evolution of water chemistry and sediment alteration following leakage from geological storage by physically simulating a leak from a hypothetical storage site. In a carbonate-free aquifer, in western Denmark, a total of 1600 kg of gas phase CO2 was injected at 5 and 10 m depth over 72 days through four inclined injection wells into aeolian and glacial sands. Water chemistry was monitored for pH, EC, and dissolved element evolution through an extensive network of multilevel sampling points over 305 days. Sediment cores were taken pre and postinjection and analyzed to search for effects on mineralogy and sediment properties. Results showed the simulated leak to evolve in two distinct phases; an advective elevated ion pulse followed by increasing persistent acidification. Spatial and temporal differences in evolution of phases suggest separate chemical mechanisms and geochemical signatures. Dissolved element concentrations developed exhibiting four behaviors: (1) advective pulse (Ca, Mg, Na, Si, Ba, and Sr), (2) pH sensitive abundance dependent (Al and Zn), (3) decreasing (Mn and Fe), and (4) unaffected (K). Concentration behaviors were characterized by: (1) a maximal front moving with advective flow, (2) continual increase in close proximity to the injection plane, (3) removal from solution, and (4) no significant change. Only Al was observed to exceed WHO guidelines, however significantly so (10-fold excess). The data indicate that pH is controlled by equilibrium with gibbsite which is again coupled to cation exchange processes. Pre and postinjection sediment analysis indicated alteration of sediment composition and properties including depletion of reactive mineral species.

Small-scale variability in peatland pore-water biogeochemistry, Hudson Bay Lowland, Canada.

PubMed

Ulanowski, T A; Branfireun, B A

2013-06-01

The Hudson Bay Lowland (HBL) of northern Ontario, Manitoba and Quebec, Canada is the second largest contiguous peatland complex in the world, currently containing more than half of Canada's soil carbon. Recent concerns about the ecohydrological impacts to these large northern peatlands resulting from climate change and resource extraction have catalyzed a resurgence in scientific research into this ecologically important region. However, the sheer size, heterogeneity and elaborate landscape arrangements of this ecosystem raise important questions concerning representative sampling of environmental media for chemical or physical characterization. To begin to quantify such variability, this study assessed the small-scale spatial (1m) and short temporal (21 day) variability of surface pore-water biogeochemistry (pH, dissolved organic carbon, and major ions) in a Sphagnum spp.-dominated, ombrotrophic raised bog, and a Carex spp.-dominated intermediate fen in the HBL. In general, pore-water pH and concentrations of dissolved solutes were similar to previously reported literature values from this region. However, systematic sampling revealed consistent statistically significant differences in pore-water chemistries between the bog and fen peatland types, and large within-site spatiotemporal variability. We found that microtopography in the bog was associated with consistent differences in most biogeochemical variables. Temporal changes in dissolved solute chemistry, particularly base cations (Na(+), Ca(2+) and Mg(2+)), were statistically significant in the intermediate fen, likely a result of a dynamic connection between surficial waters and mineral-rich deep groundwater. In both the bog and fen, concentrations of SO4(2-) showed considerable spatial variability, and a significant decrease in concentrations over the study period. The observed variability in peatland pore-water biogeochemistry over such small spatial and temporal scales suggests that under-sampling in northern peatland environments could lead to erroneous conclusions concerning the abundance and distribution of natural elements and pollutants alike. Copyright © 2013 Elsevier B.V. All rights reserved.

Instrument developments for chemical and physical characterization, mapping and sampling of extreme environments (Antarctic sub ice environment)

NASA Astrophysics Data System (ADS)

Vogel, S. W.; Powell, R. D.; Griffith, I.; Lawson, T.; Schiraga, S.; Ludlam, G.; Oen, J.

2009-12-01

A number of instrumentation is currently under development designed to enable the study of subglacial environments in Antarctica through narrow kilometer long boreholes. Instrumentation includes: - slim line Sub-Ice ROV (SIR), - Geochemical Instrumentation Package for Sub Ice Environments (GIPSIE) to study geochemical fluxes in water and across the sediment water interface (CO2, CH4, dO, NH4, NO3, Si, PO4, pH, redox, T, H2, HS, O2, N2O, CTD, particle size, turbidity, color camera, current meter and automated water sampler) with real-time telemetry for targeted sampling, - long term energy-balance mooring system, - active source slide hammer sediment corer, and - integration of a current sensor into the ITP profiler. The instrumentation design is modular and suitable for remote operated as well as autonomous long-term deployment. Of interest to the broader science community is the development of the GIPSIE and efforts to document the effect of sample recovery from depth on the sample chemistry. The GIPSIE is a geochemical instrumentation package with life stream telemetry, allowing for user controlled targeted sampling of water column and the water sediment interphase for chemical and biological work based on actual measurements and not a preprogrammed automated system. The porewater profiler (pH, redox, T, H2, HS, O2, N2O) can penetrate the upper 50 cm of sediment and penetration is documented with real time video. Associated with GIPSIE is an on-site lab set-up, utilizing a set of identical sensors. Comparison between the insitu measurements and measurements taken onsite directly after samples are recovered from depth permits assessing the effect of sample recovery on water and sediment core chemistry. Sample recovery related changes are mainly caused by changes in the pressure temperature field and exposure of samples to atmospheric conditions. Exposure of anaerobic samples to oxygen is here a specific concern. Recovery from depth effects in generally pH, solubility of gases and nutrients and can initiate complex chemical reaction, the product of which is later measured in the lab. Further information on the instrument developments can be found at http://jove.geol.niu.edu/faculty/svogel/Technology/Technology-index.html

Mapping bark pH to better understand the cortisphere

NASA Astrophysics Data System (ADS)

Levia, D. F., Jr.; Köhler, S.; Jungkunst, H. F.; Gerold, G.

2016-12-01

The biogeochemistry of the cortisphere is poorly understood, despite the fact that a large variety of microbes, epiphytes, and insects live on, within, and just beneath corticular surfaces. Bark pH is a critical parameter that partially controls the chemodynamics of the cortisphere and its habitability by bark dwelling organisms as well as the chemistry of throughfall and stemflow. This presentation articulates, tests, and validates a method to accurately determine bark pH in situ. We employed agar-agar panels, embedded with a pH marker, to determine the spatiality of bark pH on cacao trees in Indonesia. In contrast to existing ex situ methods, we were able to record spatial differences in bark pH. In particular, bark pH was observed to fluctuate in relation to both morphological features on the bark, possibly corresponding to preferential flowpaths of stemflow, and epiphytic coverage. Due to its simplicity and economical nature, our method may be attractive to a variety of researchers interested in bark pH, its spatial variability, influence on stemflow chemistry, and its effect on organisms dwelling in the cortipshere. Publication note: This presentation is based on the following article: Köhler, S., Levia, D.F., Jungkunst, H.F. and Gerold, G. 2015. An in situ method to measure and map bark pH. Journal of Wood Chemistry and Technology 35(6): 438-449. [DOI: 10.1080/02773813.2015.1025285

Influence of Water Solute Exposure on the Chemical Evolution and Rheological Properties of Asphalt.

PubMed

Pang, Ling; Zhang, Xuemei; Wu, Shaopeng; Ye, Yong; Li, Yuanyuan

2018-06-11

The properties of asphalt pavement are damaged under the effects of moisture. The pH value and salt concentration of water are the key factors that affect the chemical and rheological properties of asphalt during moisture damage. Four kinds of water solutions, including distilled water, an acidic solution, alkaline solution and saline solution were used to investigate the effects of aqueous solute compositions on the chemical and rheological properties of asphalt. Thin-layer chromatography with flame ionization detection (TLC-FID), Fourier transform infrared (FTIR) spectroscopy and dynamic shear rheometer (DSR) were applied to investigate the components, chemistry and rheology characteristics of asphalt specimens before and after water solute exposure. The experimental results show that moisture damage of asphalt is not only associated with an oxidation process between asphalt with oxygen, but it is also highly dependent on some compounds of asphalt dissolving and being removed in the water solutions. In detail, after immersion in water solute, the fraction of saturates, aromatics and resins in asphalt binders decreased, while asphaltenes increased; an increase in the carbonyl and sulphoxide indices, and a decrease in the butadiene index were also found from the FTIR analyzer test. The rheological properties of asphalt are sensitive to water solute immersing. The addition of aqueous solutes causes more serious moisture damage on asphalt binders, with the pH11 solution presenting as the most destructive during water solute exposure.

Effects of the Urban Heat Island on Aerosol pH

NASA Astrophysics Data System (ADS)

Battaglia, M., Jr.; Douglas, S.; Hennigan, C. J.

2017-12-01

The urban heat island (UHI) is a widely observed phenomenon whereby urban environments have higher temperature (T) and lower relative humidity (RH) than surrounding suburban and rural areas. Both of these factors affect the partitioning of semi-volatile species found in the atmosphere, such as nitric acid and ammonia. These species are inherently tied to aerosol pH, which is a key parameter driving some atmospheric chemical processes and environmental effects of aerosols. In this study, we characterized the effect of the UHI on aerosol pH in Baltimore, MD and Chicago, IL. These cities were selected based on differences in climatology, source influences, and atmospheric composition. Meteorological and atmospheric composition data from the urban centers and surrounding rural locations were used as inputs to the ISORROPIA-II aerosol thermodynamic model to compute gas/particle partitioning, aerosol liquid water content, and aerosol pH. Dramatic differences in aerosol liquid water (ALW) content were found in both cities and were attributable to the T and RH differences (UHI effect). The urban-rural differences in ALW result in urban aerosol pH that is systematically lower (more acidic) than rural aerosol pH for identical atmospheric composition. The UHI in Baltimore is most intense during the summer and at night, with differences of up to 1 pH unit predicted during these times. Similarly, the UHI in Chicago is most intense during the summer and at night; however, the atmospheric composition in Chicago shows a mediating effect, with differences of up to 0.65 pH units predicted during these times. These results are likely to have broad implications for chemistry occurring in and around urban atmospheres globally, although the magnitude of the effect may differ based on the UHI characteristic of each urban environment.

Gas flushing through hyper-acidic crater lakes: the next steps within a reframed monitoring time window

NASA Astrophysics Data System (ADS)

Rouwet, Dmitri

2016-04-01

Tracking variations in the chemical composition, water temperature and pH of brines from peak-activity crater lakes is the most obvious way to forecast phreatic activity. Volcano monitoring intrinsically implies a time window of observation that should be synchronised with the kinetics of magmatic processes, such as degassing and magma intrusion. To decipher "how much time ago" a variation in degassing regime actually occurred before eventually being detected in a crater lake is key, and depends on the lake water residence time. The above reasoning assumes that gas is preserved as anions in the lake water (SO4, Cl, F anions), in other words, that scrubbing of acid gases is complete and irreversible. Less is true. Recent work has confirmed, by direct MultiGas measurement from evaporative plumes, that even the strongest acid in liquid medium (i.e. SO2) degasses from hyper-acidic crater lakes. The less strong acid HCl has long been recognised as being more volatile than hydrophyle in extremely acidic solutions (pH near 0), through a long-term steady increase in SO4/Cl ratios in the vigorously evaporating crater lake of Poás volcano. We now know that acidic gases flush through hyper-acidic crater lake brines, but we don't know to which extend (completely or partially?), and with which speed. The chemical composition hence only reflects a transient phase of the gas flushing through the lake. In terms of volcanic surveillance this brings the advantage that the monitoring time window is definitely shorter than defined by the water chemistry, but yet, we do not know how much shorter. Empirical experiments by Capaccioni et al. (in press) have tried to tackle this kinetic problem for HCl degassing from a "lab-lake" on the short-term (2 days). With this state of the art in mind, two new monitoring strategies can be proposed to seek for precursory signals of phreatic eruptions from crater lakes: (1) Tracking variations in gas compositions, fluxes and ratios between species in evaporative degassing plumes can be useful as monitoring tool on the short-term, but only if the underlying process of gas flushing through acidic lakes is better understood, and linked with the lake water chemistry; (2) The second method forgets about chemical kinetics, degassing models and dynamics of phreatic eruptions, and sticks to the classical principle in geology of "the past is the key for the future". How did lake chemistry parameters vary during the various stages of unrest and eruption, on a purely mathematical basis? Can we recognise patterns in the numerical values related to the changes in volcanic activity? Water chemistry only as a monitoring tool for extremely dynamic and erupting crater lake systems, is inefficient in revealing short-term precursors for single phreatic eruptions, within the current perspective of the residence time dependent monitoring time window. The monitoring rules established since decades based only on water chemistry have thus somehow become obsolete and need revision.

Protein adsorption at the electrified air-water interface: implications on foam stability.

PubMed

Engelhardt, Kathrin; Rumpel, Armin; Walter, Johannes; Dombrowski, Jannika; Kulozik, Ulrich; Braunschweig, Björn; Peukert, Wolfgang

2012-05-22

The surface chemistry of ions, water molecules, and proteins as well as their ability to form stable networks in foams can influence and control macroscopic properties such as taste and texture of dairy products considerably. Despite the significant relevance of protein adsorption at liquid interfaces, a molecular level understanding on the arrangement of proteins at interfaces and their interactions has been elusive. Therefore, we have addressed the adsorption of the model protein bovine serum albumin (BSA) at the air-water interface with vibrational sum-frequency generation (SFG) and ellipsometry. SFG provides specific information on the composition and average orientation of molecules at interfaces, while complementary information on the thickness of the adsorbed layer can be obtained with ellipsometry. Adsorption of charged BSA proteins at the water surface leads to an electrified interface, pH dependent charging, and electric field-induced polar ordering of interfacial H(2)O and BSA. Varying the bulk pH of protein solutions changes the intensities of the protein related vibrational bands substantially, while dramatic changes in vibrational bands of interfacial H(2)O are simultaneously observed. These observations have allowed us to determine the isoelectric point of BSA directly at the electrolyte-air interface for the first time. BSA covered air-water interfaces with a pH near the isoelectric point form an amorphous network of possibly agglomerated BSA proteins. Finally, we provide a direct correlation of the molecular structure of BSA interfaces with foam stability and new information on the link between microscopic properties of BSA at water surfaces and macroscopic properties such as the stability of protein foams.

Long-term geochemical evolution of the near field repository: Insights from reactive transport modelling and experimental evidences

NASA Astrophysics Data System (ADS)

Arcos, David; Grandia, Fidel; Domènech, Cristina; Fernández, Ana M.; Villar, María V.; Muurinen, Arto; Carlsson, Torbjörn; Sellin, Patrik; Hernán, Pedro

2008-12-01

The KBS-3 underground nuclear waste repository concept designed by the Swedish Nuclear Fuel and Waste Management Co. (SKB) includes a bentonite buffer barrier surrounding the copper canisters and the iron insert where spent nuclear fuel will be placed. Bentonite is also part of the backfill material used to seal the access and deposition tunnels of the repository. The bentonite barrier has three main safety functions: to ensure the physical stability of the canister, to retard the intrusion of groundwater to the canisters, and in case of canister failure, to retard the migration of radionuclides to the geosphere. Laboratory experiments (< 10 years long) have provided evidence of the control exerted by accessory minerals and clay surfaces on the pore water chemistry. The evolution of the pore water chemistry will be a primordial factor on the long-term stability of the bentonite barrier, which is a key issue in the safety assessments of the KBS-3 concept. In this work we aim to study the long-term geochemical evolution of bentonite and its pore water in the evolving geochemical environment due to climate change. In order to do this, reactive transport simulations are used to predict the interaction between groundwater and bentonite which is simulated following two different pathways: (1) groundwater flow through the backfill in the deposition tunnels, eventually reaching the top of the deposition hole, and (2) direct connection between groundwater and bentonite rings through fractures in the granite crosscutting the deposition hole. The influence of changes in climate has been tested using three different waters interacting with the bentonite: present-day groundwater, water derived from ice melting, and deep-seated brine. Two commercial bentonites have been considered as buffer material, MX-80 and Deponit CA-N, and one natural clay (Friedland type) for the backfill. They show differences in the composition of the exchangeable cations and in the accessory mineral content. Results from the simulations indicate that pore water chemistry is controlled by the equilibrium with the accessory minerals, especially carbonates. pH is buffered by precipitation/dissolution of calcite and dolomite, when present. The equilibrium of these minerals is deeply influenced by gypsum dissolution and cation exchange reactions in the smectite interlayer. If carbonate minerals are initially absent in bentonite, pH is then controlled by surface acidity reactions in the hydroxyl groups at the edge sites of the clay fraction, although its buffering capacity is not as strong as the equilibrium with carbonate minerals. The redox capacity of the bentonite pore water system is mainly controlled by Fe(II)-bearing minerals (pyrite and siderite). Changes in the groundwater composition lead to variations in the cation exchange occupancy, and dissolution-precipitation of carbonate minerals and gypsum. The most significant changes in the evolution of the system are predicted when ice-melting water, which is highly diluted and alkaline, enters into the system. In this case, the dissolution of carbonate minerals is enhanced, increasing pH in the bentonite pore water. Moreover, a rapid change in the population of exchange sites in the smectite is expected due to the replacement of Na for Ca.

Long-term geochemical evolution of the near field repository: insights from reactive transport modelling and experimental evidences.

PubMed

Arcos, David; Grandia, Fidel; Domènech, Cristina; Fernández, Ana M; Villar, María V; Muurinen, Arto; Carlsson, Torbjörn; Sellin, Patrik; Hernán, Pedro

2008-12-12

The KBS-3 underground nuclear waste repository concept designed by the Swedish Nuclear Fuel and Waste Management Co. (SKB) includes a bentonite buffer barrier surrounding the copper canisters and the iron insert where spent nuclear fuel will be placed. Bentonite is also part of the backfill material used to seal the access and deposition tunnels of the repository. The bentonite barrier has three main safety functions: to ensure the physical stability of the canister, to retard the intrusion of groundwater to the canisters, and in case of canister failure, to retard the migration of radionuclides to the geosphere. Laboratory experiments (< 10 years long) have provided evidence of the control exerted by accessory minerals and clay surfaces on the pore water chemistry. The evolution of the pore water chemistry will be a primordial factor on the long-term stability of the bentonite barrier, which is a key issue in the safety assessments of the KBS-3 concept. In this work we aim to study the long-term geochemical evolution of bentonite and its pore water in the evolving geochemical environment due to climate change. In order to do this, reactive transport simulations are used to predict the interaction between groundwater and bentonite which is simulated following two different pathways: (1) groundwater flow through the backfill in the deposition tunnels, eventually reaching the top of the deposition hole, and (2) direct connection between groundwater and bentonite rings through fractures in the granite crosscutting the deposition hole. The influence of changes in climate has been tested using three different waters interacting with the bentonite: present-day groundwater, water derived from ice melting, and deep-seated brine. Two commercial bentonites have been considered as buffer material, MX-80 and Deponit CA-N, and one natural clay (Friedland type) for the backfill. They show differences in the composition of the exchangeable cations and in the accessory mineral content. Results from the simulations indicate that pore water chemistry is controlled by the equilibrium with the accessory minerals, especially carbonates. pH is buffered by precipitation/dissolution of calcite and dolomite, when present. The equilibrium of these minerals is deeply influenced by gypsum dissolution and cation exchange reactions in the smectite interlayer. If carbonate minerals are initially absent in bentonite, pH is then controlled by surface acidity reactions in the hydroxyl groups at the edge sites of the clay fraction, although its buffering capacity is not as strong as the equilibrium with carbonate minerals. The redox capacity of the bentonite pore water system is mainly controlled by Fe(II)-bearing minerals (pyrite and siderite). Changes in the groundwater composition lead to variations in the cation exchange occupancy, and dissolution-precipitation of carbonate minerals and gypsum. The most significant changes in the evolution of the system are predicted when ice-melting water, which is highly diluted and alkaline, enters into the system. In this case, the dissolution of carbonate minerals is enhanced, increasing pH in the bentonite pore water. Moreover, a rapid change in the population of exchange sites in the smectite is expected due to the replacement of Na for Ca.

Molecular mechanisms for generating transmembrane proton gradients

PubMed Central

Gunner, M.R.; Amin, Muhamed; Zhu, Xuyu; Lu, Jianxun

2013-01-01

Membrane proteins use the energy of light or high energy substrates to build a transmembrane proton gradient through a series of reactions leading to proton release into the lower pH compartment (P-side) and proton uptake from the higher pH compartment (N-side). This review considers how the proton affinity of the substrates, cofactors and amino acids are modified in four proteins to drive proton transfers. Bacterial reaction centers (RCs) and photosystem II (PSII) carry out redox chemistry with the species to be oxidized on the P-side while reduction occurs on the N-side of the membrane. Terminal redox cofactors are used which have pKas that are strongly dependent on their redox state, so that protons are lost on oxidation and gained on reduction. Bacteriorhodopsin is a true proton pump. Light activation triggers trans to cis isomerization of a bound retinal. Strong electrostatic interactions within clusters of amino acids are modified by the conformational changes initiated by retinal motion leading to changes in proton affinity, driving transmembrane proton transfer. Cytochrome c oxidase (CcO) catalyzes the reduction of O2 to water. The protons needed for chemistry are bound from the N-side. The reduction chemistry also drives proton pumping from N- to P-side. Overall, in CcO the uptake of 4 electrons to reduce O2 transports 8 charges across the membrane, with each reduction fully coupled to removal of two protons from the N-side, the delivery of one for chemistry and transport of the other to the P-side. PMID:23507617

Impact of water chemistry on the particle-specific toxicity of copper nanoparticles to Daphnia magna.

PubMed

Xiao, Yinlong; Peijnenburg, Willie J G M; Chen, Guangchao; Vijver, Martina G

2018-01-01

Toxicity of metallic nanoparticle suspensions (NP (total) ) is generally assumed to result from the combined effect of the particles present in suspensions (NP (particle) ) and their released ions (NP (ion) ). Evaluation and consideration of how water chemistry affects the particle-specific toxicity of NP (total) are critical for environmental risk assessment of nanoparticles. In this study, it was found that the toxicity of Cu NP (particle) to Daphnia magna, in line with the trends in toxicity for Cu NP (ion) , decreased with increasing pH and with increasing concentrations of divalent cations and dissolved organic carbon (DOC). Without the addition of DOC, the toxicity of Cu NP (total) to D. magna at the LC50 was driven mainly by Cu NP (ion) (accounting for ≥53% of the observed toxicity). However, toxicity of Cu NP (total) in the presence of DOC at a concentration ranging from 5 to 50mg C/L largely resulted from the NP (particle) (57%-85%), which could be attributable to the large reduction of the concentration of Cu NP (ion) and the enhancement of the stability of Cu NP (particle) when DOC was added. Our results indicate that water chemistry needs to be explicitly taken into consideration when evaluating the role of NP (particle) and NP (ion) in the observed toxicity of NP (total) . Copyright © 2017 Elsevier B.V. All rights reserved.

Clean Energy for the Commonwealth Powered by UMass

DTIC Science & Technology

2009-04-15

Nanomagnetics Zeolite membranes Polymer-inorganic nanocomposites MEMS Nanostructured catalysts Plant Biotechnology Biochem., Cell wall struct., Agronomy Crambe...power management Low-power device networks Energy scavenging Flame Modeling Combustion chemistry Molecular-beam mass spectrometry Building Design...Thayumanavan, PhD. UMass Amherst Professor of Chemistry and Director, Fueling the Future Center for Chemical Innovation – Paul Osenar, PhD. Chief

Changes in Fe Oxidation Rate in Hydrothermal Plumes as a Potential Driver of Enhanced Hydrothermal Input to Near-Ridge Sediments During Glacial Terminations

NASA Astrophysics Data System (ADS)

Cullen, J. T.; Coogan, L. A.

2017-12-01

Recent studies have hypothesized that changes in sea level due to glacial-interglacial cycles lead to changes in the rate of melt addition to the crust at mid-ocean ridges with globally significant consequences. Arguably the most compelling evidence for this comes from increases in the hydrothermal component in near-ridge sediments during glacial-interglacial transitions. Here we explore the hypothesis that changes in ocean bottom water [O2] and pH across glacial-interglacial transitions would lead to changes in the rate of Fe oxidation in hydrothermal plumes. A simple model shows that a several fold increase in the rate of Fe oxidation is expected at glacial-interglacial transitions. Uncertainty in bottom water chemistry and the relationship between oxidation and sedimentation rates prevent direct comparison of the model and data. However, it appears that the null hypothesis of invariant hydrothermal vent fluxes into ocean bottom water that changed in O2 content and pH across these transitions cannot currently be discounted.

Chromium removal from ground water by Ion exchange resins

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

Skiadas, P.

1994-05-06

The ground water at several monitoring wells at LLNL has been found to exceed the Surface Water Discharge Limits for Cr(VI). Ion exchange resins have been selected for its removal. A research study is underway to determine which commercial resin is preferred for LLNL`s ground water. The choice of an appropriate resin will be based on Cr(VI) exchange capacity, regeneration efficiency, and pH stabilization. A sequestering agent must also be selected to be used for the elimination of scaling at the treatment facilities. The chemistry of ion exchange resins, and instrumentation and procedures are explained and described in the followingmore » paper. Comparison of the different resins tested lead us to the selection of the most effective one to be used in the treatment facilities.« less

A Conversation with James J. Morgan

NASA Astrophysics Data System (ADS)

Morgan, James J.; Newman, Dianne K.

2015-05-01

In conversation with professor Dianne Newman, Caltech geobiologist, James "Jim" J. Morgan recalls his early days in Ireland and New York City, education in parochial and public schools, and introduction to science in Cardinal Hayes High School, Bronx. In 1950, Jim entered Manhattan College, where he elected study of civil engineering, in particular water quality. Donald O'Connor motivated Jim's future study of O2 in rivers at Michigan, where in his MS work he learned to model O2 dynamics of rivers. As an engineering instructor at Illinois, Jim worked on rivers polluted by synthetic detergents. He chose to focus on chemical studies, seeing it as crucial for the environment. Jim enrolled for PhD studies with Werner Stumm at Harvard, who mentored his research in chemistry of particle coagulation and oxidation processes of Mn(II) and (IV). In succeeding decades, until retirement in 2000, Jim's teaching and research centered on aquatic chemistry; major themes comprised rates of abiotic manganese oxidation on particle surfaces and flocculation of natural water particles, and chemical speciation proved the key.

Enhancing boron rejection in FO using alkaline draw solutions.

PubMed

Wang, Yi-Ning; Li, Weiyi; Wang, Rong; Tang, Chuyang Y

2017-07-01

This study provides a novel method to enhance boron removal in a forward osmosis (FO) process. It utilizes the reverse solute diffusion (RSD) of ions from alkaline draw solutions (DSs) and the concentration polarization of the hydroxyl ions to create a highly alkaline environment near the membrane active surface. The results show that boron rejection can be significantly enhanced by increasing the pH of NaCl DS to 12.5 in the active-layer-facing-feed-solution (AL-FS) orientation. The effect of RSD enhanced boron rejection was further promoted in the presence of concentration polarization (e.g., in the active-layer-facing-draw-solution (AL-DS) orientation). The current study opens a new dimension for controlling contaminant removal by FO using tailored DS chemistry, where the RSD-induced localized water chemistry change is taken advantage in contrast to the conventional method of chemical dosing to the bulk feed water. Copyright © 2017 Elsevier Ltd. All rights reserved.

Microfluidics for High School Chemistry Students.

PubMed

Hemling, Melissa; Crooks, John A; Oliver, Piercen M; Brenner, Katie; Gilbertson, Jennifer; Lisensky, George C; Weibel, Douglas B

2014-01-14

We present a laboratory experiment that introduces high school chemistry students to microfluidics while teaching fundamental properties of acid-base chemistry. The procedure enables students to create microfluidic systems using nonspecialized equipment that is available in high school classrooms and reagents that are safe, inexpensive, and commercially available. The experiment is designed to ignite creativity and confidence about experimental design in a high school chemistry class. This experiment requires a computer program (e.g., PowerPoint), Shrinky Dink film, a readily available silicone polymer, weak acids, bases, and a colorimetric pH indicator. Over the span of five 45-min class periods, teams of students design and prepare devices in which two different pH solutions mix in a predictable way to create five different pH solutions. Initial device designs are instructive but rarely optimal. During two additional half-class periods, students have the opportunity to use their initial observations to redesign their microfluidic systems to optimize the outcome. The experiment exposes students to cutting-edge science and the design process, and solidifies introductory chemistry concepts including laminar flow, neutralization of weak acids-bases, and polymers.

Microfluidics for High School Chemistry Students

PubMed Central

Hemling, Melissa; Crooks, John A.; Oliver, Piercen M.; Brenner, Katie; Gilbertson, Jennifer; Lisensky, George C.; Weibel, Douglas B.

2014-01-01

We present a laboratory experiment that introduces high school chemistry students to microfluidics while teaching fundamental properties of acid–base chemistry. The procedure enables students to create microfluidic systems using nonspecialized equipment that is available in high school classrooms and reagents that are safe, inexpensive, and commercially available. The experiment is designed to ignite creativity and confidence about experimental design in a high school chemistry class. This experiment requires a computer program (e.g., PowerPoint), Shrinky Dink film, a readily available silicone polymer, weak acids, bases, and a colorimetric pH indicator. Over the span of five 45-min class periods, teams of students design and prepare devices in which two different pH solutions mix in a predictable way to create five different pH solutions. Initial device designs are instructive but rarely optimal. During two additional half-class periods, students have the opportunity to use their initial observations to redesign their microfluidic systems to optimize the outcome. The experiment exposes students to cutting-edge science and the design process, and solidifies introductory chemistry concepts including laminar flow, neutralization of weak acids–bases, and polymers. PMID:25584013

Water-quality data from two agricultural drainage basins in northwestern Indiana and northeastern Illinois: I. Lagrangian and synoptic data, 1999-2002

USGS Publications Warehouse

Antweiler, Ronald C.; Smith, Richard L.; Voytek, Mary A.; Bohlke, John Karl; Richards, Kevin D.

2005-01-01

Methods of data collection and results of analyses are presented for Lagrangian and synoptic water-quality data collected from two agricultural drainages, the Iroquois River in northwestern Indiana and Sugar Creek in northwestern Indiana and northeastern Illinois. During six separate sampling trips, in April, June and September 1999, May 2000, September 2001 and April 2002, 152 discrete water samples were collected to characterize the water chemistry over the course of 2 to 4 days on each of these drainages. Data were collected for nutrients, major inorganic constituents, dissolved organic carbon, trace elements, dissolved gases, total bacterial cell counts, chlorophyll-a concentrations, and suspended sediment concentrations. In addition, field measurements of streamflow, pH, specific conductance, water temperature, and dissolved oxygen concentration were made during all trips except April 1999.

Modeling hot spring chemistries with applications to martian silica formation

NASA Astrophysics Data System (ADS)

Marion, G. M.; Catling, D. C.; Crowley, J. K.; Kargel, J. S.

2011-04-01

Many recent studies have implicated hydrothermal systems as the origin of martian minerals across a wide range of martian sites. Particular support for hydrothermal systems include silica (SiO 2) deposits, in some cases >90% silica, in the Gusev Crater region, especially in the Columbia Hills and at Home Plate. We have developed a model called CHEMCHAU that can be used up to 100 °C to simulate hot springs associated with hydrothermal systems. The model was partially derived from FREZCHEM, which is a colder temperature model parameterized for broad ranges of temperature (<-70 to 25 °C), pressure (1-1000 bars), and chemical composition. We demonstrate the validity of Pitzer parameters, volumetric parameters, and equilibrium constants in the CHEMCHAU model for the Na-K-Mg-Ca-H-Cl-ClO 4-SO 4-OH-HCO 3-CO 3-CO 2-O 2-CH 4-Si-H 2O system up to 100 °C and apply the model to hot springs and silica deposits. A theoretical simulation of silica and calcite equilibrium shows how calcite is least soluble with high pH and high temperatures, while silica behaves oppositely. Such influences imply that differences in temperature and pH on Mars could lead to very distinct mineral assemblages. Using measured solution chemistries of Yellowstone hot springs and Icelandic hot springs, we simulate salts formed during the evaporation of two low pH cases (high and low temperatures) and a high temperature, alkaline (high pH) sodic water. Simulation of an acid-sulfate case leads to precipitation of Fe and Al minerals along with silica. Consistency with martian mineral assemblages suggests that hot, acidic sulfate solutions are plausibility progenitors of minerals in the past on Mars. In the alkaline pH (8.45) simulation, formation of silica at high temperatures (355 K) led to precipitation of anhydrous minerals (CaSO 4, Na 2SO 4) that was also the case for the high temperature (353 K) low pH case where anhydrous minerals (NaCl, CaSO 4) also precipitated. Thus we predict that secondary minerals associated with massive silica deposits are plausible indicators on Mars of precipitation environments and aqueous chemistry. Theoretical model calculations are in reasonable agreement with independent experimental silica concentrations, which strengthens the validity of the new CHEMCHAU model.

Modeling hot spring chemistries with applications to martian silica formation

USGS Publications Warehouse

Marion, G.M.; Catling, D.C.; Crowley, J.K.; Kargel, J.S.

2011-01-01

Many recent studies have implicated hydrothermal systems as the origin of martian minerals across a wide range of martian sites. Particular support for hydrothermal systems include silica (SiO2) deposits, in some cases >90% silica, in the Gusev Crater region, especially in the Columbia Hills and at Home Plate. We have developed a model called CHEMCHAU that can be used up to 100??C to simulate hot springs associated with hydrothermal systems. The model was partially derived from FREZCHEM, which is a colder temperature model parameterized for broad ranges of temperature (<-70 to 25??C), pressure (1-1000 bars), and chemical composition. We demonstrate the validity of Pitzer parameters, volumetric parameters, and equilibrium constants in the CHEMCHAU model for the Na-K-Mg-Ca-H-Cl-ClO4-SO4-OH-HCO3-CO3-CO2-O2-CH4-Si-H2O system up to 100??C and apply the model to hot springs and silica deposits.A theoretical simulation of silica and calcite equilibrium shows how calcite is least soluble with high pH and high temperatures, while silica behaves oppositely. Such influences imply that differences in temperature and pH on Mars could lead to very distinct mineral assemblages. Using measured solution chemistries of Yellowstone hot springs and Icelandic hot springs, we simulate salts formed during the evaporation of two low pH cases (high and low temperatures) and a high temperature, alkaline (high pH) sodic water. Simulation of an acid-sulfate case leads to precipitation of Fe and Al minerals along with silica. Consistency with martian mineral assemblages suggests that hot, acidic sulfate solutions are plausibility progenitors of minerals in the past on Mars. In the alkaline pH (8.45) simulation, formation of silica at high temperatures (355K) led to precipitation of anhydrous minerals (CaSO4, Na2SO4) that was also the case for the high temperature (353K) low pH case where anhydrous minerals (NaCl, CaSO4) also precipitated. Thus we predict that secondary minerals associated with massive silica deposits are plausible indicators on Mars of precipitation environments and aqueous chemistry. Theoretical model calculations are in reasonable agreement with independent experimental silica concentrations, which strengthens the validity of the new CHEMCHAU model. ?? 2011 Elsevier Inc.

Computing the carbonate chemistry of the coral calcifying medium and its response to ocean acidification.

PubMed

Raybaud, Virginie; Tambutté, Sylvie; Ferrier-Pagès, Christine; Reynaud, Stéphanie; Venn, Alexander A; Tambutté, Éric; Nival, Paul; Allemand, Denis

2017-07-07

Critical to determining vulnerability or resilience of reef corals to Ocean Acidification (OA) is a clearer understanding of the extent to which corals can control carbonate chemistry in their Extracellular Calcifying Medium (ECM) where the CaCO 3 skeleton is produced. Here, we employ a mathematical framework to calculate ECM aragonite saturation state (Ω arag.(ECM) ) and carbonate system ion concentration using measurements of calcification rate, seawater characteristics (temperature, salinity and pH) and ECM pH (pH (ECM) ). Our calculations of ECM carbonate chemistry at current-day seawater pH, indicate that Ω arag.(ECM) ranges from ∼10 to 38 (mean 20.41), i.e. about 5 to 6-fold higher than seawater. Accordingly, Dissolved Inorganic Carbon (DIC) and Total Alkalinity (TA) were calculated to be around 3 times higher in the ECM than in seawater. We also assessed the effects of acidification on ECM chemical properties of the coral Stylophora pistillata. At reduced seawater pH our calculations indicate that Ω arag.(ECM) remains almost constant. DIC (ECM) and TA (ECM) gradually increase as seawater pH declines, reaching values about 5 to 6-fold higher than in seawater, respectively for DIC and TA. We propose that these ECM characteristics buffer the effect of acidification and explain why certain corals continue to produce CaCO 3 even when seawater chemistry is less favourable. Copyright © 2017 Elsevier Ltd. All rights reserved.

Acid precipitation studies in Colorado and Wyoming: interim report of surveys of montane amphibians and water chemistry

USGS Publications Warehouse

Corn, Paul Stephen; Stolzenburg, William; Bury, R. Bruce

1989-01-01

Acid deposition may be detrimental or stressful to native populations of wildlife. Because many species of amphibians breed in shallow ponds created by spring rains or melting snow, they may be particularly vulnerable to the effects of acidification. From 1986 to 1988, we surveyed 105 locations in the central Rocky Mountains where amphibians had been recorded previously, and we found that two species of amphibians had experiences major losses. We found the northern leopard frog (Rana pipiens) at only 4 of 33 (12%) historically known localities, and the boreal toad (Bufo boreas) was present at 10 of 59 (17%) known localities. Three other species have not suffered region-wide declines. Tiger salamanders (Ambystoma tigrinum) and wood frogs (Rana sylvatica) were present at 45% and 69% of known localities respectively, and were observed at several localities were they had not been recorded previously. Chorus frogs (Pseudacris triseriata) suffered a catastrophic decline in population size in one population monitored since 1961, but regionally, this species was observed in 36 of 56 (64%) known localities and in another 19 localities where there were no previous records. Complete water chemistry was recorded for 41 localities, and pH was measured at 110 sites in total. Acid neutralizing capacity, pH, specific conductivity, and cation concentrations were negatively correlated with elevation. However, in mountain ponds and lakes, pH was rarely less than 6.0 during the amphibian breeding season. We tested the tolerance of embryos of the four species of frogs to low pH. The LC50 pH was 4.8 for chorus frogs, 4.4-4.7 for leopard frogs, 4.4-4.5 for boreal toads, and 4.2-4.3 for wood frogs. Survival of wood frog embryos declined when exposed to aluminum concentrations of 100 µg/L or greater, but boreal toad embryos survived exposure to aluminum concentrations of 400 µg/L. Acid deposition does not appear to be a major factor in the decline of leopard frogs and boreal toads. However, we have not yet investigated effects of sublethal pH on growth and development of tadpoles. Pollution remains suspect, but other factors, including natural fluctuations in population size, may account for the observed declines.

Is coccolithophore distribution in the Mediterranean Sea related to seawater carbonate chemistry?

NASA Astrophysics Data System (ADS)

Oviedo, A.; Ziveri, P.; Álvarez, M.; Tanhua, T.

2015-01-01

The Mediterranean Sea is considered a "hot spot" for climate change, being characterized by oligotrophic to ultra-oligotrophic waters and rapidly increasing seasurface temperature and changing carbonate chemistry. Coccolithophores are considered a dominant phytoplankton group in these waters. As marine calcifying organisms they are expected to respond to the ongoing changes in seawater carbonate chemistry. We provide here a description of the springtime coccolithophore distribution in the Mediterranean Sea and relate this to a broad set of in situ-measured environmental variables. Samples were taken during the R/V Meteor (M84/3) oceanographic cruise in April 2011, between 0 and 100 m water depth from 28 stations. Total diatom and silicoflagellate cell concentrations are also presented. Our results highlight the importance of seawater carbonate chemistry, especially [CO32-] but also [PO43-] in unraveling the distribution of heterococcolithophores, the most abundant coccolithophore life phase. Holo- and heterococcolithophores respond differently to environmental factors. For instance, changes in heterococcolithophore assemblages were best linked to the combination of [CO32-], pH, and salinity (ρ = 0.57), although salinity might be not functionally related to coccolithophore assemblage distribution. Holococcolithophores, on the other hand, showed higher abundances and species diversity in oligotrophic areas (best fit, ρ = 0.32 for nutrients), thriving in nutrient-depleted waters. Clustering of heterococcolithophores revealed three groups of species sharing more than 65% similarities. These clusters could be assigned to the eastern and western basins and deeper layers (below 50 m), respectively. In addition, the species Gephyrocapsa oceanica, G. muellerae, and Emiliania huxleyi morphotype B/C are spatially distributed together and trace the influx of Atlantic waters into the Mediterranean Sea. The results of the present work emphasize the importance of considering holo- and heterococcolithophores separately when analyzing changes in species assemblages and diversity. Our findings suggest that coccolithophores are a main phytoplankton group in the entire Mediterranean Sea and can dominate over siliceous phytoplankton. They have life stages that are expected to respond differently to the variability in seawater carbonate chemistry and nutrient concentrations.

The coordination chemistry of the neutral tris-2-pyridyl silicon ligand [PhSi(6-Me-2-py)3].

PubMed

Plajer, Alex J; Colebatch, Annie L; Enders, Markus; García-Romero, Álvaro; Bond, Andrew D; García-Rodríguez, Raúl; Wright, Dominic S

2018-05-22

Difficulties in the preparation of neutral ligands of the type [RSi(2-py)3] (where 2-py is an unfunctionalised 2-pyridyl ring unit) have thwarted efforts to expand the coordination chemistry of ligands of this type. However, simply switching the pyridyl substituents to 6-methyl-pyridyl groups (6-Me-2-py) in the current paper has allowed smooth, high-yielding access to the [PhSi(6-Me-2-py)3] ligand (1), and the first exploration of its coordination chemistry with transition metals. The synthesis, single-crystal X-ray structures and solution dynamics of the new complexes [{PhSi(6-Me-2-py)3}CuCH3CN][PF6], [{PhSi(6-Me-2-py)3}CuCH3CN][CuCl2], [{PhSi(6-Me-2-py)3}FeCl2], [{PhSi(6-Me-2-py)3}Mo(CO)3] and [{PhSi(6-Me-2-py)3}CoCl2] are reported. The paramagnetic Fe2+ and Co2+ complexes show strongly shifted NMR resonances for the coordinated pyridyl units due to large Fermi-contact shifts. However, magnetic anisotropy also leads to considerable pseudo-contact shifts so that both contributions have to be included in the paramagnetic NMR analysis.

Regional Sediment Management Studies of Matagorda Ship Channel and Matagorda Bay System, Texas

DTIC Science & Technology

2013-08-01

types of sediment, as there is more silt and clay (cohesive) material in the Lavaca Bay and upper Matagorda Bay and sandy (non- cohesive) sediment in the...Sediment varies from silt to clay in the upper and mid bays and sandy material in the lower bay. 2.5 Dredging History The SWG maintains the deep...diameter  clay mineralogy  rate of deformation (shear rate)  percentage of organic material  water chemistry (especially pH, salinity, etc

Tailored Granular Activated Carbon Treatment of Perchlorate in Drinking Water. ESTCP Cost and Performance Report

DTIC Science & Technology

2011-08-01

sodium nitrate NaOCl sodium hypochlorite NAVFAC-ESC Naval Facilities Engineering Command-Engineering Service Center NDMA n-nitrosodimethylamine NL...nitrosodimethylamine ( NDMA ) was measured in effluent from the second TGAC bed at 39 ng/L. No other nitrosamines were detected in any other sampling event...was 6.3 ng/L NDMA in an effluent sample of the prechlorination/oxidant train. 6.6.3.4 General Chemistry Results With a few exceptions, values of pH

Impact of pH on Urine Chemistry Assayed on Roche Analyzers.

PubMed

Cohen, R; Alkouri, R; Tostivint, I; Djiavoudine, S; Mestari, F; Dever, S; Atlan, G; Devilliers, C; Imbert-Bismut, F; Bonnefont-Rousselot, D; Monneret, D

2017-10-01

The pH may impact the concentration of certain urinary parameters, making urine pre-treatment questionable. 1) Determining the impact of pH in vitro on the urinary concentration of chemistry parameters assayed on Roche Modular analyzers. 2) Evaluating whether concentrations depended on pH in non-pretreated urines from patients. 1) The optimal urinary pH values for each measurement were: 6.3 ± 0.8 (amylase), < 5.5 (calcium and magnesium), < 6.5 (phosphorus), > 6.5 (uric acid). Urinary creatinine, sodium and urea concentrations were not pH-dependent. 2) In urines from patients, the pH was negatively associated with the concentration of some urinary parameters. However, concentrations of all the parameters were strongly and positively correlated with urinary creatinine, and relationships with pH were no longer evidenced after creatinine-normalization. The need for urine pH adjustment does not seem necessary when considering renal function. However, from an analytical and accreditation standpoint, the relationship between urine pH and several parameters justifies its measurement.

Preparation of a Natural Product Extract Library for Investigation Against Disease States Specific to Defence Health: A Mini Long Range Research Project

DTIC Science & Technology

2009-02-01

Sci in 1994 and with a BSc(Hons) in 1995 from The University of Melbourne. In 1999 he completed a PhD in marine natural products chemistry from the...BSc(Hons) in 1994 from the University of Melbourne. In 1998 she completed a PhD in organic chemistry , developing new free-radical syntheses of some...Melissa began work in the area of medicinal chemistry , developing partial agonists of adenosine A1 receptors; firstly at Deakin University and

Sequential Excitation Preparation of Molecular Energy Levels with Special Structural and Chemical Properties.

DTIC Science & Technology

1986-01-06

D.E. Reisner, and P.H. Vaccaro, pp. 393-404 in Lasers as Reactants and Probes in Chemistry, (eds. W.M. Jackson and A.B. Harvey) Howard University Press...as Reactants and Probes in Chemistry, Howard University (May 1982). 4. J.L. Kinsey, "An Outsider’s View of the Spectroscopy of Polyatomic Systems...Kinsey, C. Kittrell, D.E. Reisner, and P.H. Vaccaro, pp. 393-404 in Lasers as Reactants and Probes in Chemistry (eds. W.M. Jackson and A.B. Harvey), Howard

Processes Driving Natural Acidification of Western Pacific Coral Reef Waters

NASA Astrophysics Data System (ADS)

Shamberger, K. E.; Cohen, A. L.; Golbuu, Y.; McCorkle, D. C.; Lentz, S. J.; Barkley, H. C.

2013-12-01

Rising levels of atmospheric carbon dioxide (CO2) are acidifying the oceans, reducing seawater pH, aragonite saturation state (Ωar) and the availability of carbonate ions (CO32-) that calcifying organisms use to build coral reefs. Today's most extensive reef ecosystems are located where open ocean CO32- concentration ([CO32-]) and Ωar exceed 200 μmol kg-1 and 3.3, respectively. However, high rates of biogeochemical cycling and long residence times of water can result in carbonate chemistry conditions within coral reef systems that differ greatly from those of nearby open ocean waters. In the Palauan archipelago, water moving across the reef platform is altered by both biological and hydrographic processes that combine to produce seawater pH, Ωar, [CO32-] significantly lower than that of open ocean source water. Just inshore of the barrier reefs, average Ωar values are 0.2 to 0.3 and pH values are 0.02 to 0.03 lower than they are offshore, declining further as water moves across the back reef, lagoon and into the meandering bays and inlets that characterize the Rock Islands. In the Rock Island bays, coral communities inhabit seawater with average Ωar values of 2.7 or less, and as low as 1.9. Levels of Ωar as low as these are not predicted to occur in the western tropical Pacific open ocean until near the end of the century. Calcification by coral reef organisms is the principal biological process responsible for lowering Ωar and pH, accounting for 68 - 99 % of the difference in Ωar between offshore source water and reef water at our sites. However, in the Rock Island bays where Ωar is lowest, CO2 production by net respiration contributes between 17 - 30 % of the difference in Ωar between offshore source water and reef water. Furthermore, the residence time of seawater in the Rock Island bays is much longer than at the well flushed exposed sites, enabling calcification and respiration to drive Ωar to very low levels despite lower net ecosystem calcification rates in the Rock Island bays than on the barrier reef.

Marine bivalve shell geochemistry and ultrastructure from modern low pH environments: environmental effect versus experimental bias

NASA Astrophysics Data System (ADS)

Hahn, S.; Rodolfo-Metalpa, R.; Griesshaber, E.; Schmahl, W. W.; Buhl, D.; Hall-Spencer, J. M.; Baggini, C.; Fehr, K. T.; Immenhauser, A.

2012-05-01

Bivalve shells can provide excellent archives of past environmental change but have not been used to interpret ocean acidification events. We investigated carbon, oxygen and trace element records from different shell layers in the mussels Mytilus galloprovincialis combined with detailed investigations of the shell ultrastructure. Mussels from the harbour of Ischia (Mediterranean, Italy) were transplanted and grown in water with mean pHT 7.3 and mean pHT 8.1 near CO2 vents on the east coast of the island. Most prominently, the shells recorded the shock of transplantation, both in their shell ultrastructure, textural and geochemical record. Shell calcite, precipitated subsequently under acidified seawater responded to the pH gradient by an in part disturbed ultrastructure. Geochemical data from all test sites show a strong metabolic effect that exceeds the influence of the low-pH environment. These field experiments showed that care is needed when interpreting potential ocean acidification signals because various parameters affect shell chemistry and ultrastructure. Besides metabolic processes, seawater pH, factors such as salinity, water temperature, food availability and population density all affect the biogenic carbonate shell archive.

The role of pH in structuring communities of Maine wetland macrophytes and chironomid larvae (Diptera)

USGS Publications Warehouse

Woodcock, T.S.; Longcore, J.R.; McAuley, D.G.; Mingo, T.M.; Bennatti, C.R.; Stromborg, K.L.

2005-01-01

Aquatic vascular plants, or macrophytes, are an important habitat component for many wetland organisms, and larvae of chironomid midges are ubiquitous components of wetland fauna. Many chironomids are primary consumers of algae and detritus and form an essential energetic link between allochthonous and autochthonous primary production and higher trophic levels, while others are predators and feed on smaller invertebrates. Live macrophytes serve mostly as habitat, whereas plant detritus serves as both habitat and as a food source. Assemblages of macrophytes and chironomid larvae were surveyed in ten Maine wetlands, five with low pH (5.5), and explained in terms of physical and chemical habitat variables. Macrophyte richness was significantly greater, and richness of chironomid larvae was lower, in low pH wetlands. There was no difference in chironomid abundance related to pH. However, community structure was related to pH, suggesting that competitive dominance of a few taxa was responsible for lower richness in low pH wetlands, whereas competition was weaker in high pH wetlands, making coexistence of more chironomid taxa possible. An examination of individual chironomid taxa by stepwise multiple regression showed that distribution of most taxa was controlled by water chemistry variables and macrophyte habit (i.e., floating, submergent).

Evaluation of modeled cloud chemistry mechanism against laboratory irradiation experiments: The HxOy/iron/carboxylic acid chemical system

NASA Astrophysics Data System (ADS)

Long, Yoann; Charbouillot, Tiffany; Brigante, Marcello; Mailhot, Gilles; Delort, Anne-Marie; Chaumerliac, Nadine; Deguillaume, Laurent

2013-10-01

Currently, cloud chemistry models are including more detailed and explicit multiphase mechanisms based on laboratory experiments that determine such values as kinetic constants, stability constants of complexes and hydration constants. However, these models are still subject to many uncertainties related to the aqueous chemical mechanism they used. Particularly, the role of oxidants such as iron and hydrogen peroxide in the oxidative capacity of the cloud aqueous phase has typically never been validated against laboratory experimental data. To fill this gap, we adapted the M2C2 model (Model of Multiphase Cloud Chemistry) to simulate irradiation experiments on synthetic aqueous solutions under controlled conditions (e.g., pH, temperature, light intensity) and for actual cloud water samples. Various chemical compounds that purportedly contribute to the oxidative budget in cloud water (i.e., iron, oxidants, such as hydrogen peroxide: H2O2) were considered. Organic compounds (oxalic, formic and acetic acids) were taken into account as target species because they have the potential to form iron complexes and are good indicators of the oxidative capacity of the cloud aqueous phase via their oxidation in this medium. The range of concentrations for all of the chemical compounds evaluated was representative of in situ measurements. Numerical outputs were compared with experimental data that consisted of a time evolution of the concentrations of the target species. The chemical mechanism in the model describing the “oxidative engine” of the HxOy/iron (HxOy = H2O2, HO2rad /O2rad - and HOrad ) chemical system was consistent with laboratory measurements. Thus, the degradation of the carboxylic acids evaluated was closely reproduced by the model. However, photolysis of the Fe(C2O4)+ complex needs to be considered in cloud chemistry models for polluted conditions (i.e., acidic pH) to correctly reproduce oxalic acid degradation. We also show that iron and formic acid lead to a stable complex whose photoreactivity has currently not been investigated. The updated aqueous chemical mechanism was compared with data from irradiation experiments using natural cloud water. The new reactions considered in the model (i.e., iron complex formation with oxalic and formic acids) correctly reproduced the experimental observations.

Use of a PhET Interactive Simulation in General Chemistry Laboratory: Models of the Hydrogen Atom

ERIC Educational Resources Information Center

Clark, Ted M.; Chamberlain, Julia M.

2014-01-01

An activity supporting the PhET interactive simulation, Models of the Hydrogen Atom, has been designed and used in the laboratory portion of a general chemistry course. This article describes the framework used to successfully accomplish implementation on a large scale. The activity guides students through a comparison and analysis of the six…

21 CFR 862.1120 - Blood gases (PCO2, PO2) and blood pH test system.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Blood gases (PCO2, PO2) and blood pH test system. 862.1120 Section 862.1120 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) MEDICAL DEVICES CLINICAL CHEMISTRY AND CLINICAL TOXICOLOGY DEVICES Clinical Chemistry...

Analysis of Citations to Books in Chemistry PhD Dissertations in an Era of Transition

ERIC Educational Resources Information Center

Flaxbart, David

2018-01-01

A citation analysis of chemistry PhD dissertations at the University of Texas at Austin yielded data on how often graduate students cite books in their bibliographies, and on the characteristics of the books cited, in terms of age and local ownership. The analysis examined samples of dissertations selected from five discrete years--1988, 2006,…

21 CFR 862.1120 - Blood gases (PCO2, PO2) and blood pH test system.

Code of Federal Regulations, 2011 CFR

2011-04-01

... 21 Food and Drugs 8 2011-04-01 2011-04-01 false Blood gases (PCO2, PO2) and blood pH test system. 862.1120 Section 862.1120 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) MEDICAL DEVICES CLINICAL CHEMISTRY AND CLINICAL TOXICOLOGY DEVICES Clinical Chemistry...

21 CFR 862.1120 - Blood gases (PCO2, PO2) and blood pH test system.

Code of Federal Regulations, 2013 CFR

2013-04-01

... 21 Food and Drugs 8 2013-04-01 2013-04-01 false Blood gases (PCO2, PO2) and blood pH test system. 862.1120 Section 862.1120 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) MEDICAL DEVICES CLINICAL CHEMISTRY AND CLINICAL TOXICOLOGY DEVICES Clinical Chemistry...

21 CFR 862.1120 - Blood gases (PCO2, PO2) and blood pH test system.

Code of Federal Regulations, 2012 CFR

2012-04-01

... 21 Food and Drugs 8 2012-04-01 2012-04-01 false Blood gases (PCO2, PO2) and blood pH test system. 862.1120 Section 862.1120 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) MEDICAL DEVICES CLINICAL CHEMISTRY AND CLINICAL TOXICOLOGY DEVICES Clinical Chemistry...

A model for late Archean chemical weathering and world average river water

NASA Astrophysics Data System (ADS)

Hao, Jihua; Sverjensky, Dimitri A.; Hazen, Robert M.

2017-01-01

Interpretations of the geologic record of late Archean near-surface environments depend very strongly on an understanding of weathering and resultant riverine transport to the oceans. The late Archean atmosphere is widely recognized to be anoxic (pO2,g =10-5 to 10-13 bars; pH2,g =10-3 to 10-5 bars). Detrital siderite (FeCO3), pyrite (FeS2), and uraninite (UO2) in late Archean sedimentary rocks also suggest anoxic conditions. However, whether the observed detrital minerals could have been thermodynamically stable during weathering and riverine transport under such an atmosphere remains untested. Similarly, interpretations of fluctuations recorded by trace metals and isotopes are hampered by a lack of knowledge of the chemical linkages between the atmosphere, weathering, riverine transport, and the mineralogical record. In this study, we used theoretical reaction path models to simulate the chemistry involved in rainwater and weathering processes under present-day and hypothetical Archean atmospheric boundary conditions. We included new estimates of the thermodynamic properties of Fe(II)-smectites as well as smectite and calcite solid solutions. Simulation of present-day weathering of basalt + calcite by world-average rainwater produced hematite, kaolinite, Na-Mg-saponite, and chalcedony after 10-4 moles of reactant minerals kg-1 H2O were destroyed. Combination of the resultant water chemistry with results for granitic weathering produced a water composition comparable to present-day world average river water (WARW). In contrast, under late Archean atmospheric conditions (pCO2,g =10-1.5 and pH2,g =10-5.0 bars), weathering of olivine basalt + calcite to the same degree of reaction produced kaolinite, chalcedony, and Na-Fe(II)-rich-saponite. Late Archean weathering of tonalite-trondhjemite-granodiorite (TTG) formed Fe(II)-rich beidellite and chalcedony. Combining the waters from olivine basalt and TTG weathering resulted in a model for late Archean WARW with the composition Na+-Ca2+-Fe2+-Mg2+-Cl--HCO-3-SiO2,aq. The pH of the water was 6.3 and it is much richer in HCO-3, and in Mg + Fe relative to Ca + Na, compared to present-day WARW. At higher pH2,g (e.g. 10-4.0 bars) organic acid anions could be metastable. Our results are consistent with the thermodynamic stability of Fe(II)-clays, pyrite, uraninite, and, under some conditions, siderite during weathering and riverine transport. Overall, our results provide a basis for assessing the formation of organic hazes and the mobility of trace elements and nutrients due to fluctuations of the late Archean atmosphere.

The Coral Reef pH-stat: An Important Defense Against Ocean Acidification? (Invited)

NASA Astrophysics Data System (ADS)

Andersson, A. J.; Yeakel, K.; Bates, N.; de Putron, S.; Collins, A.

2013-12-01

Concerns have been raised on how coral reefs will be affected by ocean acidification (OA), but there are currently no direct predictions on how seawater CO2 chemistry and pH within coral reefs might change in response to OA. Projections of future changes in seawater pH and aragonite saturation state have only been applied to open ocean conditions surrounding coral reef environments rather than the reef systems themselves. The seawater CO2 chemistry within heterogenous coral reef systems can be significantly different from that of the open ocean depending on the residence time, community composition and the major biogeochemical processes occurring on the reef, i.e., net ecosystem organic carbon production and calcification, which combined act to modify the seawater chemistry. We argue that these processes and coral reefs in general could as a pH-stat, partly regulating seawater pH on the reef and offsetting changes in seawater chemistry imposed by ocean acidification. Based on observations from the Bermuda coral reef, we show that a range of anticipated biogeochemical responses of coral reef communities to OA by the end of this century could partially offset changes in seawater pH by an average of 12% to 24%.

Constructing a Baseline Model of Alpine Wetlands of the Uinta Mountains, Utah, USA

NASA Astrophysics Data System (ADS)

Matyjasik, M.; Ford, R. L.; Bartholomew, L. M.; Welsh, S. B.; Hernandez, M.; Koerner, D.; Muir, M.

2008-12-01

Alpine wetlands of the Uinta Mountains, northeastern Utah, contain a variety of groundwater-dependent ecosystems. Unlike their counterparts in other areas of the Rocky Mountains, these systems have been relatively unstudied. The Reader Lakes area on the southern slope of the range was selected for detailed study because of its variety of wetland plant communities, homogenous bedrock geology, and minimal human impact. The primary goal of this interdisciplinary study is to establish the functional links between the geomorphology and hydrogeology of these high mountain wetlands and their constituent plant communities. In addition to traditional field studies and water chemistry, geospatial technologies are being used to organize and analyze both field data (water chemistry and wetland vegetation) and archived multispectral imagery (2006 NAIP images). The hydrology of these wetlands is dominated by groundwater discharge and their surface is dominated by string-and-flark morphology of various spatial scales, making these montane wetlands classic patterned fens. The drainage basin is organized into a series of large-scale stair-stepping wetlands, bounded by glacial moraines at their lower end. Wetlands are compartmentalized by a series of large strings (roughly perpendicular to the axial stream) and flarks. This pattern may be related to small ridges on the underlying ground moraine and possibly modified by beaver activity along the axial stream. Small-scale patterning occurs along the margins of the wetlands and in sloping-fen settings. The smaller-scale strings and flarks form a complex; self-regulating system in which water retention is enhanced and surface flow is minimized. Major plant communities have been identified within the wetlands for example: a Salix planifolia community associated with the peaty strings; Carex aquatilis, Carex limosa, and Eriophorum angustifolium communities associated with flarks; as well as a Sphagnum sp.- rich hummocky transition zone between wetland and non-wetland areas. On-going analyses of water-chemistry data will be used to identify discrete water sources and to characterize the degree of horizontal and vertical water mixing within the system, as well as to help identify the biochemical requirements of the different plant communities. Results indicate that the chemical composition of the main creek reflects the accumulative effect that the peaty flarks have on the creek as it passes through the wetland system, with pH overall decreasing from 7.3 to 7.0, dissolved oxygen decreasing from 9400 to 8400 micrograms per liter and total dissolved solids increasing from 9 mg/L to 13 mg/L. String ground water is characterized by relatively high pH (ranging from 6.0 to 7.1), high oxidizing-reducing potential (ORP) (ranging from 50 mV to 180 mV), high dissolved oxygen (from 2500 μg/L to 9600 μg /L) while flark ground water has relatively lower pH (5.6 to 6.8), low oxidizing reducing potential (ORP) (ranging from -66 mV to 150 mV), low dissolved oxygen (from 900 μg /L to 9000 μg /L).

Acidic, neutral and alkaline forest ponds as a landscape element affecting the biodiversity of freshwater snails

NASA Astrophysics Data System (ADS)

Spyra, Aneta

2017-10-01

In recent years, the number of areas remaining under the influence of acidity has increased. At all levels of ecosystems, biodiversity decreases with acidification, due to the elimination of species that are most sensitive to low pH. Forest ponds belong to a specific group that varied in location, a huge amount of leaf litter, and isolation from other aquatic environments. They are crucial in the industrial landscape with well-developed industry and human activity. The aim was to investigate the relative importance of water chemistry in explaining snail assemblage compositions and species richness in forest ponds of contrasting pH. Patterns in gastropod communities were determined from an analysis in 26 forest ponds with multivariate gradient analysis. Ponds ranged in a base mean pH from 3.0 to 9.0. pH has been found to be an important factor influencing gastropod fauna. Neutral ponds support diverse communities, typical of small water bodies. In two acidic pond types, snail fauna was different. Among the species characteristic for acidic ponds (pH < 6) were Anisus spirorbis and Aplexa hypnorum. The greatest distinct characterised alkaline ponds with the numerous appearance of alien Physa acuta. The most diverse gastropod fauna was found in neutral ponds, whereas the lowest degree of diversity was found in ponds with the lowest pH. Current knowledge of pH-associated changes in aquatic ecosystems is still incomplete because anthropogenic acidification is a recent phenomenon. It is extremely important in forest habitats, since they react more intensively to climatic factors and are often used in landscape management and planning.

Impacts of ocean acidification on coral calcification: experimental results from a field study around submarine springs

NASA Astrophysics Data System (ADS)

Paytan, A.; Martínez Fernández, A.; Varona, N.

2017-12-01

Reef building corals are facing the effects of ocean acidification on calcification. Atmospheric carbon dioxide dissolves into the oceans and decreases the pH and the availability of carbonate ions in seawater. Carbonate ions are used by calcifying corals to create their calcium carbonate exoskeletons in the form of aragonite. As carbon dioxide emissions increase, corals may have problems precipitating their aragonite skeleton in low carbonate saturation seawater. Natural submarine groundwater springs discharge low pH seawater into the Caribbean Sea, in the Yucatan Peninsula (Mexico). These submarine springs serve as a natural laboratory to study the effects of low aragonite saturation water on coral growth. Here we show the skeletal growth parameters of three coral species under an in situ ocean acidification experiment. Nubbins of Porites porites, Porites astreoides and Siderastrea radians were collected at low pH springs and control sites and reciprocally transplanted into a low pH discharge site and into a control site not impacted by discharge. After two years, the nubbins were collected and linear extension, density and calcification rates were analyzed. Preliminary results show that coral skeleton density is significantly lower in corals transplanted into the low pH than in corals transplanted in control sites. Infaunal bioerosion is present in corals deployed at low pH sites. In contrast, linear extension and hence calcification rates do not seem to show a significant difference among sites. However, the coral species show diverse calcification responses under ocean acidification conditions, suggesting some species may be more vulnerable than others to a change in water chemistry.

CO2-assisted phosphorus extraction from poultry litter and selective recovery of struvite and potassium struvite.

PubMed

Shashvatt, Utsav; Benoit, Josh; Aris, Hannah; Blaney, Lee

2018-06-18

Phosphorus recovery from industrialized poultry operations is necessary to ensure sustainable waste management and resource consumption. To realize these goals, an innovative, two-stage process chemistry has been developed to extract nutrients from poultry litter and recover value-added products. Over 75% phosphorus extraction was achieved by bubbling carbon dioxide into poultry litter slurries and adding strong acid to reach pH 4.5-5.5. After separating the nutrient-deficient poultry litter solids and the nutrient-rich liquid, the extract pH was increased through aeration and strong base addition. Over 95% of the extracted phosphorus was recovered as solid precipitate at pH 8.5-9.0. High-purity struvite and potassium struvite products were selectively recovered through pH control, introduction of a calcium-complexing agent, and addition of magnesium chloride. The nitrogen-to-phosphorus-to-potassium (NPK) ratio of the recovered solids was controlled through aeration and pH adjustment. Precipitation at pH 8.5-9.0 and 10.5-11.0 resulted in NPK ratios of 2.0:1.0:0.1 and 0.9:1.0:0.2, respectively. The process effluent was effectively recycled as makeup water for the subsequent batch of poultry litter, thereby decreasing water consumption and increasing overall nutrient recovery. Sequencing batch operation yielded greater than 70% phosphorus recovery within a 45-min process, demonstrating the potential for this technology to alleviate nutrient pollution in agricultural settings and generate an alternative supply of phosphorus fertilizers. Copyright © 2018. Published by Elsevier Ltd.

The effects of liming an Adirondack lake watershed on downstream water chemistry: Effects of liming on stream chemistry

USGS Publications Warehouse

Burns, Douglas A.

1996-01-01

Calcite treatment of chronically acidic lakes has improved fish habitat, but the effects on downstream water quality have not previously been examined. In this study, the spatial and temporal effects of watershed CaCO3 treatment on the chemistry of a lake outlet stream in the Adirondack Mountains of New York were examined. Before CaCO3 treatment, the stream was chronically acidic. During spring snowmelt before treatment, pH and acid-neutralizing capacity (ANC) in the outlet stream declined, and NO3- and inorganic monomeric aluminum (AlIM) concentrations increased sharply. During that summer, SO42- and NO3- concentrations decreased downstream, and dissolved organic carbon (DOC) concentrations and ANC increased, in association with the seasonal increase in decomposition of organic matter and the attendant SO42--reduction process. A charge-balance ANC calculation closely matched measured downstream changes in ANC in the summer and indicated that SO42- reduction was the major process contributing to summer increases in ANC. Increases in Ca2+ concentration and ANC began immediately after CaCO3 application, and within 3 months, exceeded their pretreatment values by more than 130 ??eq/L. Within 2 months after treatment, downstream decreases in Ca2+ concentration, ANC, and pH, were noted. Stream mass balances between the lake and the sampling site 1.5 km downstream revealed that the transport of all chemical constituents was dominated by conservative mixing with tributaries and ground water; however, non-conservative processes resulted in significant Ca2+ losses during the 13-month period after CaCO3 treatment. Comparison of substrate samples from the buffered outlet stream with those from its untreated tributaries showed that the percentage of cation-exchange sites occupied by Ca2+, as well as non-exchangeable Ca, were higher in the outlet-stream substrate than in tributary-stream substrate. Mass-balance data for Ca2+, H+, AlIM, and DOC revealed net downstream losses of these constituents and indicated that a reasonable set of hypothesized reactions involving AlIM, HCO3-, Ca2+, SO42-, NO3-7, and DOC could have caused the measured changes in stream acid/base chemistry. In the summer, the sharp decrease in ANC continued despite significant downstream decreases in SO42- concentrations. After CaCO3 treatment, reduction of SO42- was only a minor contributor to ANC changes relative to those caused by Ca2+ dilution from acidic tributaries and acidic ground water, and Ca2+ interactions with stream substrate. ?? 1996 Kluwer Academic Publishers.

Isoelectric points of viruses.

PubMed

Michen, B; Graule, T

2010-08-01

Viruses as well as other (bio-)colloids possess a pH-dependent surface charge in polar media such as water. This electrostatic charge determines the mobility of the soft particle in an electric field and thus governs its colloidal behaviour which plays a major role in virus sorption processes. The pH value at which the net surface charge switches its sign is referred to as the isoelectric point (abbreviations: pI or IEP) and is a characteristic parameter of the virion in equilibrium with its environmental water chemistry. Here, we review the IEP measurements of viruses that replicate in hosts of kingdom plantae, bacteria and animalia. IEPs of viruses are found in pH range from 1.9 to 8.4; most frequently, they are measured in a band of 3.5 < IEP < 7. However, the data appear to be scattered widely within single virus species. This discrepancy is discussed and should be considered when IEP values are used to account for virus sorption processes.

[Impact of Rocky Desertification Treatment on Underground Water Chemistry and Dissolved Inorganic Carbon Isotope in Karst Areas].

PubMed

Xiao, Shi-zhen; Xiong, Kang-ning; Lan, Jia-cheng; Zhang, Hui; Yang, Long

2015-05-01

Five springs representing different land-use types and different karst rocky desertification treatment models were chosen at the Huajiang Karst Rocky Desertification Treatment Demonstration Site in Guanling-Zhenfeng Counties in Guizhou, to analyze the features of underground water chemistry and dissolved inorganic carbon isotopes (δ13C(DIC)) and reveal the effect of rocky desertification treatment on karstification and water quality. It was found that, the underground water type of the research area was HCO3-Ca; the water quality of the springs which were relatively less affected by human activities including Shuijingwan Spring (SJW) , Gebei Spring (GB), and Maojiawan Spring (MJW) was better than those relatively more affected by human activities including Diaojing Spring (DJ) and Tanjiazhai Spring (TJZ) , the main ion concentrations and electrical conductivity of which were higher; pH, SIc and pCO2 were sensitive to land-use types and rocky desertification treatment, which could be shown by the higher pH and SIc and lower pCO2 in MJW than those in the other four springs; (Ca(2+) + Mg2+)/HCO(3-) of SJW, MJW and GB were nearly 1:1, dominated by carbonate rock weathering by carbon acid, while the (Ca(2+) + Mg2+) of DJ and TJZ was much higher than HCO3-, suggesting that sulfate and nitrate might also dissolve carbonate rock because of the agricultural activities; δ13C(DIC) was lighter in wet season because of the higher biological activities; the average δ13C(DIC) was in the order of DJ (-12.79 per thousand) < SJW (-12.48 per thousand) < GB (-10.76 per thousand)) < MJW (-10.30 per thousand) < TJZ (-6.70 per thousand), which demonstrated that δ13C(DIC) would be heavier after rocky desertification and lighter after the rocky desertification are treated and controlled.

In-Package Chemistry Abstraction

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

E. Thomas

2004-11-09

This report was developed in accordance with the requirements in ''Technical Work Plan for: Regulatory Integration Modeling and Analysis of the Waste Form and Waste Package'' (BSC 2004 [DIRS 171583]). The purpose of the in-package chemistry model is to predict the bulk chemistry inside of a breached waste package and to provide simplified expressions of that chemistry as function of time after breach to Total Systems Performance Assessment for the License Application (TSPA-LA). The scope of this report is to describe the development and validation of the in-package chemistry model. The in-package model is a combination of two models, amore » batch reactor model that uses the EQ3/6 geochemistry-modeling tool, and a surface complexation model that is applied to the results of the batch reactor model. The batch reactor model considers chemical interactions of water with the waste package materials and the waste form for commercial spent nuclear fuel (CSNF) waste packages and codisposed waste packages that contain both high-level waste glass (HLWG) and DOE spent fuel. The surface complexation model includes the impact of fluid-surface interactions (i.e., surface complexation) on the resulting fluid composition. The model examines two types of water influx: (1) the condensation of water vapor that diffuses into the waste package, and (2) seepage water that enters the waste package from the drift as a liquid. (1) Vapor Influx Case: The condensation of vapor onto the waste package internals is simulated as pure H2O and enters at a rate determined by the water vapor pressure for representative temperature and relative humidity conditions. (2) Water Influx Case: The water entering a waste package from the drift is simulated as typical groundwater and enters at a rate determined by the amount of seepage available to flow through openings in a breached waste package. TSPA-LA uses the vapor influx case for the nominal scenario for simulations where the waste package has been breached but the drip shield remains intact, so all of the seepage flow is diverted from the waste package. The chemistry from the vapor influx case is used to determine the stability of colloids and the solubility of radionuclides available for transport by diffusion, and to determine the degradation rates for the waste forms. TSPA-LA uses the water influx case for the seismic scenario, where the waste package has been breached and the drip shield has been damaged such that seepage flow is actually directed into the waste package. The chemistry from the water influx case that is a function of the flow rate is used to determine the stability of colloids and the solubility of radionuclides available for transport by diffusion and advection, and to determine the degradation rates for the CSNF and HLW glass. TSPA-LA does not use this model for the igneous scenario. Outputs from the in-package chemistry model implemented inside TSPA-LA include pH, ionic strength, and total carbonate concentration. These inputs to TSPA-LA will be linked to the following principle factors: dissolution rates of the CSNF and HLWG, dissolved concentrations of radionuclides, and colloid generation.« less

Associations between water quality, Pasteurella multocida, and avian cholera at Sacramento National Wildlife Refuge

USGS Publications Warehouse

Lehr, M.A.; Botzler, R.G.; Samuel, M.D.; Shadduck, D.J.

2005-01-01

We studied patterns in avian cholera mortality, the presence of Pasteurella multocida in the water or sediment, and water chemistry characteristics in 10 wetlands at the Sacramento National Wildlife Refuge Complex (California, USA), an area of recurrent avian cholera epizootics, during the winters of 1997 and 1998. Avian cholera outbreaks (a?Y50 dead birds) occurred on two wetlands during the winter of 1997, but no P. multocida were recovered from 390 water and 390 sediment samples from any of the 10 wetlands. No mortality events were observed on study wetlands during the winter of 1998; however, P. multocida was recovered from water and sediment samples in six of the 10 study wetlands. The pH levels were higher for wetlands experiencing outbreaks during the winter of 1997 than for nonoutbreak wetlands, and aluminum concentrations were higher in wetlands from which P. multocida were recovered during the winter of 1998. Water chemistry parameters (calcium, magnesium, sodium, and dissolved protein) previously linked with P. multocida and avian cholera mortality were not associated with the occurrence of avian cholera outbreaks or the presence of P. multocida in our study wetlands. Overall, we found no evidence to support the hypothesis that wetland characteristics facilitate the presence of P. multocida and, thereby, allow some wetlands to serve as long-term sources (reservoirs) for P. multocida.

Adsorption of dyes by ACs prepared from waste tyre reinforcing fibre. Effect of texture, surface chemistry and pH.

PubMed

Acevedo, Beatriz; Rocha, Raquel P; Pereira, Manuel F R; Figueiredo, José L; Barriocanal, Carmen

2015-12-01

This paper compares the importance of the texture and surface chemistry of waste tyre activated carbons in the adsorption of commercial dyes. The adsorption of two commercial dyes, Basic Astrazon Yellow 7GLL and Reactive Rifafix Red 3BN on activated carbons made up of reinforcing fibres from tyre waste and low-rank bituminous coal was studied. The surface chemistry of activated carbons was modified by means of HCl-HNO3 treatment in order to increase the number of functional groups. Moreover, the influence of the pH on the process was also studied, this factor being of great importance due to the amphoteric characteristics of activated carbons. The activated carbons made with reinforcing fibre and coal had the highest SBET, but the reinforcing fibre activated carbon samples had the highest mesopore volume. The texture of the activated carbons was not modified upon acid oxidation treatment, unlike their surface chemistry which underwent considerable modification. The activated carbons made with a mixture of reinforcing fibre and coal experienced the largest degree of oxidation, and so had more acid surface groups. The adsorption of reactive dye was governed by the mesoporous volume, whilst surface chemistry played only a secondary role. However, the surface chemistry of the activated carbons and dispersive interactions played a key role in the adsorption of the basic dye. The adsorption of the reactive dye was more favored in a solution of pH 2, whereas the basic dye was adsorbed more easily in a solution of pH 12. Copyright © 2015 Elsevier Inc. All rights reserved.

Water geochemistry of shallow lakes from the southeastern Pampa plain, Argentina and their implications on mollusk shells preservation.

PubMed

Cristini, Paula A; Tietze, Eleonor; De Francesco, Claudio G; Martínez, Daniel E

2017-12-15

A seasonal sampling of sediments, column and interstitial water for physico-chemical analysis were performed in littoral and open water areas in three freshwater shallow lakes (Nahuel Rucá, Las Mostazas and Los Carpinchos) from Southeastern Pampa plain, Argentina. The main objective of the present study is to evaluate how the characteristics of the depositional environments could be affecting mollusk shell preservation. These lakes are very shallow (2m) and are characterized by an extensive littoral area, dominated by the emergent macrophyte Schoenoplectus californicus, which forms a complete ring around the lake, and an open water area, in general free of vegetation. Five samples of sediments in each compartment were extracted for analysis of pH, moisture, organic matter and carbonates content using a gravity corer, while five samples from column and interstitial water were extracted for chemical analysis (pH, conductivity, major ions, minor ions and hardness). Besides, calcite and aragonite saturation indices and the redox potential were calculated for each lake. The results show the significant impact of water chemistry and redox conditions on the preservation potential of freshwater mollusk and consequently in the quality of paleonvironmental reconstruction based on the biological record from the study region. The higher concentration of organic matter and lower pH registered in the littoral area, mainly during warm months (autumn and summer), suggest worst environments for mollusk preservation, compared to open waters. Moreover, water geochemistry analysis showed aragonite and calcite indices near equilibrium or slightly subsaturated in interstitial water associated with more acid pHs, while column water is strongly oversaturated related to alkaline pHs. These results suggest that carbonate remains within sediments will be subject to dissolution affecting negatively their preservation potential. However, mollusk shells in contact with the column water are not expected to be dissolved. Copyright © 2017 Elsevier B.V. All rights reserved.

Using Chemistry and Color To Analyze Household Products: A 10-12-Hour Laboratory Project at the General Chemistry Level.

ERIC Educational Resources Information Center

Bosma, Wayne B.

1998-01-01

Describes a set of experiments using a UV-VIS spectrometer to identify food colorings and to measure the pH of soft drinks. The first laboratory component uses locations and shapes of visible absorption peaks as a means of identifying dyes while the second portion uses the spectrometer for determining pH. (PVD)

Spectral changes induced by pH variation of aqueous extracts derived from biomass burning aerosols: Under dark and in presence of simulated sunlight irradiation

NASA Astrophysics Data System (ADS)

Cai, Jing; Zhi, Guorui; Yu, Zhiqiang; Nie, Peng; Gligorovski, Sasho; Zhang, Yuzhe; Zhu, Like; Guo, Xixiang; Li, Pei; He, Tan; He, Youjiang; Sun, Jianzhong; Zhang, Yang

2018-07-01

Water soluble organic carbon (WSOC) can significantly influence the aerosol optical properties and the aqueous phase chemistry in cloudwater, fogwater and aerosol liquid water. Here, we examine how the changing pH (in acidic range) affects the absorption spectra of aqueous extracts from field biomass burning aerosols, under dark conditions and in presence of simulated sunlight illumination. The observation under dark conditions indicates that pH variation from 2 to 5 induces significantly enhanced light absorbance in the wavelength ranges of 235-270 nm and 300-550 nm, whereas the light absorbance decreased in the range of 270-300 nm, which might be partially ascribed to the deprotonation of carboxylic acids and phenols. During the extract photolysis, light absorption exhibits photo-bleaching below 380 nm and photo-enhancement above 380 nm, indicating that at acidic levels (pH = 2-5), the particle extracts could undergo a significant composition evolution leading to a modification of absorptive properties. Meanwhile, after 12 h-photolysis, the acidity ([H+]) normalized by WSOC concentration in aqueous extracts ([WSOCae]) increased with a variation of Δ[H+]/[WSOCae]=(3.7 ± 0.7) × 10-7 mol mgC-1 (mean ± standard deviation), suggesting the formation of new acidic substances. Although these findings were acquired in aqueous solutions more relevant to cloud and fog water, the similar evolution likely occurs in wetted aerosols. This calls more attention to the effect of acidity on the wetted aerosols in order to better estimate the aerosol radiative forcing.

Hyun Suk Kang | NREL

Science.gov Websites

Hyun Suk Kang Albert Kang Postdoctoral Researcher-Chemistry Albert.Kang@nrel.gov | 303-384-6667 Dr , Chemistry, and Mathematics and his Master of Science degree in Chemistry from Northwestern University in 2009. He earned his Ph.D. degree in Physical Chemistry from Washington University in St. Louis in 2016

Role of solution chemistry in the retention and release of ...

EPA Pesticide Factsheets

Upon increasing production and use of graphene oxide nanoparticles (GONPs), concerns agitate over their potential impacts and risks to the environment, ecosystem, and human health. An improved understanding of the fate and transport including remobilization of GONPs in the subsurface environment enables us to better expedite the benign use of GONPs in a sustainable fashion but also evaluate their environmental impacts and health risks. In this study, the deposition and release of GONPs were systematically examined in water-saturated columns packed with either uncoated sand or iron oxide-coated sand (U-S and Fe-S, respectively) at environmentally relevant solution chemistry conditions (1–100 mM KCl and 0.1–10 mM CaCl2 at pH 7.0). Our results indicate that, in line with the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory, increasing influent ionic strength (IS) resulted in the reduced mobility of GONPs; and the impact of monovalent K+ was less than divalent Ca2+ in weakening the mobility of GONPs in both U-S and Fe-S. The positively charged iron oxide coating on the sand surface strongly immobilized the negatively charged GONPs at pH 7.0, producing the hyperexponential retention profiles for GONPs particularly in the presence of CaCl2 due primarily to the synergistic effects between iron oxide coating and Ca2+ (e.g., aggravate physical straining). A stepwise decreasing in pore-water transient IS initiated detachment of GONPs that were previously retained in the

Effects of acidic precipitation on the water quality of streams in the Laurel Hill area, Somerset County, Pennsylvania, 1983-86

USGS Publications Warehouse

Barker, J.L.; Witt, E. C.

1990-01-01

Five headwater streams in the Laurel Hill area in southwestern Pennsylvania were investigated from September 1983 through February 1986 to determine possible effects of acidic precipitation on water quality. Precipitation in the Laurel Hill area is among the most acidic in the Nation, with a mean volume-weighted pH of 4.06. Sulfate is the dominant acid-forming anion, averaging 3.6 milligrams per liter or about 50 kilograms per hectare in wet deposition alone. Nitrate averages about 2 milligrams per liter or 7 kilograms per hectare in the study area. Stream chemistry in the five streams is quite variable and apparently is influenced to a large degree by the bedrock geology and by small amounts of alkaline material in watershed soils. Three of the five streams with no or little acid-neutralizing capacity presently are devoid of fish because of low pH and elevated aluminum concentrations. Aluminum concentrations increase in the other two streams during rainfall and snowmelt despite comparatively higher base flow and acid-neutralizing capacities. Comparison of the chemistry of streamflow during 14 storm events at South Fork Bens Creek and North Fork Bens Creek reveals similar chemical responses when discharge suddenly increases. Concentrations of dissolved metals and sulfate increased during stormflow and snowmelt runoff, whereas concentrations of base cations, silica, and chloride decreased. Nitrate concentrations were not affected by rainfall runoff by tended to increase with snowmelt runoff.

PhET Interactive Simulations: Transformative Tools for Teaching Chemistry

ERIC Educational Resources Information Center

Moore, Emily B.; Chamberlain, Julia M.; Parson, Robert; Perkins, Katherine K.

2014-01-01

Developing fluency across symbolic-, macroscopic-, and particulate-level representations is central to learning chemistry. Within the chemistry education community, animations and simulations that support multi-representational fluency are considered critical. With advances in the accessibility and sophistication of technology,…

Reactive transport modelling of groundwater chemistry in a chalk aquifer at the watershed scale

NASA Astrophysics Data System (ADS)

Mangeret, A.; De Windt, L.; Crançon, P.

2012-09-01

This study investigates thermodynamics and kinetics of water-rock interactions in a carbonate aquifer at the watershed scale. A reactive transport model is applied to the unconfined chalk aquifer of the Champagne Mounts (France), by considering both the chalk matrix and the interconnected fracture network. Major element concentrations and main chemical parameters calculated in groundwater and their evolution along flow lines are in fair agreement with field data. A relative homogeneity of the aquifer baseline chemistry is rapidly reached in terms of pH, alkalinity and Ca concentration since calcite equilibrium is achieved over the first metres of the vadose zone. However, incongruent chalk dissolution slowly releases Ba, Mg and Sr in groundwater. Introducing dilution effect by rainwater infiltration and a local occurrence of dolomite improves the agreement between modelling and field data. The dissolution of illite and opal-CT, controlling K and SiO2 concentrations in the model, can be approximately tackled by classical kinetic rate laws, but not the incongruent chalk dissolution. An apparent kinetic rate has therefore been fitted on field data by inverse modelling: 1.5 × 10- 5 molchalk L - 1water year - 1. Sensitivity analysis indicates that the CO2 partial pressure of the unsaturated zone is a critical parameter for modelling the baseline chemistry over the whole chalk aquifer.

Carbon nanotube sensors integrated inside a microfluidic channel for water quality monitoring

NASA Astrophysics Data System (ADS)

Liu, Yu; Li, Xinghui; Dokmeci, Mehmet R.; Wang, Ming L.

2011-04-01

Single-walled carbon nanotubes (SWNTs) with their unique electrical properties and large surface area are remarkable materials for detecting low concentration of toxic and hazardous chemicals (both from the gaseous and liquid phases). Ionic adsorbates in water will attach on to SWNTs and drastically alter their electrical properties. Several SWNTs based pH and chemical sensors have been demonstrated. However, most of them require external components to test and analyze the response of SWNTs to ions inside the liquid samples. Here, we report a water quality monitoring sensor composed of SWNTs integrated inside microfluidic channels and on-chip testing components with a wireless transmission board. To detect multiple analytes in water requires the functionalization of SWNTs with different chemistries. In addition, microfluidic channels are used to guide liquid samples to individual nanotube sensors in an efficient manner. Furthermore, the microfluidic system enables sample mixing and separation before testing. To realize the nanosensors, first microelectrodes were fabricated on an oxidized silicon substrate. Next, PDMS micro channels were fabricated and bonded on the substrate. These channels can be incorporated with a microfluidic system which can be designed to manipulate different analytes for specific molecule detection. Low temperature, solution based Dielectrophoretic (DEP) assembly was conducted inside this microfluidic system which successfully bridged SWNTs between the microelectrodes. The SWNTs sensors were next characterized with different pH buffer solutions. The resistance of SWNTs had a linearly increase as the pH values ranged from 5 to 8. The nanosensor incorporated within the microfluidic system is a versatile platform and can be utilized to detect numerous water pollutants, including toxic organics and microorganisms down to low concentrations. On-chip processing and wireless transmission enables the realization of a full autonomous system for real time monitoring of water quality.

Increases in dissolved organic carbon accelerate loss of toxic Al in Adirondack lakes recovering from acidification

USGS Publications Warehouse

Lawrence, Gregory B.; Dukett, James E; Houck, Nathan; Snyder, Phillip; Capone, Susan B.

2013-01-01

Increasing pH and decreasing Al in surface waters recovering from acidification have been accompanied by increasing concentrations of dissolved organic carbon (DOC) and associated organic acids that partially offset pH increases and complicate assessments of recovery from acidification. To better understand the processes of recovery, monthly chemistry from 42 lakes in the Adirondack region, NY, collected from 1994 to 2011, were used to (1) evaluate long-term changes in DOC and associated strongly acidic organic acids and (2) use the base-cation surplus (BCS) as a chemical index to assess the effects of increasing DOC concentrations on the Al chemistry of these lakes. Over the study period, the BCS increased (p < 0.01) and concentrations of toxic inorganic monomeric Al (IMAl) decreased (p < 0.01). The decreases in IMAl were greater than expected from the increases in the BCS. Higher DOC concentrations that increased organic complexation of Al resulted in a decrease in the IMAl fraction of total monomeric Al from 57% in 1994 to 23% in 2011. Increasing DOC concentrations have accelerated recovery in terms of decreasing toxic Al beyond that directly accomplished by reducing atmospheric deposition of strong mineral acids.

Increases in dissolved organic carbon accelerate loss of toxic Al in Adirondack lakes recovering from acidification.

PubMed

Lawrence, Gregory B; Dukett, James E; Houck, Nathan; Snyder, Phil; Capone, Sue

2013-07-02

Increasing pH and decreasing Al in surface waters recovering from acidification have been accompanied by increasing concentrations of dissolved organic carbon (DOC) and associated organic acids that partially offset pH increases and complicate assessments of recovery from acidification. To better understand the processes of recovery, monthly chemistry from 42 lakes in the Adirondack region, NY, collected from 1994 to 2011, were used to (1) evaluate long-term changes in DOC and associated strongly acidic organic acids and (2) use the base-cation surplus (BCS) as a chemical index to assess the effects of increasing DOC concentrations on the Al chemistry of these lakes. Over the study period, the BCS increased (p < 0.01) and concentrations of toxic inorganic monomeric Al (IMAl) decreased (p < 0.01). The decreases in IMAl were greater than expected from the increases in the BCS. Higher DOC concentrations that increased organic complexation of Al resulted in a decrease in the IMAl fraction of total monomeric Al from 57% in 1994 to 23% in 2011. Increasing DOC concentrations have accelerated recovery in terms of decreasing toxic Al beyond that directly accomplished by reducing atmospheric deposition of strong mineral acids.

Critical loads of acidity for 90,000 lakes in northern Saskatchewan: A novel approach for mapping regional sensitivity to acidic deposition

NASA Astrophysics Data System (ADS)

Cathcart, H.; Aherne, J.; Jeffries, D. S.; Scott, K. A.

2016-12-01

Atmospheric emissions of sulphur dioxide (SO2) from large point sources are the primary concern for acidic deposition in western Canada, particularly in the Athabasca Oil Sands Region (AOSR) where prevailing winds may potentially carry SO2 over acid-sensitive lakes in northern Saskatchewan. A novel catchment-scale regression kriging approach was used to assess regional sensitivity and critical loads of acidity for the total lake population of northern Saskatchewan (89,947 lakes). Lake catchments were delineated using Thiessen polygons, and surface water chemistry was predicted for sensitivity indicators (calcium, pH, alkalinity, and acid neutralizing capacity). Critical loads were calculated with the steady state water chemistry model using regression-kriged base cations, sulphate, and dissolved organic carbon concentrations modelled from surface water observations (n > 800) and digital landscape-scale characteristics, e.g., climate, soil, vegetation, landcover, and geology maps. A large region (>13,726 km2) of two or more indicators of acid sensitivity (pH < 6 and acid neutralizing capacity, alkalinity, calcium < 50 μeq L-1) and low critical loads < 5 meq m-2 yr-1 were predicted on the Athabasca Basin. Exceedance of critical loads under 2006 modelled total sulphate deposition was predicted for 12% of the lakes (covering an area of 3742 km2), primarily located on the Athabasca Basin, within 100 km of the AOSR. There have been conflicting scientific reports of impacts from atmospheric emissions from the AOSR; the results of this study suggest that catchments in the Athabasca Basin within 100 km of the AOSR have received acidic deposition in excess of their critical loads and many of them may be at risk of ecosystem damage owing to their sensitivity.

Impacts on water quality and biota from natural acid rock drainage in Colorado's Lake Creek watershed

USGS Publications Warehouse

Bird, D.A.; Sares, Matthew A.; Policky, Greg A.; Schmidt, Travis S.; Church, Stan E.

2006-01-01

Colorado's Lake Creek watershed hosts natural acid rock drainage that significantly impacts surface water, streambed sediment, and aquatic life. The source of the ARD is a group of iron-rich springs that emerge from intensely hydrothermally altered, unexploited, low-grade porphyry copper mineralization in the Grizzly Peak Caldera. Source water chemistry includes pH of 2.5 and dissolved metal concentrations of up to 277 mg/L aluminum, 498 mg/L iron, and 10 mg/L copper. From the hydrothermally altered area downstream for 27 kilometers to Twin Lakes Reservoir, metal concentrations in streambed sediment are elevated and the watershed experiences locally severe adverse impacts to aquatic life due to the acidic, metal-laden water. The water and sediment quality of Twin Lakes Reservoir is sufficiently improved that the reservoir supports a trout fishery, and remnants of upstream ARD are negligible.

Limnological and water-quality data from Wonder Lake, Chilchukabena Lake, and Lake Minchumina, Denali National Park and Preserve and surrounding area, Alaska, June 2006-August 2008

USGS Publications Warehouse

Long, D.A.; Arp, C.D.

2011-01-01

Growing visitor traffic and resource use, as well as natural and anthropogenic land and climatic changes, can place increasing stress on lake ecosystems in Denali National Park and Preserve. Baseline data required to substantiate impact assessment in this sub-arctic region is sparse to non-existent. The U.S. Geological Survey, in cooperation with the National Park Service, conducted a water-quality assessment of several large lakes in and around the Park from June 2006 to August 2008. Discrete water-quality samples, lake profiles of pH, specific conductivity, dissolved-oxygen concentration, water temperature, turbidity, and continuous-record temperature profile data were collected from Wonder Lake, Chilchukabena Lake, and Lake Minchumina. In addition, zooplankton, snow chemistry data, fecal coliform, and inflow/outflow water-quality samples also were collected from Wonder Lake.

Magnetic iron oxide and manganese-doped iron oxide nanoparticles for the collection of alpha-emitting radionuclides from aqueous solutions

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

O'Hara, Matthew J.; Carter, Jennifer C.; Warner, Cynthia L.

Magnetic nanoparticles are well known to possess chemically active surfaces and high surface areas that can be employed to extract a range of ions from aqueous solutions. Additionally, their paramagnetic property provides a convenient means for bulk collection of the material from solution after the targeted ions have been adsorbed. Herein, two nanoscale amphoteric metal oxides, each possessing useful magnetic attributes, were evaluated for their ability to collect both naturally occurring radioactive isotopes (polonium (Po), radium (Ra), and uranium (U)) as well as the transuranic element americium (Am) from a suite of naturally occurring aqueous matrices. The nanomaterials include commerciallymore » available paramagnetic magnetite (Fe3O4) and magnetite that was modified to incorporate manganese (Mn) into the crystal structure. The chemical stability of these nanomaterials was evaluated in Hanford Site, WA ground water between the natural pH (~8) and pH 1 (acidified with HCl). Whereas the magnetite was observed to have good stability over the pH range, the Mn-doped material was observed to leach Mn at low pH. The materials were evaluated in parallel to characterize their uptake performance of the aforementioned alpha-emitting radionuclide spikes from Hanford Site ground water across a range of pH (from ~8 down to 2). In addition, radiotracer uptake experiments were performed on Columbia River water, seawater, and human urine at their natural pH and at pH 2. Despite the observed leaching of Mn from the Mn-doped nanomaterial in the lower pH range, it exhibited generally superior analyte extraction performance compared to the magnetite, and analyte uptake was observed across a broader pH range. The uptake behavior of the various radiotracers on these two materials at different pH levels can generally be explained by the amphoteric nature of the nanoparticle surfaces. Finally, the rate of sorption of the radiotracers on the two materials in unacidified groundwater was evaluated. The uptake curves generally indicate that equilibrium is obtained within a few minutes, which is attributed to the high surface areas of the nanomaterials and the high level of dispersion in the liquids. Overall, the results indicate that these nanomaterials may have the potential to be employed for a range of applications to extract radionuclides from aqueous solutions. These applications may include analytical chemistry, waste water treatment and remediation, mining, and in vitro radiobioassay.« less

Differential modification of seawater carbonate chemistry by major coral reef benthic communities

NASA Astrophysics Data System (ADS)

Page, Heather N.; Andersson, Andreas J.; Jokiel, Paul L.; Rodgers, Ku'ulei S.; Lebrato, Mario; Yeakel, Kiley; Davidson, Charlie; D'Angelo, Sydney; Bahr, Keisha D.

2016-12-01

Ocean acidification (OA) resulting from uptake of anthropogenic CO2 may negatively affect coral reefs by causing decreased rates of biogenic calcification and increased rates of CaCO3 dissolution and bioerosion. However, in addition to the gradual decrease in seawater pH and Ω a resulting from anthropogenic activities, seawater carbonate chemistry in these coastal ecosystems is also strongly influenced by the benthic metabolism which can either exacerbate or alleviate OA through net community calcification (NCC = calcification - CaCO3 dissolution) and net community organic carbon production (NCP = primary production - respiration). Therefore, to project OA on coral reefs, it is necessary to understand how different benthic communities modify the reef seawater carbonate chemistry. In this study, we used flow-through mesocosms to investigate the modification of seawater carbonate chemistry by benthic metabolism of five distinct reef communities [carbonate sand, crustose coralline algae (CCA), corals, fleshy algae, and a mixed community] under ambient and acidified conditions during summer and winter. The results showed that different communities had distinct influences on carbonate chemistry related to the relative importance of NCC and NCP. Sand, CCA, and corals exerted relatively small influences on seawater pH and Ω a over diel cycles due to closely balanced NCC and NCP rates, whereas fleshy algae and mixed communities strongly elevated daytime pH and Ω a due to high NCP rates. Interestingly, the influence on seawater pH at night was relatively small and quite similar across communities. NCC and NCP rates were not significantly affected by short-term acidification, but larger diel variability in pH was observed due to decreased seawater buffering capacity. Except for corals, increased net dissolution was observed at night for all communities under OA, partially buffering against nighttime acidification. Thus, algal-dominated areas of coral reefs and increased net CaCO3 dissolution may partially counteract reductions in seawater pH associated with anthropogenic OA at the local scale.

Calcite saturation in the River Dee, NE Scotland.

PubMed

Wade, A J; Neal, C; Smart, R P; Edwards, A C

2002-01-23

The spatial and temporal variations in calcite (calcium carbonate) solubility within the Dee basin of NE Scotland were assessed using water chemistry data gathered from a network of 59 sites monitored for water quality from June 1996 to May 1997. Calcite solubility, expressed in terms of a saturation index (SIcalcite), was determined from measured streamwater pH, Gran alkalinity and calcium concentrations and water temperature. In general, the waters of the Dee system are undersaturated with respect to calcite, though the saturation index is higher during the summer months indicating a dependency on flow conditions and biological activity. Under low-flow conditions, the streamwaters are dominated by water derived from the lower soil horizons and deeper groundwater stores and therefore, ions such as Gran alkalinity and calcium are at their highest concentrations as they are derived mainly from bedrock weathering. The influence of biological activity on the carbonate system is also evident as the observed pH and estimated EpCO2 values indicate strong seasonal patterns, with the highest pH and lowest EpCO2 values occurring during the summer low-flow periods. Only at three sites in the lowland region of the catchment, during the summer low-flow period, are the waters oversaturated. As such, the Dee system represents an extreme 'end-member' case when compared to many UK rivers that span both under- and oversaturated conditions during the year. Regression analysis highlights a systematic change in the SIcalcite-pH relationship in a broad east-west direction across the Dee system. At sites draining the relatively impermeable upland areas, the regression of SIcalcite against pH gives a straight line with a gradient in the range 1.6-2.4. Correspondingly, under the most extreme alkaline conditions found at sites draining lowland agricultural areas, a straight-line relationship exists but with a gradient of unity. It is concluded that these changes in the SIcalcite-pH relationship are due to variations in the bicarbonate system induced by the flow conditions and biological activity. Given the waters are undersaturated, then calcite precipitation and hence phosphorus co-precipitation cannot occur within the water column.

Questa baseline and pre-mining ground-water quality investigation. 14. Interpretation of ground-water geochemistry in catchments other than the Straight Creek catchment, Red River Valley, Taos County, New Mexico, 2002-2003

USGS Publications Warehouse

Nordstrom, D. Kirk; McCleskey, R. Blaine; Hunt, Andrew G.; Naus, Cheryl A.

2005-01-01

The U.S. Geological Survey, in cooperation with the New Mexico Environment Department, is investigating the pre-mining ground-water chemistry at the Molycorp molybdenum mine in the Red River Valley, New Mexico. The primary approach is to determine the processes controlling ground-water chemistry at an unmined, off-site but proximal analog. The Straight Creek catchment, chosen for this purpose, consists of the same Tertiary-age quartz-sericite-pyrite altered andesite and rhyolitic volcanics as the mine site. Straight Creek is about 5 kilometers east of the eastern boundary of the mine site. Both Straight Creek and the mine site are at approximately the same altitude, face south, and have the same climatic conditions. Thirteen wells in the proximal analog drainage catchment were sampled for ground-water chemistry. Eleven wells were installed for this study and two existing wells at the Advanced Waste-Water Treatment (AWWT) facility were included in this study. Eight wells were sampled outside the Straight Creek catchment: one each in the Hansen, Hottentot, and La Bobita debris fans, four in a well cluster in upper Capulin Canyon (three in alluvial deposits and one in bedrock), and an existing well at the U.S. Forest Service Questa Ranger Station in Red River alluvial deposits. Two surface waters from the Hansen Creek catchment and two from the Hottentot drainage catchment also were sampled for comparison to ground-water compositions. In this report, these samples are evaluated to determine if the geochemical interpretations from the Straight Creek ground-water geochemistry could be extended to other ground waters in the Red River Valley , including the mine site. Total-recoverable major cations and trace metals and dissolved major cations, selected trace metals, anions, alkalinity; and iron-redox species were determined for all surface- and ground-water samples. Rare-earth elements and low-level As, Bi, Mo, Rb, Re, Sb, Se, Te, Th, U, Tl, V, W, Y, and Zr were determined on selected samples. Dissolved organic carbon (DOC), mercury, sulfate stable isotope composition (d34S and d18O of sulfate), stable isotope composition of water (d2H and d18O of water) were measured for selected samples. Chlorofluorocarbons (CFC) and 3He and 3H were measured for age dating on selected samples. Linear regressions from the Straight Creek ground-water data were used to compare ground-water chemistry trends in non-Straight Creek ground waters with Straight Creek alluvial ground-water chemistry dilution trends. Most of the solute trends for the ground waters are similar to those for Straight Creek but there are some notable exceptions. In lithologies that contain substantial pyrite mineralization, acid waters form with similar chemistries to those in Straight Creek and all the waters tend to be calcium-sulfate type. Hottentot ground waters contain substantially lower calcium concentrations relative to those in Straight Creek. This anomaly results from the exposure of rhyolite porphyry in the Hottentot scar and weathering zone. The rhyolite contains less calcium than the altered andesites and tuffs in the Straight Creek catchment and probably does not have the abundant gypsum and calcite. The Hansen ground waters have reached gypsum saturation and have similar calcium, magnesium, and beryllium concentrations as Straight Creek ground waters but have lower concentrations of fluoride, manganese, zinc, cobalt, nickel, copper, and lithium. Lower concentrations of elements related to mineralization at Hansen likely reflect the more distal location of Hansen with respect to intrusive centers that provided the heat source for hydrothermal alteration. The other ground water with water chemistry trends that are outside the Straight Creek trends was from an alluvial well from Capulin Canyon (CC2A). Although it had pH values near 6.0 and most major ions similar to the other Capulin Canyon ground waters, it contained high concentrations

A Chemist’s Perspective on the Role of Phosphorus at the Origins of Life

PubMed Central

Fernández-García, Christian; Coggins, Adam J.

2017-01-01

The central role that phosphates play in biological systems, suggests they also played an important role in the emergence of life on Earth. In recent years, numerous important advances have been made towards understanding the influence that phosphates may have had on prebiotic chemistry, and here, we highlight two important aspects of prebiotic phosphate chemistry. Firstly, we discuss prebiotic phosphorylation reactions; we specifically contrast aqueous electrophilic phosphorylation, and aqueous nucleophilic phosphorylation strategies, with dry-state phosphorylations that are mediated by dissociative phosphoryl-transfer. Secondly, we discuss the non-structural roles that phosphates can play in prebiotic chemistry. Here, we focus on the mechanisms by which phosphate has guided prebiotic reactivity through catalysis or buffering effects, to facilitating selective transformations in neutral water. Several prebiotic routes towards the synthesis of nucleotides, amino acids, and core metabolites, that have been facilitated or controlled by phosphate acting as a general acid–base catalyst, pH buffer, or a chemical buffer, are outlined. These facile and subtle mechanisms for incorporation and exploitation of phosphates to orchestrate selective, robust prebiotic chemistry, coupled with the central and universally conserved roles of phosphates in biochemistry, provide an increasingly clear message that understanding phosphate chemistry will be a key element in elucidating the origins of life on Earth. PMID:28703763

Interactions Between Atmospheric Aerosols and Marine Boundary Layer Clouds on Regional and Global Scales

NASA Astrophysics Data System (ADS)

Wang, Zhen

Airborne aerosols are crucial atmospheric constituents that are involved in global climate change and human life qualities. Understanding the nature and magnitude of aerosol-cloud-precipitation interactions is critical in model predictions for atmospheric radiation budget and the water cycle. The interactions depend on a variety of factors including aerosol physicochemical complexity, cloud types, meteorological and thermodynamic regimes and data processing techniques. This PhD work is an effort to quantify the relationships among aerosol, clouds, and precipitation on both global and regional scales by using satellite retrievals and aircraft measurements. The first study examines spatial distributions of conversion rate of cloud water to rainwater in warm maritime clouds over the globe by using NASA A-Train satellite data. This study compares the time scale of the onset of precipitation with different aerosol categories defined by values of aerosol optical depth, fine mode fraction, and Angstrom Exponent. The results indicate that conversion time scales are actually quite sensitive to lower tropospheric static stability (LTSS) and cloud liquid water path (LWP), in addition to aerosol type. Analysis shows that tropical Pacific Ocean is dominated by the highest average conversion rate while subtropical warm cloud regions (far northeastern Pacific Ocean, far southeastern Pacific Ocean, Western Africa coastal area) exhibit the opposite result. Conversion times are mostly shorter for lower LTSS regimes. When LTSS condition is fixed, higher conversion rates coincide with higher LWP and lower aerosol index categories. After a general global view of physical property quantifications, the rest of the presented PhD studies is focused on regional airborne observations, especially bulk cloud water chemistry and aerosol aqueous-phase reactions during the summertime off the California coast. Local air mass origins are categorized into three distinct types (ocean, ships, and land) with their influences on cloud water composition examined and implications of wet deposition discussed. Chemical analysis of cloud water samples indicates a wide pH range between 2.92 and 7.58, with an average as 4.46. The highest pH values were observed north of San Francisco, coincident with the strongest land mass influence (e.g. Si, B, and Cs). Conversely, the lowest pH values were observed south of San Francisco where there is heavy ship traffic, resulting in the highest concentrations of sulfate, nitrate, V, Fe, Al, P, Cd, Ti, Sb, P, and Mn. The acidic cloud environment with influences from various air mass types can affect the California coastal aquatic ecosystem since it can promote the conversion of micronutrients to more soluble forms. Beyond characterization of how regional air mass sources affect cloud water composition, aircraft cloud water collection provides precious information on tracking cloud processing with specific species such as oxalic acid, which is the most abundant dicarboxylic acid in tropospheric aerosols. Particular attention is given to explore relationship between detected metals with oxalate aqueous-phase production mechanisms. A number of case flights show that oxalate concentrations drop by nearly an order of magnitude relative to samples in the same vicinity with similar environmental and cloud physical conditions. Such a unique feature was consistent with an inverse relationship between oxalate and Fe. In order to examine the hypothesis that oxalate decreasing is potentially related to existing of Fe, chemistry box model simulations were conducted. The prediction results show that the loss of oxalate due to the photolysis of iron oxalato complexes is likely a significant oxalate sink in the study region due to the ubiquity of oxalate precursors, clouds, and metal emissions from ships, the ocean, and continental sources.

Effects of Urban Development on Water-Quality in the Piedmont of North Carolina-- The NAWQA Urban Land-Use Gradient Study

NASA Astrophysics Data System (ADS)

Harned, D. A.; Cuffney, T. F.; Giddings, E. M.; McMahon, G.

2004-12-01

A study of urban basins located in the Piedmont of North Carolina is underway as part of the U. S. Geological Survey National Water-Quality Assessment (NAWQA) to determine the relation between level of urban development and water quality. Data were collected from 30 basins on water chemistry (nutrient, pesticide, and ion concentrations), geomorphic and habitat characteristics, hydrologic stage, discharge, water temperature, pH, dissolved-oxygen concentration, specific conductance, benthic algae, invertebrate communities, and fish communities. Collection frequency for water chemistry ranged from 2 samples (at 20 sites) to 6 samples (at 10 sites). Biological data were collected in each basin twice. Investigation of the effects of urbanization on water quality must control for the effects of natural factors, while varying the degree of urbanization between study basins. A regional framework was used to control variability in natural factors that influence water-quality. The urban intensity in each basin was measured by using an index to integrate information on human influences. The Urban Index includes information about land cover, infrastructure, population, and socioeconomic characteristics. Sites were selected to represent the full gradient of undeveloped to fully urbanized basins. A preliminary review of the stream water-chemistry data indicates distinct relations between ionic composition and the Urban Index. Mean specific conductance was positively correlated with the Urban Index (Spearman correlation coefficient (r) = 0.77; 95-percent confidence limits (95CL) 0.61 - 0.93; probability (pr) <0.0001; N=30). Specific conductance ranged from 56 microsiemens (uS) at the least developed site to 607 uS at the most developed site. Dissolved sulfate (r=0.74; 95CL 0.57 - 0.91; pr <0.0001) and chloride (r=0.71; 95CL 0.52 - 0.90; pr <0.0001) were also positively correlated with the Urban Index. Sulfate ranged from 2.3 to 66 milligrams per liter (mg/L), and chloride ranged from 3.5 to 96 mg/L. Urban sources of sulfate include domestic sewage and emissions from the combustion of automotive and diesel fuels. Sources of chloride include sewage and road salting. pH was positively correlated with the Urban Index (r=0.60; 95CL 0.38 - 0.84; pr= 0.0005) with a range from 6.5 at the least urban site to 7.5 at the most urban site. The increase in pH may be due in part to conversion of organic forest soils to less acidic soils of urban lawns. The overall trend of increasing total dissolved nitrogen (r=0.46; 95CL 0.12 - 0.80; pr=0.0103) and nitrite plus nitrate (r=0.46; 95CL 0.09 - 0.83; pr=0.0109) concentrations, with increasing Urban Index may reflect sources such as sewage and lawn fertilizer use in the more urban basins. However, some of the least urban basins also had elevated nitrogen concentrations reflecting possible agricultural influences such as fertilizer use and animal waste. Total nitrogen concentration ranged from 0.31 to 14 mg/L. Unit-area stream discharge during low-flow periods was negatively correlated with the Urban Index (r= -0.56; 95CL -0.74 - -0.37; pr=0.0014). Reduced discharge with greater urban development may be a result of reduced infiltration caused by impervious surfaces. Unit discharge ranged from 0.47 to 2.27 cubic feet per second per square mile of drainage area.

An interview with James Wilbur, Ph.D. General Manager, Life Sciences, Meso Scale Discovery.

PubMed

Wilbur, James

2004-06-01

James L. Wilbur, Ph.D. received a Bachelor's degree from the University of California, San Diego and a Ph.D. in Chemistry from Stanford University. After completing an NIH Postdoctoral Fellowship with Professor George M. Whitesides in the Department of Chemistry at Harvard University, he joined IGEN International, Inc., where he held a variety of positions in Research and Development. During that time, he was part of the team that developed the core technology and products for Meso Scale Discovery. He assumed his current position in 2001 when Meso Scale Discovery launched the products discussed here.

Bioretention storm water control measures decrease the toxicity of copper roof runoff.

PubMed

LaBarre, William J; Ownby, David R; Rader, Kevin J; Lev, Steven M; Casey, Ryan E

2017-06-01

The present study evaluated the ability of 2 different bioretention storm water control measures (SCMs), planter boxes and swales, to decrease the toxicity of sheet copper (Cu) roofing runoff to Daphnia magna. The present study quantified changes in storm water chemistry as it passed through the bioretention systems and utilized the biotic ligand model (BLM) to assess whether the observed D. magna toxicity could be predicted by variations found in water chemistry. Laboratory toxicity tests were performed using select storm samples with D. magna cultured under low ionic strength conditions that were appropriate for the low ionic strength of the storm water samples being tested. The SCMs decreased toxicity of Cu roof runoff in both the BLM results and the storm water bioassays. Water exiting the SCMs was substantially higher than influent runoff in pH, ions, alkalinity, and dissolved organic carbon and substantially lower in total and dissolved Cu. Daphnids experienced complete mortality in untreated runoff from the Cu roof (the SCM influent); however, for planter and swale effluents, survival averaged 86% and 95%, respectively. The present study demonstrated that conventional bioretention practices, including planter boxes and swales, are capable of decreasing the risk of adverse effects from sheet Cu roof runoff to receiving systems, even before considering dilution of effluents in those receiving systems and associated further reductions in copper bioavailability. Environ Toxicol Chem 2017;36:1680-1688. © 2016 SETAC. © 2016 SETAC.

Remote assessment of instantaneous changes in water chemistry after liming in a Nova Scotia catchment

NASA Astrophysics Data System (ADS)

Angelidis, Christine

2013-04-01

Remote assessment of instantaneous changes in water chemistry after liming in a Nova Scotia catchment ANGELIDIS, C.1, STERLING, S.1, BREEN, A.2, BIAGI, K.1., and CLAIR, T.A.1 1Dalhousie University, christine.angelidis@dal.ca, 2Bluenose Coastal Action Foundation, andrew@coastalaction.org Southwestern Nova Scotia has some of the most acidic freshwaters in North America due to its location downwind of the major emission sources in eastern Canada and the US and due to a resistant geology which offers little acid buffering capacity (Clair et al. 2007). Because of the poor buffering and regionally high runoff values, hydrological events such as snowmelt and rain storms are frequent and can cause sudden changes in water chemistry which can have devastating effects on freshwater biota due to increases in acidity and metals (Dennis and Clair in press). Clair et al. (2001) have estimated the potential frequency of acidic episodes in this region based on a number of hydrological factors, though the technology available at the time to monitor short-term changes was not dependable. Recent advances in equipment have made the assessment of the frequency and severity of acidic episodes easier and more accurate, allowing better interpretation and prediction of hydrogeochemical changes with variations in weather and deposition patterns. Here we take advantage of these recent advances to monitor water chemistry in an experimental catchment, and explore the response to catchment liming. Catchment liming is one way of mitigating the effects of acid deposition in sensitive areas. We limed a 50 ha catchment at a rate of 5 t/ha in the Gold River watershed of southwest Nova Scotia to examine the interactions between application of lime with the geological and climatological conditions of this region and acid episode frequency. In order to assess changes of episode frequency caused by liming, we established two mobile environmental monitoring platforms in the catchment: a control site located immediately above the limed area, and a treatment site 10 m below the limed area. We monitored pH, DO, water temperature, conductivity, stage height, air temperature, wind speed and direction as well as precipitation every 15 minutes since November 2011 with the data being accessed in real-time. The high frequency measurements were supplemented by a full chemical analysis of bi-weekly to monthly grab-samples at the site since December 2010. Pre-treatment stream chemistry and hydrology data at the control and treatment sites show identical patterns. pH values before treatment were as low as 4.9 and Ca2+ as low as 0.7 mg•L-1 demonstrating the need for the lime treatment. In this work, we show real-time outputs of pre- and post-treatment stream chemistry and present the short-term effects of liming on this uniquely acid sensitive ecosystem. Clair, T.A., Bobba, A.G., & Miller, K. 2001. Yearly changes in the seasonal frequency and duration of short-term acid pulses in Nova Scotia, Canada streams. Env. Geol. 40: 582-591. Clair, T.A., Dennis, I.F., Scruton, D.A., & Gilliss, M. 2007. Freshwater acidification research in Atlantic Canada: a review of results and predictions for the future. Env. Reviews 15: 153-167. Dennis, I.F. & Clair, T.A. (in press) The distribution of dissolved aluminum in Atlantic salmon (Salmo salar) rivers of Atlantic Canada and its potential effect on aquatic populations. Can. J.Fish Aquat. Sci.

A general quantitative pH sensor developed with dicyandiamide N-doped high quantum yield graphene quantum dots.

PubMed

Wu, Zhu Lian; Gao, Ming Xuan; Wang, Ting Ting; Wan, Xiao Yan; Zheng, Lin Ling; Huang, Cheng Zhi

2014-04-07

A general quantitative pH sensor for environmental and intracellular applications was developed by the facile hydrothermal preparation of dicyandiamide (DCD) N-doped high quantum yield (QY) graphene quantum dots (GQDs) using citric acid (CA) as the carbon source. The obtained N-doped GQDs have excellent photoluminesence (PL) properties with a relatively high QY of 36.5%, suggesting that N-doped chemistry could promote the QY of carbon nanomaterials. The possible mechanism for the formation of the GQDs involves the CA self-assembling into a nanosheet structure through intermolecular H-bonding at the initial stage of the reaction, and then the pure graphene core with many function groups formed through the dehydration between the carboxyl and hydroxyl of the intermolecules under hydrothermal conditions. These N-doped GQDs have low toxicity, and are photostable and pH-sensitive between 1.81 to 8.96, giving a general pH sensor with a wide range of applications from real water to intracellular contents.

Groundwater chemistry near an impoundment for produced water, Powder River Basin, Wyoming, USA

USGS Publications Warehouse

Healy, R.W.; Bartos, T.T.; Rice, C.A.; McKinley, M.P.; Smith, B.D.

2011-01-01

The Powder River Basin is one of the largest producers of coal-bed natural gas (CBNG) in the United States. An important environmental concern in the Basin is the fate of the large amounts of groundwater extracted during CBNG production. Most of this produced water is disposed of in unlined surface impoundments. A 6-year study of groundwater flow and water chemistry at one impoundment, Skewed Reservoir, has produced the most detailed data set for any impoundment in the Basin. Data were collected from a network of 21 observation wells and three suction lysimeters. A groundwater mound formed atop bedrock within initially unsaturated, unconsolidated deposits underlying the reservoir. Heterogeneity in physical and chemical properties of sediments resulted in complex groundwater flow paths and highly variable groundwater chemistry. Sulfate, bicarbonate, sodium, and magnesium were the dominant ions in all areas, but substantial variability existed in relative concentrations; pH varied from less than 3 to more than 9, and total dissolved solids concentrations ranged from less than 5000 to greater than 100,000 mg/L. Selenium was a useful tracer of reservoir water; selenium concentrations exceeded 300 μg/L in samples obtained from 18 of the 24 sampling points. Groundwater travel time from the reservoir to a nearby alluvial aquifer (a linear distance of 177 m) was calculated at 474 days on the basis of selenium concentrations. The produced water is not the primary source of solutes in the groundwater. Naturally occurring salts and minerals within the unsaturated zone, dissolved and mobilized by infiltrating impoundment water, account for most of the solute mass in groundwater. Gypsum dissolution, cation-exchange, and pyrite oxidation appear to be important reactions. The complex geochemistry and groundwater flow paths at the study site underscore the difficulty in assessing effects of surface impoundments on water resources within the Powder River Basin.

Acidic, neutral and alkaline forest ponds as a landscape element affecting the biodiversity of freshwater snails.

PubMed

Spyra, Aneta

2017-08-22

In recent years, the number of areas remaining under the influence of acidity has increased. At all levels of ecosystems, biodiversity decreases with acidification, due to the elimination of species that are most sensitive to low pH. Forest ponds belong to a specific group that varied in location, a huge amount of leaf litter, and isolation from other aquatic environments. They are crucial in the industrial landscape with well-developed industry and human activity. The aim was to investigate the relative importance of water chemistry in explaining snail assemblage compositions and species richness in forest ponds of contrasting pH. Patterns in gastropod communities were determined from an analysis in 26 forest ponds with multivariate gradient analysis. Ponds ranged in a base mean pH from 3.0 to 9.0. pH has been found to be an important factor influencing gastropod fauna. Neutral ponds support diverse communities, typical of small water bodies. In two acidic pond types, snail fauna was different. Among the species characteristic for acidic ponds (pH < 6) were Anisus spirorbis and Aplexa hypnorum. The greatest distinct characterised alkaline ponds with the numerous appearance of alien Physa acuta. The most diverse gastropod fauna was found in neutral ponds, whereas the lowest degree of diversity was found in ponds with the lowest pH. Current knowledge of pH-associated changes in aquatic ecosystems is still incomplete because anthropogenic acidification is a recent phenomenon. It is extremely important in forest habitats, since they react more intensively to climatic factors and are often used in landscape management and planning.

Humic Acid Effects on the Transport of Colloidal Particles in Unsaturated Porous Media: Humic Acid Dosage, pH, and Ionic Strength Dependence

NASA Astrophysics Data System (ADS)

Morales, V. L.; Gao, B.; Steenhuis, T. S.

2008-12-01

Soil colloids and biocolloids can facilitate contaminant transport within the soil profile through the complexation of pollutants previously thought to have limited mobility. Dissolved organic substances are qualitatively known to alter the behavior of colloids and surface chemistry of soil particles in aquatic environments when adsorbed to their surfaces. Specifically, it has been observed that even small amounts of adsorbed humic acids result in a pronounced increase in colloid mobility in saturated porous systems, presumably by a combination of electrostatic and steric stabilization. However, the degree to which adsorbed humic acids stabilize colloidal suspension is highly sensitive to the system's solution chemistry; mainly in terms of pH, ionic strength, and metal ions present. The objective of this study is to expound quantitatively on the role that combined stabilizing and destabilizing solution chemistry components have on humic acid-colloid transport in unsaturated media by isolating experimentally some underlying mechanisms that regulate colloid transport in realistic aquatic systems. We hypothesize that in chemically heterogeneous porous media, with ionic strength values above 0 and pH ranges from 4 to 9, the effect of humic acid on colloid suspensions cannot be simply characterized by increased stability and mobility. That a critical salt concentration must exists for a given humic acid concentration and pH, above which the network of humic acid collapses by forming coordination complexes with other suspended or adsorbed humic acids, thus increasing greatly the retention of colloids in the porous medium by sweep flocculation. In addition, capillary forces in unsaturated media may contribute further to overcome repulsive forces that prevent flocculation of humic acid-colloid complexes. The experimental work in this study will include: jar tests to determine critical solution concentration combinations for desired coagulation/flocculation rates, column experiments to obtain effluent breakthrough data, in-situ visualization of internal processes with bright field microscopy, batch adsorption measurements, and changes in hydrophobic interaction energy of colloid and media surfaces for realistic aqueous ionic strength and pH ranges. Such experimental results are expected to provide sufficient evidence to corroborate our speculations that under natural soil water conditions, humic acids may greatly contribute to the immobilization of colloidal particles.

Competition for spectral irradiance between epilimnetic optically active dissolved and suspended matter and phytoplankton in the metalimnion. Consequences for limnology and chemistry.

PubMed

Bracchini, Luca; Dattilo, Arduino Massimo; Falcucci, Margherita; Hull, Vincent; Tognazzi, Antonio; Rossi, Claudio; Loiselle, Steven Arthur

2011-06-01

In deep lakes, water column stratification isolates the surface water from the deeper bottom layers, creating a three dimensional differentiation of the chemical, physical, biological and optical characteristics of the waters. Chromophoric dissolved organic matter (CDOM) and total suspended solids (TSS) play an important role in the attenuation of ultraviolet and photosynthetically active radiation. In the present analysis of spectral irradiance, we show that the wavelength composition of the metalimnetic visible irradiance was influenced by epilimnetic spatial distribution of CDOM. We found a low occurrence of blue-green photons in the metalimnion where epilimnetic concentrations of CDOM are high. In this field study, the spatial variation of the spectral irradiance in the metalimnion correlates with the observed metalimnetic concentrations of chlorophyll a as well as chlorophyll a : chlorophyll b/c ratios. Dissolved oxygen, pH, and nutrients trends suggest that chlorophyll a concentrations were representative of the phytoplankton biomass and primary production. Thus, metalimnetic changes of spectral irradiance may have a direct impact on primary production and an indirect effect on the spatial trends of pH, dissolved oxygen, and inorganic nutrients in the metalimnion.

Crystal-chemistry of alteration products of vitrified wastes: Implications on the retention of polluting elements

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

Sterpenich, Jerome

2008-07-01

Alteration products of vitrified wastes coming from the incineration of household refuse (MSW) are described. Two vitrified wastes containing 50% and 70% of fly ash and a synthetic stained-glass with a composition close to that of an ancient glass (medieval stained-glass) were altered under different pH conditions (1, 5.5 corresponding to demineralized water and 10) during 181 days. Under acidic condition, the alteration layer is made of an amorphous hydrated silica gel impoverished in most of the initial elements. A minor phase MPO{sub 4} . nH{sub 2}O, where M represents Fe, Ti, Al, Ca and K cations, also constitutes themore » altered layer of the synthetic stained-glass. Under neutral and basic conditions, the altered layer is made of an amorphous hydrated silica gel and a crystallized calcium phosphate phase. The silica gel is depleted in alkalis and alkali-earth elements but contains significant amounts of aluminium, magnesium and transition elements, whereas the calcium phosphate is a hydroxylapatite-like phase with P-Si substitutions and a Ca/P ratio depending on the pH of the solution. This study shows: (i) the strong influence of pH conditions on the crystal-chemistry of alteration products and thus on the mechanisms of weathering resulting in different trapping of polluting elements, and (ii) that glass alteration does not necessary produce thermodynamically stable phases which has to be taken into account for the prediction of the long-term behavior.« less

Effect of groundwater geochemistry on pentachlorophenol remediation by smectite-templated nanosized Pd0/Fe0.

PubMed

Jia, Hanzhong; Gu, Cheng; Li, Hui; Fan, Xiaoyun; Li, Shouzhu; Wang, Chuanyi

2012-09-01

Zero-valent iron holds great promise in treating groundwater, and its reactivity and efficacy depend on many surrounding factors. In the present work, the effects of solution chemistry such as pH, humic acid (HA), and inorganic ions on pentachlorophenol (PCP) dechlorination by smectite-templated Pd(0)/Fe(0) were systematically studied. Smectite-templated Pd(0)/Fe(0) was prepared by saturating the negatively charged sites of smectite clay with Fe(III) and a small amount of Pd(II), followed by borohydride reduction to convert Fe(III) and Pd(II) into zero-valent metal clusters. Batch experiments were conducted to investigate the effects of water chemistry on PCP remediation. The PCP dechlorination rate critically depends on the reaction pH over the range 6.0~10.0; the rate constant (k (obs)) increases with decreasing the reaction pH value. Also, the PCP remediation is inhibited by HA, which can be attributed to the electron competition of HA with H(+). In addition, the reduction of PCP can be accelerated by various anions, following the order: Cl(-) > HCO (3) (-) > SO (4) (2-) ~no anion. In the case of cations, Ca(2+) and Mg(2+) (10 mM) decrease the dechlorination rate to 0.7959 and 0.7798 from 1.315 h(-1), respectively. After introducing HA into the reaction systems with cations or/and anions, the dechlorination rates are similar to that containing HA alone. This study reveals that low pH and the presence of some anions such as Cl(-) facilitate the PCP dechlorination and induce the rapid consumption of nanosized zero-valent iron simultaneously. However, the dechlorination rate is no longer correlated to the inhibitory or accelerating effects by cations and anions in the presence of 10 mg/L HA.

Direct observation and determination of the mechanisms governing mobility of asbestos in porous media

NASA Astrophysics Data System (ADS)

Seiphoori, A.; Ortiz, C. P.; Jerolmack, D. J.

2017-12-01

Transport of asbestos through soil by groundwater is typically considered to be negligible. There are indications, however, that under some conditions of pore-water/soil chemistry asbestos may become mobile, implying that buried contaminants could migrate from a disposal site and surface elsewhere. Shape, size and surface charge may influence the physical and chemical interactions of colloids with the soil matrix, and asbestos consists of elongated particles with different size and unique surface charge properties. Although chemical factors such as pH and ionic strength of pore water may affect the transport properties, the presence of dissolved organic carbon (DOC) has been identified to remarkably enhance the mobility of colloids including asbestos. To date, there is no explanation for how the presence of DOC may facilitate the mobilization of asbestos in soil - mainly because the soil medium has been treated as a black box without the possibility of observing particles within the matrix. Here, we investigated the mobility of chrysotile asbestos particles ( 10 um long) in porous media by developing a flow cell with an optically-transparent porous medium composed of granules of a refractive-index matched material. This enabled us to observe and track the particles within the water-saturated porous medium using in situ microscopy. The aqueous suspension of asbestos fibers was passed through this artificial soil, while the physical and chemical interaction of asbestos particles with the medium and their pore-scale distribution were analyzed. We studied the effects of changing solution chemistry (e.g., ionic strength, pH, and DOC content) on transport, attachment and aggregation of chrysotile particles. Experiments revealed a novel mechanism where the DOC-associated nanoparticles attach to chrysotile fibers by an electrostatic attraction, which facilitates their mobilization through the porous medium while modulating aggregation among fibers. Although pH and ionic strength also influenced aggregation and the attachment rate of particles to the substrate, the effect of DOC was more pronounced. This work may lead to enhanced predictions for the fate and transport of asbestos (as well as other contaminants) in the environment, and has implications for the mobility of asbestos particles in the human body.

Effect of makeup water properties on the condenser fouling in power planr cooling system

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

Safari, I.; Walker, M.; Abbasian, J.

2011-01-01

The thermoelectric power industry in the U.S. uses a large amount of fresh water. As available freshwater for use in thermoelectric power production becomes increasingly limited, use of nontraditional water sources is of growing interest. Utilization of nontraditional water, in cooling systems increases the potential for mineral precipitation on heat exchanger surfaces. In that regard, predicting the accelerated rate of scaling and fouling in condenser is crucial to evaluate the condenser performance. To achieve this goal, water chemistry should be incorporated in cooling system modeling and simulation. This paper addresses the effects of various makeup water properties on the coolingmore » system, namely pH and aqueous speciation, both of which are important factors affecting the fouling rate in the main condenser. Detailed modeling of the volatile species desorption (i.e. CO{sub 2} and NH{sub 3}), the formation of scale in the recirculating system, and the relationship between water quality and the corresponding fouling rates is presented.« less

Benthic metabolic feedbacks to carbonate chemistry on coral reefs:implications for ocean acidification

NASA Astrophysics Data System (ADS)

Price, N.; Rohwer, F. L.; Stuart, S. A.; Andersson, A.; Smith, J.

2012-12-01

The metabolic activity of resident organisms can cause spatio-temporal variability in carbonate chemistry within the benthic boundary layer, and thus potentially buffer the global impacts of ocean acidification. But, little is known about the capacity for particular species assemblages to contribute to natural daily variability in carbonate chemistry. We encapsulated replicate areas (~3m2) of reef across six Northern Line Islands in the central Pacific for 24 hrs to quantify feedbacks to carbonate chemistry within the benthic boundary layer from community metabolism. Underneath each 'tent', we quantified relative abundance and biomass of each species of corals and algae. We coupled high temporal resolution time series data on the natural diurnal variability in pH, dissolved oxygen, salinity, and temperature (using autonomous sensors) with resident organisms' net community calcification and productivity rates (using change in total dissolved carbon and total alkalinity over time) to examine feedbacks from reef metabolism to boundary layer carbonate chemistry. These reefs experienced large ranges in pH (> 0.2 amplitude) each day, similar to the magnitude of 'acidification' expected over the next century. Daily benthic pH, pCO2, and aragonite saturation state (Ωaragonite) were contrasted with seasonal threshold values estimated from open ocean climatological data extrapolated at each island to determine relative inter-island feedbacks. Diurnal amplitude in pH, pCO2, and Ωaragonite at each island was dependent upon the resident species assemblage of the benthos and was particularly reliant upon the biomass, productivity, and calcification rate of Halimeda. Net primary productivity of fleshy algae (algal turfs and Lobophora spp.) predominated on degraded, inhabited islands where net community calcification was negligible. In contrast, the chemistry over reefs on 'pristine', uninhabited islands was driven largely by net calcification of calcareous algae and stony corals. Knowledge about species specific physiological rates and relative abundances of key taxa whose metabolism significantly alters carbonate chemistry may give insight to the ability for a reef to buffer against or exacerbate ocean acidification.

A mathematical model of pH, based on the total stoichiometric concentration of acids, bases and ampholytes dissolved in water.

PubMed

Mioni, Roberto; Mioni, Giuseppe

2015-10-01

In chemistry and in acid-base physiology, the Henderson-Hasselbalch equation plays a pivotal role in studying the behaviour of the buffer solutions. However, it seems that the general function to calculate the valence of acids, bases and ampholytes, N = f(pH), at any pH, has only been provided by Kildeberg. This equation can be applied to strong acids and bases, pluriprotic weak acids, bases and ampholytes, with an arbitrary number of acid strength constants, pKA, including water. By differentiating this function with respect to pH, we obtain the general equation for the buffer value. In addition, by integrating the titration curve, TA, proposed by Kildeberg, and calculating its Legendre transform, we obtain the Gibbs free energy of pH (or pOH)-dependent titratable acid. Starting from the law of electroneutrality and applying suitable simplifications, it is possible to calculate the pH of the buffer solutions by numerical methods, available in software packages such as Excel. The concept of buffer capacity has also been clarified by Urbansky, but, at variance with our approach, not in an organic manner. In fact, for each set of monobasic, dibasic, tribasic acids, etc., various equations are presented which independently fit each individual acid-base category. Consequently, with the increase in acid groups (pKA), the equations become more and more difficult, both in practice and in theory. Some examples are proposed to highlight the boundary that exists between acid-base physiology and the thermodynamic concepts of energy, chemical potential, amount of substance and acid resistance.

Deposition of acidifying species in the Waterberg region of South Africa and the potential for stream chemistry impacts

NASA Astrophysics Data System (ADS)

Piketh, S.; Curtis, C.; Pienaar, K.; Khuzwayo, L.; van Zyl, P. G.; Conradie, E.

2016-12-01

South Africa is rich in natural resources that include large deposits of coal. As a result more than 90% of the energy in the country is generated by 13 coal fired power stations located on the Highveld region. Over the past 7 years South Africa has experienced severe power shortages which has resulted in the approval of two new mega coal fired power stations each with a 4800 Mw generating capacity. One of these power stations is at Lephalale in the Waterberg. This region is largely dominated by a natural to semi-natural landscape, but some areas have acid sensitive sub-soils (pH < 5.5) rendering their headwater streams vulnerable to acidification. There are only three other important sources of emissions close to Lephalale, a second coal fired power station, a char plant and domestic coal combustion. In an attempt to determine baseline conditions of air pollution, deposition and stream chemistry impacts prior to the commissioning of the new PS the following measurements have been undertaken, ambient concentrations of SO2, NOx, NH3 and O3 (at seven sites since 2010), rain water chemistry ( at one site for 2015 and 2016) and headwater stream vulnerability (2015 and 2016). Concentrations of sodium (Na+), ammonium (NH4+), potassium (K+), calcium (Ca2+), magnesium (Mg2+), nitrate 21 (NO3-), chloride (Cl-), sulphate (SO42-) in the rain water will be presented and compared to other long term sites around South Africa. Total deposition of S and N will in the Lephalale region will be presented. At least 30 acid-sensitive headwater streams, many with low pH <6 and low acid neutralizing capacity that are extremely sensitive to acid deposition inputs have been identified. Future deposition in the area of acidifying species will be modelled by including emissions from the new Power station and estimates of the potential impact will be assessed.

21 CFR 862.1550 - Urinary pH (nonquantitative) test system.

Code of Federal Regulations, 2010 CFR

2010-04-01

... (CONTINUED) MEDICAL DEVICES CLINICAL CHEMISTRY AND CLINICAL TOXICOLOGY DEVICES Clinical Chemistry Test... the monitoring of patients with certain diets. (b) Classification. Class I (general controls). The...

Microbial metabolism alters pore water chemistry and increases consolidation of oil sands tailings.

PubMed

Arkell, Nicholas; Kuznetsov, Petr; Kuznetsova, Alsu; Foght, Julia M; Siddique, Tariq

2015-01-01

Tailings produced during bitumen extraction from surface-mined oil sands ores (tar sands) comprise an aqueous suspension of clay particles that remain dispersed for decades in tailings ponds. Slow consolidation of the clays hinders water recovery for reuse and retards volume reduction, thereby increasing the environmental footprint of tailings ponds. We investigated mechanisms of tailings consolidation and revealed that indigenous anaerobic microorganisms altered porewater chemistry by producing CO and CH during metabolism of acetate added as a labile carbon amendment. Entrapped biogenic CO decreased tailings pH, thereby increasing calcium (Ca) and magnesium (Mg) cations and bicarbonate (HCO) concentrations in the porewater through dissolution of carbonate minerals. Soluble ions increased the porewater ionic strength, which, with higher exchangeable Ca and Mg, decreased the diffuse double layer of clays and increased consolidation of tailings compared with unamended tailings in which little microbial activity was observed. These results are relevant to effective tailings pond management strategies. Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.

Chemical and physical microenvironments at the Viking landing sites

NASA Technical Reports Server (NTRS)

Clark, B. C.

1979-01-01

Physical and chemical considerations permit the division of the near-surface regolith on Mars into at least six zones of distinct microenvironments. The zones are euphotic, duricrust/peds, tempofrost, permafrost, endolithic, and interfacial/transitional. Microenvironments vary significantly in temperature extremes, mean temperature, salt content, relative pressure of water vapor, UV and visible light irradiance, and exposure to ionizing radiation events (100 Mrad) and oxidative molecular species. From what is known of the chemistry of the atmosphere and regolith fines (soil), limits upon the aqueous chemistry of soil pastes may be estimated. Heat of wetting could reach 45 cal/g dry soil; initial pH is indeterminate between 1 and 10; ionic strength and salinity are predicted to be extremely high; freezing point depression is inadequate to provide quantities of liquid water except in special cases. The prospects for biotic survival are grim by terrestrial standards, but the extremes of biological resiliency are inaccessible to evaluation. Second-generation in situ experiments which will better define Martian microenvironments are clearly possible. Antarctic dry valleys are approximations to Martian conditions, but deviate significantly by at least half-a-dozen criteria.

Chemical and physical microenvironments at the Viking landing sites.

PubMed

Clark, B C

1979-12-01

Physical and chemical considerations permit the division of the near-surface regolith on Mars into at least six zones of distinct microenvironments. The zones are euphotic, duricrust/peds, tempofrost, permafrost, endolithic, and interfacial/transitional. Microenvironments vary significantly in temperature extremes, mean temperature, salt content, relative pressure of water vapor, UV and visible light irradiance, and exposure to ionizing radiation events (100 Mrad) and oxidative molecular species. From what is known of the chemistry of the atmosphere and regolith fines (soil), limits upon the aqueous chemistry of soil pastes may be estimated. Heat of wetting could reach 45 cal/g dry soil; initial pH is indeterminate between 1 and 10; ionic strength and salinity are predicted to be extremely high; freezing point depression is inadequate to provide quantities of liquid water except in special cases. The prospects for biotic survival are grim by terrestrial standards, but the extremes of biological resiliency are inaccessible to evaluation. Second-generation in situ experiments which will better define Martian microenvironments are clearly possible. Antarctic dry valleys are approximations to Martian conditions, but deviate significantly by at least half-a-dozen criteria.

Characterizations of the Formation of Polydopamine-Coated Halloysite Nanotubes in Various pH Environments.

PubMed

Feng, Junran; Fan, Hailong; Zha, Dao-An; Wang, Le; Jin, Zhaoxia

2016-10-11

Recent studies demonstrated that polydopamine (PDA) coating is universal to nearly all substrates, and it endows substrates with biocompatibility, postfunctionality, and other useful properties. Surface chemistry of PDA coating is important for its postmodifications and applications. However, there is less understanding of the formation mechanism and surface functional groups of PDA layers generated in different conditions. Halloysite is a kind of clay mineral with tubular nanostructure. Water-swellable halloysite has unique reactivity. In this study, we have investigated the reaction of dopamine in the presence of water-swellable halloysite. We have tracked the reaction progresses in different pH environments by using UV-vis spectroscopy and surface-enhanced Raman spectroscopy (SERS). The surface properties of PDA on halloysite were clarified by X-ray photoelectron spectroscopy (XPS), SERS, Fourier transform infrared (FTIR) characterizations, zeta potential, surface wettability, and morphological characterizations. We noticed that the interaction between halloysite surface and dopamine strongly influences the surface functionality of coated PDA. In addition, pH condition further modulates surface functional groups, resulting in less content of secondary/aromatic amine in PDA generated in weak acidic environment. This study demonstrates that the formation mechanism of polydopamine becomes complex in the presence of inorganic nanomaterials. Substrate property and reaction condition dominate the functionality of obtained PDA together.

Environmental setting of fixed sites in the western Lake Michigan drainages, Michigan and Wisconsin

USGS Publications Warehouse

Sullivan, D.J.; Peterson, E.M.; Richards, K.D.

1995-01-01

This report describes selected environmental- setting features for 11 fixed surface-water sites in the Western Lake Michigan Drainages study unit of the National Water-Quality Assessment Pro- gram. The study unit, which includes 10 major river systems draining to Lake Michigan, is bounded on the south by the Illinois State line and extends north to about 31 miles north of Escanaba, Mich. The fixed sites are on the following streams: Peshekee River, Popple River, Menominee River, Pensaukee River, Duck Creek, Tomorrow River, East River, Fox River, North Branch Milwaukee River, Lincoln Creek, and Milwaukee River. Drainage basins above these sites receive runoff from land uses and land covers, bedrock types, and surficial deposits representative of the main types of each of these characteristics in the study unit. Data types collected at the fixed sites include water chemistry; organic compounds and trace elements in streambed sediment and biological tissues; algal, benthic-invertebrate, and fish communities; and aquatic habitat. Field measurements include water temperature, pH, specific conductance, alkalinity, and dissolved oxygen. Results of water- quality field measurements indicate little variation in temperature among the fixed sites. Specific conductance and alkalinity were generally higher at sites underlain by carbonate bedrock than at sites underlain by igneous/metamorphic bedrock. Differences in pH among the fixed sites were less than those for specific conductance and alkalinity, but pH seemed to increase slightly from north to south. Dissolved-oxygen concentration varied more at agricultural sites than at forested and urban sites, perhaps because of higher nutrient inputs at agricultural sites. The information included in this report has been assembled as reference material for ongoing studies at the fixed sites.

Six Month In Situ High-Resolution Carbonate Chemistry and Temperature Study on a Coral Reef Flat Reveals Asynchronous pH and Temperature Anomalies.

PubMed

Kline, David I; Teneva, Lida; Hauri, Claudine; Schneider, Kenneth; Miard, Thomas; Chai, Aaron; Marker, Malcolm; Dunbar, Rob; Caldeira, Ken; Lazar, Boaz; Rivlin, Tanya; Mitchell, Brian Gregory; Dove, Sophie; Hoegh-Guldberg, Ove

2015-01-01

Understanding the temporal dynamics of present thermal and pH exposure on coral reefs is crucial for elucidating reef response to future global change. Diel ranges in temperature and carbonate chemistry parameters coupled with seasonal changes in the mean conditions define periods during the year when a reef habitat is exposed to anomalous thermal and/or pH exposure. Anomalous conditions are defined as values that exceed an empirically estimated threshold for each variable. We present a 200-day time series from June through December 2010 of carbonate chemistry and environmental parameters measured on the Heron Island reef flat. These data reveal that aragonite saturation state, pH, and pCO2 were primarily modulated by biologically-driven changes in dissolved organic carbon (DIC) and total alkalinity (TA), rather than salinity and temperature. The largest diel temperature ranges occurred in austral spring, in October (1.5 - 6.6°C) and lowest diel ranges (0.9 - 3.2°C) were observed in July, at the peak of winter. We observed large diel total pH variability, with a maximum range of 7.7 - 8.5 total pH units, with minimum diel average pH values occurring during spring and maximum during fall. As with many other reefs, the nighttime pH minima on the reef flat were far lower than pH values predicted for the open ocean by 2100. DIC and TA both increased from June (end of Fall) to December (end of Spring). Using this high-resolution dataset, we developed exposure metrics of pH and temperature individually for intensity, duration, and severity of low pH and high temperature events, as well as a combined metric. Periods of anomalous temperature and pH exposure were asynchronous on the Heron Island reef flat, which underlines the importance of understanding the dynamics of co-occurrence of multiple stressors on coastal ecosystems.

Six Month In Situ High-Resolution Carbonate Chemistry and Temperature Study on a Coral Reef Flat Reveals Asynchronous pH and Temperature Anomalies

PubMed Central

Kline, David I.; Teneva, Lida; Hauri, Claudine; Schneider, Kenneth; Miard, Thomas; Chai, Aaron; Marker, Malcolm; Dunbar, Rob; Caldeira, Ken; Lazar, Boaz; Rivlin, Tanya; Mitchell, Brian Gregory; Dove, Sophie; Hoegh-Guldberg, Ove

2015-01-01

Understanding the temporal dynamics of present thermal and pH exposure on coral reefs is crucial for elucidating reef response to future global change. Diel ranges in temperature and carbonate chemistry parameters coupled with seasonal changes in the mean conditions define periods during the year when a reef habitat is exposed to anomalous thermal and/or pH exposure. Anomalous conditions are defined as values that exceed an empirically estimated threshold for each variable. We present a 200-day time series from June through December 2010 of carbonate chemistry and environmental parameters measured on the Heron Island reef flat. These data reveal that aragonite saturation state, pH, and pCO2 were primarily modulated by biologically-driven changes in dissolved organic carbon (DIC) and total alkalinity (TA), rather than salinity and temperature. The largest diel temperature ranges occurred in austral spring, in October (1.5 – 6.6°C) and lowest diel ranges (0.9 – 3.2°C) were observed in July, at the peak of winter. We observed large diel total pH variability, with a maximum range of 7.7 – 8.5 total pH units, with minimum diel average pH values occurring during spring and maximum during fall. As with many other reefs, the nighttime pH minima on the reef flat were far lower than pH values predicted for the open ocean by 2100. DIC and TA both increased from June (end of Fall) to December (end of Spring). Using this high-resolution dataset, we developed exposure metrics of pH and temperature individually for intensity, duration, and severity of low pH and high temperature events, as well as a combined metric. Periods of anomalous temperature and pH exposure were asynchronous on the Heron Island reef flat, which underlines the importance of understanding the dynamics of co-occurrence of multiple stressors on coastal ecosystems. PMID:26039687

One year water chemistry monitoring of the flooding of the Meirama open pit (NW Spain)

NASA Astrophysics Data System (ADS)

Delgado, J.; Juncosa, R.; Vázquez, A.; Fernández-Bogo, S.

2009-04-01

In December, 2007, after 30 years of operations, the mine of Meirama finished the extraction of brown lignite. Starting in April 2008, the flooding of the open pit has started and this is leading to the formation of a large mining lake (~2 km2 surface and up to 180 m depth) in which surface (river and rain water) and ground waters are involved. Since the beginning of the flooding, lake waters are weekly sampled and analyzed for temperature, pH, redox, EC, TDS, TSS, DO,DIC, DOC, turbidity, alkalinity/acidity as well as nearly 40 inorganic chemical components. Stable water isotopes (deuterium and oxygen) are also being recorded. In order to better understand the dynamic chemical evolution of lake waters, the chemical characteristics of rain water as well as a series of lake tributaries and ground waters are also being measured. Since the beginning of the flooding process, the chemical quality of lake water has experienced an interesting evolution that obeys to a variety of circumstances. The silicic geologic substratum of the catchment determines that both ground and surface waters have a rather low alkalinity. Moreover, the presence of disseminated sulfides (mainly pyrite) within the schistous materials of the mine slopes and internal rock dumps provokes a significant acidic load. From April to October 2008, the lake waters had only the contribution of rain and ground waters. Since the beginning of October, a significant volume of surface waters has been derived to the mine hole. Taking pH as indicator, the first water body had a rather acidic pH (~3) which was progressively amended with the addition of a certain amount of lime to reach an upper value of ~8 by late August. The diminution in the addition of lime up to its elimination, in December, has conducted to the progressive acidification of the lake. At present, an instrumented floating deck is being deployed in the lake. This device will serve as a base point where it is planned to locate a series of instrumentation (complete weather monitoring station, multiparametric probe, sediment trap line) that will complement with depth profiles the surficial sampling performed so far.

Atmospheric deposition effects on the chemistry of a stream in Northeastern Georgia

USGS Publications Warehouse

Buell, G.R.; Peters, N.E.

1988-01-01

The quantity and quality of precipitation and streamwater were measured from August 1985 through September 1986 in the Brier Creek watershed, a 440-ha drainage in the Southern Blue Ridge Province of northeastern Georgia, to determine stream sensitivity to acidic deposition. Precipitation samples collected at 2 sites had a volume-weighted average pH of 4.40 whereas stream samples collected near the mouth of Brier Creek had a discharge-weighted average pH of 6.70. Computed solute fluxes through the watershed and observed changes in streamwater chemistry during stormflow suggest that cation exchange, mineral weathering, SO42- adsorption by the soil, and groundwater discharge to the stream are probable factors affecting neutralization of precipitation acidity. Net solute fluxes for the watershed indicate that, of the precipitation input, > 99% of the H+, 93% of the NH4+ and NO3-, and 77% of the SO42- were retained. Sources within the watershed yielded base cations, Cl-, and HCO3- and accounted for 84, 47, and 100% of the net transport, respectively. Although streamwater SO42- and NO3- concentrations increased during stormflow, peak concentrations of these anions were much less than average concentrations in the precipitation. This suggests retention of these solutes occurs even when water residence time is short.The quantity and quality of precipitation and streamwater were measured from August 1985 through September 1986 in the Brier Creek watershed, a 440-ha drainage in the Southern Blue Ridge Province of northeastern Georgia, to determine stream sensitivity to acidic deposition. Precipitation samples collected at 2 sites had a volume-weighted average pH of 4.40 whereas stream samples collected near the mouth of Brier Creek had a discharge-weighted average pYH of 6.70. Computed solute fluxes through the watershed and observed changes in streamwater chemistry drying stormflow suggest that cation exchange, mineral weathering, SO42- adsorption by the soil, and groundwater discharge to the stream are probable factors affecting neutralization of precipitation acidity. Although streamwater SO42- and NO3- concentrations increased during stormflow, peak concentrations of these anions were much less than average concentrations in the precipitation. This suggests retention of these solutes occurs even when water residence time is short.

Dynamic Vertical Profiles of Peat Porewater Chemistry in a Northern Peatland

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

Griffiths, Natalie A.; Sebestyen, Stephen D.

We measured pH, cations, nutrients, and total organic carbon (TOC) over 3 years to examine weekly to monthly variability in porewater chemistry depth profiles (0–3.0 m) in an ombrotrophic bog in Minnesota, USA. We also compared temporal variation at one location to spatial variation in depth profiles at 16 locations across the bog. Most solutes exhibited large gradients with depth. pH increased by two units and calcium concentrations increased over 20 fold with depth, and may reflect peatland development from minerotrophic to ombrotrophic conditions. Ammonium concentrations increased almost 20 fold and TOC concentrations decreased by half with depth, and thesemore » patterns likely reflect mineralization of peat or decomposition of TOC. There was also considerable temporal variation in the porewater chemistry depth profiles. Ammonium, soluble reactive phosphorus, and potassium showed greater temporal variation in near-surface porewater, while pH, calcium, and TOC varied more at depth. This variation demonstrates that deep peat porewater chemistry is not static. Lastly, temporal variation in solute chemistry depth profiles was greater than spatial variation in several instances, especially in shallow porewaters. In conclusion, characterizing both temporal and spatial variability is necessary to ensure representative sampling in peatlands, especially when calculating solute pools and fluxes and parameterizing process-based models.« less

Dynamic Vertical Profiles of Peat Porewater Chemistry in a Northern Peatland

DOE PAGES

Griffiths, Natalie A.; Sebestyen, Stephen D.

2016-10-14

We measured pH, cations, nutrients, and total organic carbon (TOC) over 3 years to examine weekly to monthly variability in porewater chemistry depth profiles (0–3.0 m) in an ombrotrophic bog in Minnesota, USA. We also compared temporal variation at one location to spatial variation in depth profiles at 16 locations across the bog. Most solutes exhibited large gradients with depth. pH increased by two units and calcium concentrations increased over 20 fold with depth, and may reflect peatland development from minerotrophic to ombrotrophic conditions. Ammonium concentrations increased almost 20 fold and TOC concentrations decreased by half with depth, and thesemore » patterns likely reflect mineralization of peat or decomposition of TOC. There was also considerable temporal variation in the porewater chemistry depth profiles. Ammonium, soluble reactive phosphorus, and potassium showed greater temporal variation in near-surface porewater, while pH, calcium, and TOC varied more at depth. This variation demonstrates that deep peat porewater chemistry is not static. Lastly, temporal variation in solute chemistry depth profiles was greater than spatial variation in several instances, especially in shallow porewaters. In conclusion, characterizing both temporal and spatial variability is necessary to ensure representative sampling in peatlands, especially when calculating solute pools and fluxes and parameterizing process-based models.« less

A Methodology for Characterizing Potential Uranium Transport in Deep Geological Disposal Sites

NASA Astrophysics Data System (ADS)

Dittrich, T. M.; Reimus, P. W.

2013-12-01

In order to make safe and reasonable decisions about radioactive waste disposal in deep geologic sites, it is important to understand the fate and potential transport of long half-life transuranic radionuclides over a wide range of time and distance scales. The objective of this study was to evaluate and demonstrate new experimental methods for quantifying the potential for actinide transport in deep fractured crystalline rock formations. We selected a fractured/weathered granodiorite at the Grimsel Test Site (GTS) in Switzerland as a model system because field experiments involving uranium, as well as other actinides, have already been conducted. Working on this system provides a unique opportunity to compare lab experimental results with field-scale observations. Drilled rock cores and weathered fracture fill material (FFM) from the GTS were shipped to Los Alamos National Laboratory, characterized by x-ray diffraction and microscopy, and used in batch sorption/desorption and column breakthrough experiments. Uranium solutions were made by adding uranium to a synthetic Grimsel groundwater that matched the natural water chemistry found in the GTS groundwater. Batch and breakthrough experiments were conducted using solutions between pH 6.9 and 9.0. All column experiments were conducted using syringe pumps at low flow rate (<0.3 ml h-1) in small columns containing 5 g of material with pore volumes of 2-3 ml. These small columns allow rapid and economical evaluation of sorption/desorption behavior under flowing conditions (and in duplicate or triplicate). Solutions were switched to uranium-free synthetic Grimsel groundwater after equilibration in batch experiments or after near-steady uranium breakthrough occurred in column experiments. The measurement of uranium concentrations as a function of time under these conditions allowed interrogation of desorption rates which we believe control uranium fate and transport over long time and distance scales. Uranium transport was conservative and matched tritium breakthrough for pH 9.0; however, retardation increased when pH was reduced to 7.9 and 6.9. We are currently evaluating uranium adsorption/desorption rates as a function of water chemistry (initial focus on pH), with future testing planned to evaluate the influence of carbonate concentrations, flow rates, mineralogy, bentonite colloids and other actinides (e.g., Am). Figure 1. Uranium breakthrough results for (a) 6.5 μM U, (b) U-free solution, (c) flow rate increased from 0.3 to 0.6 mL h-1, (d) pH increased from 6.8 to 7.2, and (e) pH increased from 7.2 to 8.8.

Post Gold King Mine Spill Investigation of Metal Stability in Water and Sediments of the Animas River Watershed.

PubMed

Rodriguez-Freire, Lucia; Avasarala, Sumant; Ali, Abdul-Mehdi S; Agnew, Diane; Hoover, Joseph H; Artyushkova, Kateryna; Latta, Drew E; Peterson, Eric J; Lewis, Johnnye; Crossey, Laura J; Brearley, Adrian J; Cerrato, José M

2016-11-01

We applied spectroscopy, microscopy, diffraction, and aqueous chemistry methods to investigate the persistence of metals in water and sediments from the Animas River 13 days after the Gold King Mine spill (August 5, 2015). The Upper Animas River watershed, located in San Juan Colorado, is heavily mineralized and impacted by acid mine drainage, with low pH water and elevated metal concentrations in sediments (108.4 ± 1.8 mg kg -1 Pb, 32.4 ± 0.5 mg kg -1 Cu, 729.6 ± 5.7 mg kg -1 Zn, and 51 314.6 ± 295.4 mg kg -1 Fe). Phosphate and nitrogen species were detected in water and sediment samples from Farmington, New Mexico, an intensive agricultural area downstream from the Animas River, while metal concentrations were low compared to those observed upstream. Solid-phase analyses of sediments suggest that Pb, Cu, and Zn are associated with metal-bearing jarosite and other minerals (e.g., clays, Fe-(oxy)hydroxides). The solubility of jarosite at near-neutral pH and biogeochemical processes occurring downstream could affect the stability of metal-bearing minerals in river sediments. This study contributes relevant information about the association of metal mixtures in a heavy mineralized semiarid region, providing a foundation to better understand long-term metal release in a public and agricultural water supply.

Jao Van De Lagemaat | NREL

Science.gov Websites

Jao Van De Lagemaat Photo of Jao Vandelagemaat. Jao Van De Lagemaat Center Director: Chemistry and Lagemaat is currently the Center Director of the Chemistry and Nanoscience Center at NREL. He received his university. Education Ph.D. Physical Chemistry, University of Utrecht Featured Publications View all NREL

Anthropogenic CO2 in a dense water formation area of the Mediterranean Sea

NASA Astrophysics Data System (ADS)

Ingrosso, Gianmarco; Bensi, Manuel; Cardin, Vanessa; Giani, Michele

2017-05-01

There is growing evidence that the on-going ocean acidification of the Mediterranean Sea could be favoured by its active overturning circulation. The areas of dense water formation are, indeed, preferential sites for atmospheric carbon dioxide absorption and through them the ocean acidification process can quickly propagate into the deep layers. In this study we estimated the concentration of anthropogenic CO2 (Cant) in the dense water formation areas of the middle and southern Adriatic Sea. Using the composite tracer TrOCA (Tracer combining Oxygen, inorganic Carbon, and total Alkalinity) and carbonate chemistry data collected throughout March 2013, our results revealed that a massive amount of Cant has invaded all the identified water masses. High Cant concentration was detected at the bottom layer of the Pomo Pit (middle Adriatic, 96.8±9.7 μmol kg-1) and Southern Adriatic Pit (SAP, 85.2±9.4 μmol kg-1), associated respectively with the presence of North Adriatic Dense Water (NAdDW) and Adriatic Dense Water (AdDW). This anthropogenic contamination was clearly linked to the dense water formation events, which govern strong CO2 flux from the atmosphere to the sea and the sinking of dense, CO2-rich surface waters to the deep sea. However, a very high Cant level (94.5±12.5 μmol kg-1) was also estimated at the intermediate layer, as a consequence of a recent vertical mixing that determined the physical and biogeochemical modification of the water of Levantine origin (i.e. Modified Levantine Intermediate Water, MLIW) and favoured the atmospheric CO2 intrusion. The penetration of Cant in the Adriatic Sea determined a significant pH reduction since the pre-industrial era (- 0.139±0.019 pH units on average). This estimation was very similar to the global Mediterranean Sea acidification, but it was again more pronounced at the bottom of the Pomo Pit, within the layer occupied by NAdDW (- 0.157±0.018 pH units), and at the intermediate layer of the recently formed MLIW (- 0.143±0.020 pH units). Our results indicate that the Adriatic Sea could potentially be one of the Mediterranean regions most affected by the ocean acidification and also demonstrate its active role in sequestering and storing Cant.

Hydrologic and geochemical factors affecting the chemistry of small headwater streams in response to acidic deposition on Catoctin Mountain, north-central Maryland

USGS Publications Warehouse

Rice, Karen C.; Bricker, Owen P.

1996-01-01

Hydrologic and water-quality data were collected at a precipitation-collection station and from two small watersheds on Catoctin Mountain, north- central Maryland, as part of an investigation of episodic acidification and its effects on streamwater quality. Data were collected from June 1990 through December 1993. Descriptions of the water shed instrumentation, data-collection techniques, and laboratory methods used to conduct the studies are included. Data that were collected on precipitation, throughfall, soil water, ground water, and streamwater during base flow and stormflow indicate that the streams undergo episodic acidification during storms. Both streams showed decreases in pH to less than 5.0 standard units during stormflow. The acid-neutralizing capacity (ANC) of both streams decreased during stormflow, and the ANC of one of the streams, Bear Branch, became negative. The chemistries of the different types of waters that were sampled indicate that shallow subsurface water with minimal residence time in the watersheds is routed to the streams to become stormflow and is the cause of the episodic acidification observed. Three-component hydrograph separations were performed on the data collected during several storms in each watershed. The hydrograph separations of all of the storms indicate that throughfall contributed 0 to 50 percent of the stormflow, soil water contributed 0 to 80 percent, and ground water contributed 20 to 90 percent. The results of the hydrograph separations indicate that, in general, the watershed with higher hydraulic gradients tends to have shallower and shorter flow paths than the watershed with lower hydraulic gradients.

Ocean Acidification Has Multiple Modes of Action on Bivalve Larvae

PubMed Central

Waldbusser, George G.; Hales, Burke; Langdon, Chris J.; Haley, Brian A.; Schrader, Paul; Brunner, Elizabeth L.; Gray, Matthew W.; Miller, Cale A.; Gimenez, Iria; Hutchinson, Greg

2015-01-01

Ocean acidification (OA) is altering the chemistry of the world’s oceans at rates unparalleled in the past roughly 1 million years. Understanding the impacts of this rapid change in baseline carbonate chemistry on marine organisms needs a precise, mechanistic understanding of physiological responses to carbonate chemistry. Recent experimental work has shown shell development and growth in some bivalve larvae, have direct sensitivities to calcium carbonate saturation state that is not modulated through organismal acid-base chemistry. To understand different modes of action of OA on bivalve larvae, we experimentally tested how pH, PCO2, and saturation state independently affect shell growth and development, respiration rate, and initiation of feeding in Mytilus californianus embryos and larvae. We found, as documented in other bivalve larvae, that shell development and growth were affected by aragonite saturation state, and not by pH or PCO2. Respiration rate was elevated under very low pH (~7.4) with no change between pH of ~ 8.3 to ~7.8. Initiation of feeding appeared to be most sensitive to PCO2, and possibly minor response to pH under elevated PCO2. Although different components of physiology responded to different carbonate system variables, the inability to normally develop a shell due to lower saturation state precludes pH or PCO2 effects later in the life history. However, saturation state effects during early shell development will carry-over to later stages, where pH or PCO2 effects can compound OA effects on bivalve larvae. Our findings suggest OA may be a multi-stressor unto itself. Shell development and growth of the native mussel, M. californianus, was indistinguishable from the Mediterranean mussel, Mytilus galloprovincialis, collected from the southern U.S. Pacific coast, an area not subjected to seasonal upwelling. The concordance in responses suggests a fundamental OA bottleneck during development of the first shell material affected only by saturation state. PMID:26061095

Ocean Acidification Has Multiple Modes of Action on Bivalve Larvae.

PubMed

Waldbusser, George G; Hales, Burke; Langdon, Chris J; Haley, Brian A; Schrader, Paul; Brunner, Elizabeth L; Gray, Matthew W; Miller, Cale A; Gimenez, Iria; Hutchinson, Greg

2015-01-01

Ocean acidification (OA) is altering the chemistry of the world's oceans at rates unparalleled in the past roughly 1 million years. Understanding the impacts of this rapid change in baseline carbonate chemistry on marine organisms needs a precise, mechanistic understanding of physiological responses to carbonate chemistry. Recent experimental work has shown shell development and growth in some bivalve larvae, have direct sensitivities to calcium carbonate saturation state that is not modulated through organismal acid-base chemistry. To understand different modes of action of OA on bivalve larvae, we experimentally tested how pH, PCO2, and saturation state independently affect shell growth and development, respiration rate, and initiation of feeding in Mytilus californianus embryos and larvae. We found, as documented in other bivalve larvae, that shell development and growth were affected by aragonite saturation state, and not by pH or PCO2. Respiration rate was elevated under very low pH (~7.4) with no change between pH of ~ 8.3 to ~7.8. Initiation of feeding appeared to be most sensitive to PCO2, and possibly minor response to pH under elevated PCO2. Although different components of physiology responded to different carbonate system variables, the inability to normally develop a shell due to lower saturation state precludes pH or PCO2 effects later in the life history. However, saturation state effects during early shell development will carry-over to later stages, where pH or PCO2 effects can compound OA effects on bivalve larvae. Our findings suggest OA may be a multi-stressor unto itself. Shell development and growth of the native mussel, M. californianus, was indistinguishable from the Mediterranean mussel, Mytilus galloprovincialis, collected from the southern U.S. Pacific coast, an area not subjected to seasonal upwelling. The concordance in responses suggests a fundamental OA bottleneck during development of the first shell material affected only by saturation state.

Estimates of the Direct Effect of Seawater pH on the Survival Rate of Species Groups in the California Current Ecosystem

PubMed Central

Busch, D. Shallin; McElhany, Paul

2016-01-01

Ocean acidification (OA) has the potential to restructure ecosystems due to variation in species sensitivity to the projected changes in ocean carbon chemistry. Ecological models can be forced with scenarios of OA to help scientists, managers, and other stakeholders understand how ecosystems might change. We present a novel methodology for developing estimates of species sensitivity to OA that are regionally specific, and applied the method to the California Current ecosystem. To do so, we built a database of all published literature on the sensitivity of temperate species to decreased pH. This database contains 393 papers on 285 species and 89 multi-species groups from temperate waters around the world. Research on urchins and oysters and on adult life stages dominates the literature. Almost a third of the temperate species studied to date occur in the California Current. However, most laboratory experiments use control pH conditions that are too high to represent average current chemistry conditions in the portion of the California Current water column where the majority of the species live. We developed estimates of sensitivity to OA for functional groups in the ecosystem, which can represent single species or taxonomically diverse groups of hundreds of species. We based these estimates on the amount of available evidence derived from published studies on species sensitivity, how well this evidence could inform species sensitivity in the California Current ecosystem, and the agreement of the available evidence for a species/species group. This approach is similar to that taken by the Intergovernmental Panel on Climate Change to characterize certainty when summarizing scientific findings. Most functional groups (26 of 34) responded negatively to OA conditions, but when uncertainty in sensitivity was considered, only 11 groups had relationships that were consistently negative. Thus, incorporating certainty about the sensitivity of species and functional groups to OA is an important part of developing robust scenarios for ecosystem projections. PMID:27513576

Ecological differentiation within a cosmopolitan group of planktonic freshwater bacteria (SOL cluster, Saprospiraceae, Bacteroidetes).

PubMed

Schauer, Michael; Kamenik, Christian; Hahn, Martin W

2005-10-01

Members of the monophyletic SOL cluster are large filamentous bacteria inhabiting the pelagic zone of many freshwater habitats. The abundances of SOL bacteria and compositions of SOL communities in samples from 115 freshwater ecosystems around the globe were determined by fluorescence in situ hybridization with cluster- and subcluster-specific oligonucleotide probes. The vast majority (73%) of sampled ecosystems harbored SOL bacteria, and all three previously described SOL subclusters (LD2, HAL, and GKS2-217) were detected. The morphometric and chemicophysical parameters and trophic statuses of ecosystems were related to the occurrence and subcluster-specific composition of SOL bacteria by multivariate statistical methods. SOL bacteria did not occur in acidic lakes (pH < 6), and their abundance was negatively related to high trophy and pH. The subcluster-specific variation in the compositions of SOL communities could be related to the pH, electrical conductivity, altitude, and trophic status of ecosystems. All three known SOL subclusters differed in respect to their tolerated ranges of pH and conductivity. Complete niche separation was observed between the vicarious subclusters GKS2-217 and LD2; the former occurred in soft-water lakes, whereas the latter was found in a broad range of hard-water habitats. The third subgroup (HAL) showed a wide environmental tolerance and was usually found sympatrically with the LD2 or GKS2-217 subcluster. Ecological differentiation of SOL bacteria at the subcluster level was most probably driven by differential adaptation to water chemistry. The distribution of the two vicarious taxa seems to be predominantly controlled by the geological backgrounds of the catchment areas of the habitats.

Treatment impacts on temporal microbial community dynamics during phytostabilization of acid-generating mine tailings in semiarid regions.

PubMed

Valentín-Vargas, Alexis; Neilson, Julia W; Root, Robert A; Chorover, Jon; Maier, Raina M

2018-03-15

Direct revegetation, or phytostabilization, is a containment strategy for contaminant metals associated with mine tailings in semiarid regions. The weathering of sulfide ore-derived tailings frequently drives acidification that inhibits plant establishment resulting in materials prone to wind and water dispersal. The specific objective of this study was to associate pyritic mine waste acidification, characterized through pore-water chemistry analysis, with dynamic changes in microbial community diversity and phylogenetic composition, and to evaluate the influence of different treatment strategies on the control of acidification dynamics. Samples were collected from a highly instrumented one-year mesocosm study that included the following treatments: 1) unamended tailings control; 2) tailings amended with 15% compost; and 3) the 15% compost-amended tailings planted with Atriplex lentiformis. Tailings samples were collected at 0, 3, 6 and 12months and pore water chemistry was monitored as an indicator of acidification and weathering processes. Results confirmed that the acidification process for pyritic mine tailings is associated with a temporal progression of bacterial and archaeal phylotypes from pH sensitive Thiobacillus and Thiomonas to communities dominated by Leptospirillum and Ferroplasma. Pore-water chemistry indicated that weathering rates were highest when Leptospirillum was most abundant. The planted treatment was most successful in disrupting the successional evolution of the Fe/S-oxidizing community. Plant establishment stimulated growth of plant-growth-promoting heterotrophic phylotypes and controlled the proliferation of lithoautotrophic Fe/S-oxidizers. The results suggest the potential for eco-engineering a microbial inoculum to stimulate plant establishment and inhibit proliferation of the most efficient Fe/S-oxidizing phylotypes. Copyright © 2017 Elsevier B.V. All rights reserved.

Joint neutron crystallographic and NMR solution studies of Tyr residue ionization and hydrogen bonding: Implications for enzyme-mediated proton transfer

DOE PAGES

Michalczyk, Ryszard; Unkefer, Clifford J.; Bacik, John -Paul; ...

2015-05-05

Proton transfer is a fundamental mechanism at the core of many enzyme-catalyzed reactions. It is also exquisitely sensitive to a number of factors, including pH, electrostatics, proper active-site geometry, and chemistry. Carbonic anhydrase has evolved a fast and efficient way to conduct protons through a combination of hydrophilic amino acid side chains that coordinate a highly ordered H-bonded water network. This study uses a powerful approach, combining NMR solution studies with neutron protein crystallography, to determine the effect of pH and divalent cations on key residues involved in proton transfer in human carbonic anhydrase. Lastly, the results have broad implicationsmore » for our understanding of proton transfer and how subtle changes in ionization and H-bonding interactions can modulate enzyme catalysis.« less

Use of the Biotic Ligand Model to predict metal toxicity to aquatic biota in areas of differing geology

USGS Publications Warehouse

Smith, Kathleen S.

2005-01-01

This work evaluates the use of the biotic ligand model (BLM), an aquatic toxicity model, to predict toxic effects of metals on aquatic biota in areas underlain by different rock types. The chemical composition of water, soil, and sediment is largely derived from the composition of the underlying rock. Geologic source materials control key attributes of water chemistry that affect metal toxicity to aquatic biota, including: 1) potentially toxic elements, 2) alkalinity, 3) total dissolved solids, and 4) soluble major elements, such as Ca and Mg, which contribute to water hardness. Miller (2002) compiled chemical data for water samples collected in watersheds underlain by ten different rock types, and in a mineralized area in western Colorado. He found that each rock type has a unique range of water chemistry. In this study, the ten rock types were grouped into two general categories, igneous and sedimentary. Water collected in watersheds underlain by sedimentary rock has higher mean pH, alkalinity, and calcium concentrations than water collected in watersheds underlain by igneous rock. Water collected in the mineralized area had elevated concentrations of calcium and sulfate in addition to other chemical constituents. Miller's water-chemistry data were used in the BLM (computer program) to determine copper and zinc toxicity to Daphnia magna. Modeling results show that waters from watersheds underlain by different rock types have characteristic ranges of predicted LC 50 values (a measurement of aquatic toxicity) for copper and zinc, with watersheds underlain by igneous rock having lower predicted LC 50 values than watersheds underlain by sedimentary rock. Lower predicted LC 50 values suggest that aquatic biota in watersheds underlain by igneous rock may be more vulnerable to copper and zinc inputs than aquatic biota in watersheds underlain by sedimentary rock. For both copper and zinc, there is a trend of increasing predicted LC 50 values with increasing dissolved organic carbon (DOC) concentrations. Predicted copper LC 50 values are extremely sensitive to DOC concentrations, whereas alkalinity appears to have an influence on zinc toxicity at alkalinities in excess of about 100 mg/L CaCO 3 . These findings show promise for coupling the BLM (computer program) with measured water-chemistry data to predict metal toxicity to aquatic biota in different geologic settings and under different scenarios. This approach may ultimately be a useful tool for mine-site planning, mitigation and remediation strategies, and ecological risk assessment.

A programmable soft chemo-mechanical actuator exploiting a catalyzed photochemical water-oxidation reaction.

PubMed

Yuan, P; McCracken, J M; Gross, D E; Braun, P V; Moore, J S; Nuzzo, R G

2017-10-18

We describe a composite hydrogel containing an embedding coupled chemistry for light-sensitized catalytic reactions that enables chemo-mechanical actuation of poly(acrylic acid)-based gels. In these materials, a photosensitizer and catalyst-ruthenium trisbipyridine and iridium dioxide nanoparticles, respectively-are incorporated into the hydrogel where together, with visible light irradiation, they undergo a catalytic water-oxidation reaction that lowers the pH and induces a dissipative/chemically-driven strain change in the gel. To demonstrate the capacity for 3D chemo-mechanical actuation, a layer of non-pH responsive poly(2-hydroxyethyl methacrylate) is added to the photo-active composite gel to create a model bimorph actuator. Triggering and terminating the water-oxidation reaction leads to a programmatic expansion and contraction of the active layer, which induces different modes of biomimetic curling motions in the bimorph actuator in light and dark environments. The efficiency of this system is fundamentally limited by the system-level design, which provides no capacity to sustain a local pH gradient against diffusive mixing. Even so, if the initial pH of the background solution is reestablished either actively or passively between each reaction cycle, it is possible to realize multiple cycles of reversible actuation. We describe a thermodynamic analysis of this system which identifies specific features mediating efficiency losses and conceptual requirements for mesoscopic design rules for optimization of this system and for advancing soft actuation systems in general.

Microelectrode characterization of coral daytime interior pH and carbonate chemistry.

PubMed

Cai, Wei-Jun; Ma, Yuening; Hopkinson, Brian M; Grottoli, Andréa G; Warner, Mark E; Ding, Qian; Hu, Xinping; Yuan, Xiangchen; Schoepf, Verena; Xu, Hui; Han, Chenhua; Melman, Todd F; Hoadley, Kenneth D; Pettay, D Tye; Matsui, Yohei; Baumann, Justin H; Levas, Stephen; Ying, Ye; Wang, Yongchen

2016-04-04

Reliably predicting how coral calcification may respond to ocean acidification and warming depends on our understanding of coral calcification mechanisms. However, the concentration and speciation of dissolved inorganic carbon (DIC) inside corals remain unclear, as only pH has been measured while a necessary second parameter to constrain carbonate chemistry has been missing. Here we report the first carbonate ion concentration ([CO3(2-)]) measurements together with pH inside corals during the light period. We observe sharp increases in [CO3(2-)] and pH from the gastric cavity to the calcifying fluid, confirming the existence of a proton (H(+)) pumping mechanism. We also show that corals can achieve a high aragonite saturation state (Ωarag) in the calcifying fluid by elevating pH while at the same time keeping [DIC] low. Such a mechanism may require less H(+)-pumping and energy for upregulating pH compared with the high [DIC] scenario and thus may allow corals to be more resistant to climate change related stressors.

Alternative Life Styles for Extraterrestrial Chemists

NASA Astrophysics Data System (ADS)

Benner, S.

2002-12-01

Life is no more (and no less) than a special type of organic chemistry, one that combines a frequently encountered property of organic molecules (the ability to undergo spontaneous chemical transformation) with an uncommon property (the ability to direct the synthesis of self-copies) in a way that allows new molecular features arising through spontaneous transformation to themselves be copied. Any chemical system having this combination will undergo natural selection, evolving in structure to replicate faster through more efficient use of molecular resources and energy. Axiomatically, life cannot exist in an environment at thermodynamic equilibrium. If it were, by the second law of thermodynamics, no net chemical transformation would be possible. Beyond this constraint, it is difficult to define environmental conditions or chemical structures necessary for life. Water is certainly not required for a chemical system to copy itself; in the laboratory, non-aqueous environments appear to support this behavior better. Chemical transformations that might support energy and chemical metabolisms are known in environments as acidic as the aerosols in the atmosphere of Venus, or as basic as the atmosphere of Jupiter. Laboratory experiments with analogs of the nucleic acids, proteins, sugars, and lipids show that the particular molecular structures found in terrean life need not be universal, even those life in water near neutral pH. Indeed, while both water and biological macromolecules are commonly regarded as essential for terrean-like life, water destroys terrean biological macromolecules. These chemical realities create a complex decision environment as NASA attempts to design instrumentation carried by missions, select places in the solar system to send them, and chose laboratory studies on Earth to provide their scientific support. This talk will review a hierarchy of chemical possibilities and constraints that start with the chemistry of terrean life, and takes steps towards weird life. We shall consider alternative amino acid building blocks for proteins, alternative building blocks for nucleic acids, alternative structural features of genetic and catalytic molecules, alternative nucleophile-electrophile pairs to support metabolism, non-polar reaction modes that might support metabolism, non-terrean pH (< 0, > 14) and solvent environments for life, extreme temperature ranges (especially sub zero Celsius) low temperature ranges, alternative thermodynamic design for metabolic pathways, alternative dimensionalities of genetic and catalytic molecules, and approaches for isolating life other than conventional cell structures. Each of these discussions will combine experimental and theoretical information. The first involves organic chemical synthesis that creates new forms of chemical matter to ask "What if?" and "Why not?" questions. The second draws on a century of literature in physical organic chemistry to formulate general constraints on the structure and transformation of organic matter to provide constraints on possible Darwinian chemistries in the galaxy.

Spring runoff water-chemistry data from the Standard Mine and Elk Creek, Gunnison County, Colorado, 2010

USGS Publications Warehouse

Manning, Andrew H.; Verplanck, Philip L.; Mast, M. Alisa; Marsik, Joseph; McCleskey, R. Blaine

2011-01-01

Water samples were collected approximately every two weeks during the spring of 2010 from the Level 1 portal of the Standard Mine and from two locations on Elk Creek. The objective of the sampling was to: (1) better define the expected range and timing of variations in pH and metal concentrations in Level 1 discharge and Elk Creek during spring runoff; and (2) further evaluate possible mechanisms controlling water quality during spring runoff. Samples were analyzed for major ions, selected trace elements, and stable isotopes of oxygen and hydrogen (oxygen-18 and deuterium). The Level 1 portal sample and one of the Elk Creek samples (EC-CELK1) were collected from the same locations as samples taken in the spring of 2007, allowing comparison between the two different years. Available meteorological and hydrologic data suggest that 2010 was an average water year and 2007 was below average. Field pH and dissolved metal concentrations in Level 1 discharge had the following ranges: pH, 2.90 to 6.23; zinc, 11.2 to 26.5 mg/L; cadmium, 0.084 to 0.158 mg/L; manganese, 3.23 to 10.2 mg/L; lead, 0.0794 to 1.71 mg/L; and copper, 0.0674 to 1.14 mg/L. These ranges were generally similar to those observed in 2007. Metal concentrations near the mouth of Elk Creek (EC-CELK1) were substantially lower than in 2007. Possible explanations include remedial efforts at the Standard Mine site implemented after 2007 and greater dilution due to higher Elk Creek flows in 2010. Temporal patterns in pH and metal concentrations in Level 1 discharge were similar to those observed in 2007, with pH, zinc, cadmium, and manganese concentrations generally decreasing, and lead and copper generally increasing during the snowmelt runoff period. Zinc and cadmium concentrations were inversely correlated with flow and thus apparently dilution-controlled. Lead and copper concentrations were inversely correlated with pH and thus apparently pH-controlled. Zinc, cadmium, and manganese concentrations near the mouth of Elk Creek did not display the pronounced increase observed during high flow in 2007, again perhaps due to remedial activities at the mine site or greater dilution in 2010. Zinc and cadmium loads near the mouth of Elk Creek were generally greater than those at the Level 1 portal for the six sample days in 2010. Whereas metal loads in September 2007 suggested that Level 1 portal discharge was the primary source of metals to the creek, metal loads computed for this study suggest that this may not have been the case in the spring of 2010. d18O values are well correlated with flow, becoming lighter (more negative) during snowmelt in both Level 1 discharge and Elk Creek. Seasonal variations in the chemistry of Level 1 discharge, along with portal flow tracking very closely with creek flow, are consistent with geochemical and environmental tracer data from 2007 that indicate short residence times (<1 year) for groundwater discharging from the Standard Mine.

Open-Source Low-Cost Wireless Potentiometric Instrument for pH Determination Experiments

ERIC Educational Resources Information Center

Jin, Hao; Qin, Yiheng; Pan, Si; Alam, Arif U.; Dong, Shurong; Ghosh, Raja; Deen, M. Jamal

2018-01-01

pH determination is an essential experiment in many chemistry laboratories. It requires a potentiometric instrument with extremely low input bias current to accurately measure the voltage between a pH sensing electrode and a reference electrode. In this technology report, we propose an open-source potentiometric instrument for pH determination…

The response of soil and stream chemistry to decreases in acid deposition in the Catskill Mountains, New York, USA

USGS Publications Warehouse

McHale, Michael; Burns, Douglas A.; Siemion, Jason; Antidormi, Michael

2017-01-01

The Catskill Mountains have been adversely impacted by decades of acid deposition, however, since the early 1990s, levels have decreased sharply as a result of decreases in emissions of sulfur dioxide and nitrogen oxides. This study examines trends in acid deposition, stream-water chemistry, and soil chemistry in the southeastern Catskill Mountains. We measured significant reductions in acid deposition and improvement in stream-water quality in 5 streams included in this study from 1992 to 2014. The largest, most significant trends were for sulfate (SO42−) concentrations (mean trend of −2.5 μeq L−1 yr−1); hydrogen ion (H+) and inorganic monomeric aluminum (Alim) also decreased significantly (mean trends of −0.3 μeq L−1 yr−1 for H+ and −0.1 μeq L−1 yr−1 for Alim for the 3 most acidic sites). Acid neutralizing capacity (ANC) increased by a mean of 0.65 μeq L−1 yr−1 for all 5 sites, which was 4 fold less than the decrease in SO42−concentrations. These upward trends in ANC were limited by coincident decreases in base cations (−1.3 μeq L−1 yr−1 for calcium + magnesium). No significant trends were detected in stream-water nitrate (NO3−) concentrations despite significant decreasing trends in NO3− wet deposition. We measured no recovery in soil chemistry which we attributed to an initially low soil buffering capacity that has been further depleted by decades of acid deposition. Tightly coupled decreasing trends in stream-water silicon (Si) (−0.2 μeq L−1 yr−1) and base cations suggest a decrease in the soil mineral weathering rate. We hypothesize that a decrease in the ionic strength of soil water and shallow groundwater may be the principal driver of this apparent decrease in the weathering rate. A decreasing weathering rate would help to explain the slow recovery of stream pH and ANC as well as that of soil base cations.

Is coccolithophore distribution in the Mediterranean Sea related to seawater carbonate chemistry?

NASA Astrophysics Data System (ADS)

Oviedo, A. M.; Ziveri, P.; Álvarez, M.; Tanhua, T.

2014-02-01

The Mediterranean Sea is considered a "hot-spot" for climate change, being characterized by oligotrophic to ultra-oligotrophic waters and rapidly changing carbonate chemistry. Coccolithophores are considered a dominant phytoplankton group in these waters. As a marine calcifying organism they are expected to respond to the ongoing changes in seawater CO2 systems parameters. However, very few studies have covered the entire Mediterranean physiochemical gradients from the Strait of Gibraltar to the Eastern Mediterranean Levantine Basin. We provide here an updated state of knowledge of the coccolithophore distribution in the Mediterranean Sea and relate this to a broad set of in situ measured environmental variables. Samples were taken during the Meteor (M84/3) oceanographic cruise in April 2011, between 0-100 m water depth from 28 stations. Total diatom, dinoflagellate and silicoflagellate cell concentrations are also presented. Our results highlight the importance of seawater carbonate chemistry, especially CO32-, in unraveling the distribution of heterococcolithophores, the most abundant coccolithophore life phase. Holo- and hetero-coccolithophores respond differently to environmental factors. For instance, changes in heterococcolithophore assemblages were best linked to the combination of [CO32-], pH, and salinity (ρ = 0.57) although salinity might be not functionally related to coccolithophore assemblage distribution. Holococcolithophores, on the other hand, were preferentially distributed and showed higher species diversity in oligotrophic areas (Best fit, ρ = 0.32 for nutrients), thriving in nutrient depleted waters. Clustering of heterococcolithophores revealed three groups of species sharing more than 65% similarities. These clusters could be assigned to the eastern and western basins, and deeper layers (below 50 m), respectively. In addition, the species Gephyrocapsa oceanica, G. muellerae and Emiliania huxleyi morphotype B/C are spatially distributed together and trace the influx of Atlantic waters into the Mediterranean Sea. The results of the present work emphasize the importance of considering holo- and hetero-coccolithophores separately when analyzing changes in species assemblages and diversity. Our findings clearly show that coccolithophores are a dominant phytoplankton group in the entire Mediterranean Sea; they have life stages that are expected to respond differently to the variability in seawater carbonate chemistry and nutrient concentrations.

The role of water chemistry in the distribution of Austropotamobius pallipes (Crustacea Decapoda Astacidae) in Piedmont (Italy).

PubMed

Favaro, Livio; Tirelli, Tina; Pessani, Daniela

2010-01-01

Over the last decades, the populations of Austropotamobius pallipes have decreased markedly all over Europe. If we evaluate the ecological factors that determine its presence, we will have information that could guide conservation decisions. This study aims to investigate the chemical-physical demands of A. pallipes in NW Italy. To this end, we investigated 98 sites. We performed Principal Component Analysis using chemical-physical parameters, collected in both presence and absence sites. We then used principal components with eigenvalue > 1 to run Discriminant Function Analysis and Logistic Regression. The statistics on the concentration of Ca(2+), water hardness, pH and BOD(5) were significantly different in the presence and in the absence sites. pH and BOD(5) played the most important role in separating the presence from the absence locations. These findings are further evidence that we should reduce dissolved organic matter and fine particles in order to contribute to species management and conservation. Copyright 2009 Académie des sciences. Published by Elsevier SAS. All rights reserved.

Suspension chemistry and electrophoretic deposition of zirconia electrolyte on conducting and non-conducting substrates

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

Das, Debasish; Basu, Rajendra N., E-mail: rnbasu@cgcri.res.in

2013-09-01

Graphical abstract: - Highlights: • Stable suspension of yttria stabilized zirconia (YSZ) obtained in isopropanol medium. • Suspension chemistry and process parameters for electrophoretic deposition optimized. • Deposited film quality changed with iodine and water (dispersants) concentration. • Dense YSZ film (∼5 μm) fabricated onto non-conducting porous NiO-YSZ anode substrate. - Abstract: Suspensions of 8 mol% yttria stabilized zirconia (YSZ) particulates in isopropanol medium are prepared using acetylacetone, iodine and water as dispersants. The effect of dispersants concentration on suspension stability, particle size distribution, electrical conductivity and pH of the suspensions are studied in detail to optimize the suspension chemistry.more » Electrophoretic deposition (EPD) has been conducted to produce thin and dense YSZ electrolyte films. Deposition kinetics have been studied in depth and good quality films on conducting substrate are obtained at an applied voltage of 15 V for 3 min. YSZ films are also fabricated on non-conducting NiO-YSZ anode substrate using a steel plate on the reverse side of the substrate. Upon co-firing at 1400 °C for 6 h a dense YSZ film of thickness ∼5 μm is obtained. Such a half cell (anode + electrolyte) can be used to fabricate a solid oxide fuel cell on applying a suitable cathode layer.« less

Reactive transport modelling of groundwater chemistry in a chalk aquifer at the watershed scale.

PubMed

Mangeret, A; De Windt, L; Crançon, P

2012-09-01

This study investigates thermodynamics and kinetics of water-rock interactions in a carbonate aquifer at the watershed scale. A reactive transport model is applied to the unconfined chalk aquifer of the Champagne Mounts (France), by considering both the chalk matrix and the interconnected fracture network. Major element concentrations and main chemical parameters calculated in groundwater and their evolution along flow lines are in fair agreement with field data. A relative homogeneity of the aquifer baseline chemistry is rapidly reached in terms of pH, alkalinity and Ca concentration since calcite equilibrium is achieved over the first metres of the vadose zone. However, incongruent chalk dissolution slowly releases Ba, Mg and Sr in groundwater. Introducing dilution effect by rainwater infiltration and a local occurrence of dolomite improves the agreement between modelling and field data. The dissolution of illite and opal-CT, controlling K and SiO(2) concentrations in the model, can be approximately tackled by classical kinetic rate laws, but not the incongruent chalk dissolution. An apparent kinetic rate has therefore been fitted on field data by inverse modelling: 1.5×10(-5) mol(chalk)L (-1) water year (-1). Sensitivity analysis indicates that the CO(2) partial pressure of the unsaturated zone is a critical parameter for modelling the baseline chemistry over the whole chalk aquifer. Copyright © 2012 Elsevier B.V. All rights reserved.

Predicted pH at the domestic and public supply drinking water depths, Central Valley, California

USGS Publications Warehouse

Rosecrans, Celia Z.; Nolan, Bernard T.; Gronberg, Jo Ann M.

2017-03-08

This scientific investigations map is a product of the U.S. Geological Survey (USGS) National Water-Quality Assessment (NAWQA) project modeling and mapping team. The prediction grids depicted in this map are of continuous pH and are intended to provide an understanding of groundwater-quality conditions at the domestic and public supply drinking water zones in the groundwater of the Central Valley of California. The chemical quality of groundwater and the fate of many contaminants is often influenced by pH in all aquifers. These grids are of interest to water-resource managers, water-quality researchers, and groundwater modelers concerned with the occurrence of natural and anthropogenic contaminants related to pH. In this work, the median well depth categorized as domestic supply was 30 meters below land surface, and the median well depth categorized as public supply is 100 meters below land surface. Prediction grids were created using prediction modeling methods, specifically boosted regression trees (BRT) with a Gaussian error distribution within a statistical learning framework within the computing framework of R (http://www.r-project.org/). The statistical learning framework seeks to maximize the predictive performance of machine learning methods through model tuning by cross validation. The response variable was measured pH from 1,337 wells and was compiled from two sources: USGS National Water Information System (NWIS) database (all data are publicly available from the USGS: http://waterdata.usgs.gov/ca/nwis/nwis) and the California State Water Resources Control Board Division of Drinking Water (SWRCB-DDW) database (water quality data are publicly available from the SWRCB: http://www.waterboards.ca.gov/gama/geotracker_gama.shtml). Only wells with measured pH and well depth data were selected, and for wells with multiple records, only the most recent sample in the period 1993–2014 was used. A total of 1,003 wells (training dataset) were used to train the BRT model, and 334 wells (hold-out dataset) were used to validate the prediction model. The training r-squared was 0.70, and the root-mean-square error (RMSE) in standard pH units was 0.26. The hold-out r-squared was 0.43, and RMSE in standard pH units was 0.37. Predictor variables consisting of more than 60 variables from 7 sources were assembled to develop a model that incorporates regional-scale soil properties, soil chemistry, land use, aquifer textures, and aquifer hydrology. Previously developed Central Valley model outputs of textures (Central Valley Textural Model, CVTM; Faunt and others, 2010) and MODFLOW-simulated vertical water fluxes and predicted depth to water table (Central Valley Hydrologic Model, CVHM; Faunt, 2009) were used to represent aquifer textures and groundwater hydraulics, respectively. In this work, wells were attributed to predictor variable values in ArcGIS using a 500-meter buffer.Faunt, C.C., ed., 2009, Groundwater availability in the Central Valley aquifer, California: U.S. Geological Survey Professional Paper 1776, 225 p., accessed at https://pubs.usgs.gov/pp/1766/.Faunt, C.C., Belitz, K., and Hanson, R.T., 2010, Development of a three-dimensional model of sedimentary texture in valley-fill deposits of Central Valley, California, USA: Hydrogeology Journal, v. 18, no. 3, p. 625–649, https://doi.org/10.1007/s10040-009-0539-7.

Geochemistry of leachates from the El Fraile sulfide tailings piles in Taxco, Guerrero, southern Mexico.

PubMed

Talavera Mendoza, Oscar; Armienta Hernández, Ma Aurora; Abundis, José García; Mundo, Nestor Flores

2006-06-01

Leachates from the El Fraile tailings impoundment (Taxco, Mexico) were monitored every 2 months from October 2001 to August 2002 to assess the geochemical characteristics. These leachates are of interest because they are sometimes used as alternative sources of domestic water. Alternatively, they drain into the Cacalotenango creek and may represent a major source of metal contamination of surface water and sediments. Most El Fraile leachates show characteristics of Ca-SO(4), (Ca+Mg)-SO(4), Mg-SO(4 )and Ca-(SO(4)+HCO(3)) water types and are near-neutral (pH=6.3-7.7). Some acid leachates are generated by the interaction of meteoric water with tailings during rainfall events (pH=2.4-2.5). These contain variable levels of SO(4) (2-) (280-29,500 mg l(-1)) and As (<0.01-12.0 mg l(-1)) as well as Fe (0.025-2,352 mg l(-1)), Mn (0.1-732 mg l(-1)), Zn (<0.025-1465 mg l(-1)) and Pb (<0.01-0.351 mg l(-1)). Most samples show the highest metal enrichment during the dry seasons. Leachates used as domestic water typically exceed the Mexican Drinking Water Guidelines for sulfate, hardness, Fe, Mn, Pb and As, while acidic leachates exceed the Mexican Guidelines for Industrial Discharge Waters for pH, Cu, Cd and As. Speciation shows that in near-neutral solutions, metals exist mainly as free ions, sulfates and bicarbonates, while in acidic leachates they are present as sulfates and free ions. Arsenic appears as As((V)) in all samples. Thermodynamic and mineralogical evidence indicates that precipitation of Fe oxides and oxyhydroxides, clay minerals and jarosite as well as sorption by these minerals are the main processes controlling leachate chemistry. These processes occur mainly after neutralization by interaction with bedrock and equilibration with atmospheric oxygen.

Effects of calcium, magnesium, and sodium on alleviating cadmium toxicity to Hyalella azteca

USGS Publications Warehouse

Jackson, B.P.; Lasier, P.J.; Miller, W.P.; Winger, P.V.

2000-01-01

Toxicity of trace metal ions to aquatic organisms, arising through either anthropogenic inputs or acidification of surface waters, continues to be both a regulatory and environmental problem. It is generally accepted that the free metal ion is the major toxic species (Florence et a1.,1992) and that inorganic or organic complexation renders the metal ion non-bioavailable (Meador, 1991, Galvez and Wood, 1997). However, water chemistry parameters such as alkalinity, hardness, dissolved organic carbon and pH influence metal ion toxicity either directly by lowering free metal ion concentration or indirectly through synergistic or antagonistic effects. Alkalinity and salinity can affect the speciation of metal ions by increasing ion-pair formation, thus decreasing free metal ion concentration. For example, Cu was found to be less toxic to rainbow trout in waters of high alkalinity (Miller and Mackay, 1980), due to formation of CuCO3 ion pair, and corresponding reduction in free Cu2+ concentration. The influence of salinity on the toxicity of cadmium to various organisms has been demonstrated in a number of studies (Bervoets et al., 1995, Hall et al., 1995, Lin and Dunson, 1993, Blust et al., 1992). In all these studies the apparent toxicity of cadmium was lowered as salinity was increased due to increased formation of CdC1+ and CDCl2 aqueous complexes that are non-toxic or of much lower toxicity than the free Cd2+ ion. Changes in pH exert both a biological and chemical effect on metal ion toxicity (Campbell and Stokes, 1985). Low pH favors greater metal ion solubility, and, in the absence of complexing ions, reduced speciation of the metal ion, which tends to increase toxicity compared to higher pH. However, Iow pH also enhances competition between H+ and metal ion for cell surface binding sites, which tends to decrease metal ion toxicity.

Using Chemistry and Color To Analyze Household Products: A 10-12 Hour Laboratory Project at the General Chemistry Level

NASA Astrophysics Data System (ADS)

Bosma, Wayne B.

1998-02-01

A general chemistry experiment is described in which the students use UV/Visible spectrometry as an analytical tool, for both compound identification and pH measurement. In the first portion of the experiment, the students compare spectra to determine which FD and C dyes are contained in household products. They furthermore use chromatography to separate the dyes in grape Kool-Aid, and analyze the products with the spectrometer. In the second portion of the experiment, the students use Beer's Law to determine the pH of solutions containing an acid/base indicator. The experiments are visually stimulating and provide a solid introduction to spectroscopy and perceived color.

Using streamflow and hydrochemical tracers to conceptualise hydrological function of underground channel system in a karst catchment of southwest China

NASA Astrophysics Data System (ADS)

Zhang, Zhicai; Chen, Xi; Wang, Jinli

2016-04-01

Karst hydrodynamic behaviour is complex because of special karst geology and geomorphology. The permeable multi-media consisting of soil, epikarst fractures and conduits has a key influence on karst hydrological processes. Spatial heterogeneity is high due to special landforms of vertical shafts, caves and sinkholes, which leads to a high dynamic variability of hydrological processes in space and time, and frequent exchange of surface water and groundwater. Underground water in different reach were sampled over the 1996-2001 in a karst catchment of Houzhai, with 81km2, located in Guizhou province of southwest China. Samples were analysed for water temperature, pH, conductivity and four solute concentrations. The monitoring sought to assess the combined utility of flow discharge and natural geochemical tracers in upscaling flow structure understanding in karst area. Based on previous researches and field investigation, the catchment characteristics were explored with the use of a GIS. Both flow discharge and solute concentrations exhibited clear seasonal patterns at every groundwater sampling sites. The variations of flow and chemistry are more dramatic in upstream site with less soil cover and more sinkholes development, which affect the hydrological pathways significantly. There was clear evidence that the differences in geology and soil were the main controls on hydrology and flow chemistry, which was spatially variable in different sites of underground channel. Conceptual flow structures in main hydrological response units for different area in the catchment were developed according to the variation of discharge and flow chemistry.

A modelling assessment of acidification and recovery of European surface waters

NASA Astrophysics Data System (ADS)

Jenkins, A.; Camarero, L.; Cosby, B. J.; Ferrier, R. C.; Forsius, M.; Helliwell, R. C.; Kopácek, J.; Majer, V.; Moldan, F.; Posch, M.; Rogora, M.; Schöpp, W.; Wright, R. F.

The increase in emission of sulphur oxides and nitrogen (both oxidised and reduced forms) since the mid-1800s caused a severe decline in pH and ANC in acid-sensitive surface waters across Europe. Since c.1980, these emissions have declined and trends towards recovery from acidification have been widely observed in time-series of water chemistry data. In this paper, the MAGIC model was applied to 10 regions (the SMART model to one) in Europe to address the question of future recovery under the most recently agreed emission protocols (the 1999 Gothenburg Protocol). The models were calibrated using best available data and driven using S and N deposition sequences for Europe derived from EMEP data. The wide extent and the severity of water acidification in 1980 in many regions were illustrated by model simulations which showed significant deterioration in ANC away from the pre-acidification conditions. The simulations also captured the recovery to 2000 in response to the existing emission reductions. Predictions to 2016 indicated further significant recovery towards pre-acidification chemistry in all regions except Central England (S Pennines), S Alps, S Norway and S Sweden. In these areas it is clear that further emission reductions will be required and that the recovery of surface waters will take several decades as soils slowly replenish their depleted base cation pools. Chemical recovery may not, however, ensure biological recovery and further reductions may also be required to enable these waters to achieve the "good ecological status" as required by the EU Water Framework Directive.

Microscopic Views of Martian Soils and Evidence for Incipient Diagenesis

NASA Technical Reports Server (NTRS)

Goetz, W.; Madsen, M. B.; Bridges, N.; Clark, B.; Edgett, K. S.; Fisk, M.; Grotzinger, J. P.; Hviid, S. F.; Meslin, P.-Y.; Ming, D. W.;

The influence of redox chemistry and pH on chemically active forms of arsenic in sewage sludge-amended soil

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

Carbonell-Barrachina, A.; Jugsujinda, A.; DeLaune, R.D.

1999-07-01

Chemical fractionation procedures were used to quantify the effect of the sediment redox and pH conditions on the adsorption and solubility of arsenic (As) in municipal sewage sludge and sewage sludge-amended soil. Sludge and sludge-amended soil were incubated in microcosms in which Eh-pH conditions were controlled. Samples were sequentially extracted to determine As in various chemical forms (water soluble, exchangeable, bound to carbonates, bound to iron (Fe) and manganese (Mn) oxides, bound to insoluble organics and sulfides) and the chemically inactive fraction (mineral residues). In both sewage sludge and sludge-amended soil, As chemistry was governed by large molecular humic mattermore » and sulfides and Fe and Mn-oxides. Solubility of As remained low and constant under both aerobic and anaerobic conditions in sludge-amended soil. After dissolution of Fe and Mn-oxides, As{sup 5+} was released into sludge solution, reduced to As{sup 3+} and likely precipitated as sulfide. Therefore, an organic amendment rich in sulfur compounds, such as sewage sludge, would drastically reduce the potential risks derived from As pollution under highly anoxic conditions by precipitation of this toxic metalloid as insoluble and immobile sulfides.« less

Effect of wood ash application on soil solution chemistry of tropical acid soils: incubation study.

PubMed

Nkana, J C Voundi; Demeyer, A; Verloo, M G

2002-12-01

The objective of this study was to determine the effect of wood ash application on soil solution composition of three tropical acid soils. Calcium carbonate was used as a reference amendment. Amended soils and control were incubated for 60 days. To assess soluble nutrients, saturation extracts were analysed at 15 days intervals. Wood ash application affects the soil solution chemistry in two ways, as a liming agent and as a supplier of nutrients. As a liming agent, wood ash application induced increases in soil solution pH, Ca, Mg, inorganic C, SO4 and DOC. As a supplier of elements, the increase in the soil solution pH was partly due to ligand exchange between wood ash SO4 and OH- ions. Large increases in concentrations of inorganic C, SO4, Ca and Mg with wood ash relative to lime and especially increases in K reflected the supply of these elements by wood ash. Wood ash application could represent increased availability of nutrients for the plant. However, large concentrations of basic cations, SO4 and NO3 obtained with higher application rates could be a concern because of potential solute transport to surface waters and groundwater. Wood ash must be applied at reasonable rates to avoid any risk for the environment.

Inorganic carbon dynamics in the upwelling system off the Oregon coast and implications for commercial shellfish hatcheries

NASA Astrophysics Data System (ADS)

Vance, J. M.; Hales, B. R.

2010-12-01

The increasing absorption of anthropogenic CO2 by the global ocean and concomitant decrease in pH will alter seawater carbonate chemistry in ways that may negatively impact calcifying organisms. In particular, the change in saturation state (Ω) of calcium carbonate minerals calcite and aragonite may be energetically unfavorable for shell formation while favoring shell dissolution. Eastern boundary upwelling systems may provide insights into how ecosystems respond to future conditions of ocean acidification when deep water with high dissolved inorganic carbon (DIC), low pH and low Ω is forced toward the surface. Mortality in commercial seed stock and reduced wild set of the oyster Crassostrea gigas in the northeast Pacific during 2005-2009 reinforced the need for understanding biological responses to acidified ocean water. In response, a long-term strategy to understand local carbonate chemistry dynamics, seasonal perturbations and the effects on development of calcifying bivalves was developed. At present, a time-series of pCO2 measurements was implemented in April 2010 in Netarts Bay, Oregon at Whiskey Creek Shellfish Hatchery (WCH). The intake sits at a depth of 0.5-8ft and water is pumped in at 100gpm. A line taken off the intake is run continuously through a thermosalinograph at approximately 1.5gpm into a showerhead style equilibrator in which the headspace is recirculated by aerating the water for enhanced gas exchange. CO2 in equilibrated air is analyzed by NDIR. Additionally two discrete samples of intake seawater were taken across tidal cycles weekly and analyzed for total CO2 (TCO2) according to the methods of Hales et al. (2004) and pCO2 for quality control. The pCO2 in the bay exhibits a diurnal cycle representative of daytime photosynthesis and nighttime respiration. However, the phasing and profiles of these cycles are dominated by tidal mixing and are affected by the introduction of high pCO2 water during upwelling events. Diurnal pCO2 during periods of low wind stress ranges from 100-700µatm. When strong equatorward winds induce upwelling, pCO2 levels exhibit a higher daily range of 300-2000µatm. The saturation state was calculated from the pCO2/TCO2 measurements of the discrete samples. The Ω for calcite and aragonite ranged from 2.07 and 1.15 to 8.58 and 4.69 respectively from April through August. Increased pCO2 and decreased pH have been shown to negatively impact larval development in C. gigas (Kurihara, 2007). Periods of elevated pCO2 in May and June 2010 correlated with commercial losses at WCH. The use of precise pCO2 measurements in real time has proven to be a valuable tool for use in aquaculture. As a commercial practice WCH has elected to only use source water that is below empirical pCO2 thresholds for spawning and culturing larvae. This has resulted in continued production and cost saving in an industry crucial to coast economies. A continuous TCO2/pCO2 monitoring system will be integrated into this long time-series to constrain inorganic carbon providing insight into carbonate chemistry dynamics in Netarts Bay, effects of ocean acidification on bivalve development and possible water treatment approaches for commercial aquaculture.

Europa's Compositional Evolution and Ocean Salinity

NASA Astrophysics Data System (ADS)

Vance, S.; Glein, C.; Bouquet, A.; Cammarano, F.; McKinnon, W. B.

2017-12-01

Europa's ocean depth and composition have likely evolved through time, in step with the temperature of its mantle, and in concert with the loss of water and hydrogen to space and accretion of water and other chemical species from comets, dust, and Io's volcanism. A key aspect to understanding the consequences of these processes is combining internal structure models with detailed calculations of ocean composition, which to date has not been done. This owes in part to the unavailability of suitable thermodynamic databases for aqueous chemistry above 0.5 GPa. Recent advances in high pressure aqueous chemistry and water-rock interactions allow us to compute the equilibrium ionic conditions and pH everywhere in Europa's interior. In this work, we develop radial structure and composition models for Europa that include self-consistent thermodynamics of all materials, developed using the PlanetProfile software. We will describe the potential hydration states and porosity of the rocky interior, and the partitioning of primordial sulfur between this layer, an underlying metallic core, and the ocean above. We will use these results to compute the ocean's salinity by extraction from the upper part of the rocky layer. In this context, we will also consider the fluxes of reductants from Europa's interior due to high-temperature hydrothermalism, serpentinization, and endogenic radiolysis.

Microbial communities of Hyper saline Lake Salda and Acigol, SW Turkey and Their effects on Biogeochemical cycles

NASA Astrophysics Data System (ADS)

Balci, N.; Karaguler, N. G.; Ece, I.; Romanek, C.

2009-12-01

The modern lakes Acigol and Salda, located in the “Lake District” of SW of Turkey, are known for the precipitation of sodium, magnesium, and potassium salts, and Mg-rich carbonate, respectively. As an analogue to extraterrestrial environments, these lakes provide opportunities to study microbe-mineral interactions in extreme environments, and in turn to better understand biogeochemical conditions in such environments. Lake Salda is an evaporatic alkaline lake (pH: 9) that covers an area of about 45 km2 in a partially serpentinized ophiolitic rocks. Water samples collected from the surface contain c. 295 mg/L Mg and c. 190 mg/L Na at a pH of 9.1, while the stream entering the lake (pH range 7-9.5) had values of 55 mg/L and 3 mg/L, respectively, indicating significant Na enrichment relative to Mg in the lake. Microbiological analyses of sediment samples from the stream and the lake indicate a diverse microbial community. Lake Acigol is a perennial lake with a maximum salinity of about 200 g/L and covers an area of 55-60 km2 . Water samples were taken from the lake and ponds around the lake in addition to sediment samples. The water chemistry revealed relatively high Na and SO4 concentrations both in the lake (30 gr/L, 33.36 gr/L), and the ponds (100 mg/L, 123 mg/L). The mineralogical analyses of sediments showed gypsum, halite, carbonate (aragonite, huntite) precipitation in the lake and ponds. The geochemical and microbiological data from both lakes suggest that the metabolic activity of microorganisms (cyanobacteria, sulfate reducing bacteria) significantly affect the surrounding microenvironment, overcoming the common kinetic inhibitors to carbonate mineral precipitation by raising the pH and Mg- and HCO3-ion concentration, and by reducing sulfate ion concentration of the waters. We are currently undertaking laboratory experiments to elucidate biological influences on the precipitation of carbonate minerals under field conditions.

Urine chemistry

MedlinePlus

... rate 24-hour urine protein Acid loading test (pH) Adrenalin - urine test Amylase - urine Bilirubin - urine Calcium - urine Citric acid ... Urine dermatan sulfate Urine - hemoglobin Urine metanephrine Urine pH Urine specific gravity Vanillylmandelic acid (VMA)

Validation of a portable, waterproof blood pH analyser for elasmobranchs.

PubMed

Talwar, Brendan; Bouyoucos, Ian A; Shipley, Oliver; Rummer, Jodie L; Mandelman, John W; Brooks, Edward J; Grubbs, R Dean

2017-01-01

Quantifying changes in blood chemistry in elasmobranchs can provide insights into the physiological insults caused by anthropogenic stress, and can ultimately inform conservation and management strategies. Current methods for analysing elasmobranch blood chemistry in the field are often costly and logistically challenging. We compared blood pH values measured using a portable, waterproof pH meter (Hanna Instruments HI 99161) with blood pH values measured by an i-STAT system (CG4+ cartridges), which was previously validated for teleost and elasmobranch fishes, to gauge the accuracy of the pH meter in determining whole blood pH for the Cuban dogfish ( Squalus cubensis ) and lemon shark ( Negaprion brevirostris ). There was a significant linear relationship between values derived via the pH meter and the i-STAT for both species across a wide range of pH values and temperatures (Cuban dogfish: 6.8-7.1 pH 24-30°C; lemon sharks: 7.0-7.45 pH 25-31°C). The relative error in the pH meter's measurements was ~±2.7%. Using this device with appropriate correction factors and consideration of calibration temperatures can result in both a rapid and accurate assessment of whole blood pH, at least for the two elasmobranch species examined here. Additional species should be examined in the future across a wide range of temperatures to determine whether correction factors are universal.

In situ arsenic removal in an alkaline clastic aquifer

USGS Publications Warehouse

Welch, A.H.; Stollenwerk, K.G.; Paul, A.P.; Maurer, D.K.; Halford, K.J.

2008-01-01

In situ removal of As from ground water used for water supply has been accomplished elsewhere in circum-neutral ground water containing high dissolved Fe(II) concentrations. The objective of this study was to evaluate in situ As ground-water treatment approaches in alkaline ground-water (pH > 8) that contains low dissolved Fe (

Predictive Analysis of Geochemical Controls in an Alpine Stream

NASA Astrophysics Data System (ADS)

Jochems, A. P.; Sherson, L. R.; Crossey, L. J.; Karlstrom, K. E.

2010-12-01

Alpine watersheds are increasingly relied upon for use in the American West, necessitating a more complete understanding of annual hydrologic patterns and geologic influences on water chemistry. The Jemez River is a fifth order stream in central New Mexico that flows from its source in the Jemez Mountains to its confluence with the Rio Grande north of the town of Bernalillo. Designated uses of the Jemez River include domestic water supply, recreation, and agriculture. Geothermal uses are currently being considered as well. The river recharges shallow aquifer waters used by several communities, including tribal lands of the Jemez Pueblo. The hydrogeology of the Jemez system is characterized by geothermal inputs from the Baca hydrothermal system associated with the 1.2Ma Valles caldera, as well as groundwater and surface water interactions. Freshwater input from the Rio Guadalupe and several ephemeral tributaries also influences the water chemistry of the Jemez system. Fifteen sites along a 35 km reach of the river were sampled between 2006 and 2010. Discharge of the Jemez River ranged from 10-876 cfs over the study period. The annual hydrograph is affected by annual snowmelt in the Jemez Mountains as well as surges due to monsoonal rains in July and August. Geochemical data collected over this period include temperature, conductivity, pH, dissolved oxygen (D.O.), major ions, trace elements, and stable isotopes. Continuous records of temperature, conductivity, pH, D.O. and turbidity data were collected from a water quality sonde installed in March 2010. Geochemical modeling and time series analysis were performed using PHREEQC, Geochemist’s Workbench, and MATLAB. Empirical data collected during this study gave rise to several models describing the hydrology and geochemistry of the Jemez system. Our data suggest that springs are the primary contributors to dissolved load, and that solute loading from geothermal inputs is intensified by low flows observed on hydrographs during late winter, as well as on the falling limb of flow during summer. Cation and anion concentrations experience significant declines during periods of high flow, though loadings remain high. Solute concentrations were found to increase downstream regardless of season. Downstream increases take place abruptly where the river crosses fault systems that localize discharge of hot spring brines from the hydrothermal system. Analyses completed during the spring of 2010 indicate that arsenic greatly exceeds EPA drinking water standards at low flows (<30 cfs). TDS and sulfate concentrations in the Jemez also exceed these standards at similar discharge. Stable isotope analyses demonstrate contributions from geothermal systems, with isotopically enriched values of δ18O for thermal waters, and near-meteoric values for most river waters. A model predicting solute concentrations as a function of snowmelt demonstrates that the Jemez River is susceptible to significant degradation of water quality under scenarios of decreasing snowpack. Fluctuations in water chemistries of this system directly affect recreational use and water quality of the Jemez River and shallow aquifer recharge, and must be considered for any proposed domestic or municipal use in the future.

Proximal renal tubular acidosis

MedlinePlus

... Tests The health care provider will perform a physical exam and ask about the symptoms. Tests that may be ordered include: Arterial blood gas Blood chemistry Blood pH level Urine pH and acid-loading ...

Meet EPA Scientist Tim Shafer, Ph.D.

EPA Pesticide Factsheets

Tim Shafer earned his bachelor’s degree in biology and chemistry from Hope College in Holland, MI, in 1986 and his Ph.D. in pharmacology and environmental toxicology from Michigan State University in 1991.

The oxidation of SO2 by NO2(g) at the air-water interface of aquated aerosol: implications for the rapid onset of haze-aerosol events in China

NASA Astrophysics Data System (ADS)

Li, L.; Colussi, A. J.; Hoffmann, M. R.

2017-12-01

Aqueous phase chemistry plays a vital role in the global atmosphere. The importance of heterogeneous chemistry has been recently underscored by the severe haze-fog pollution episodes experienced in Chinese megacities. A key finding is that despite reduced photochemistry during the wintertime haze events, the oxidation of S(IV) into sulfate aerosol occurs rapidly in spite of the low levels of ozone and H2O2. Field observations suggest that NO2 could serve as a suitable oxidant of S(IV) during the events under neutral pH conditions. However, the haze aerosols are mostly acidic. Furthermore, the air-water interface is more acidic than bulk-phase aquated system according to our recent findings. This work investigates the chemistry taking place as NO2(g) collides with the surface of aqueous S(IV) microdroplets as a function of pH to closely simulate actual haze aerosol events under atmospheric conditions. The reaction between NO2(g) and HSO3- (aq) is studied in situ under ambient temperature and pressure via online electrospray ionization mass spectrometry. The aqueous aerosols containing HSO3- is generated using a microjet which is exposed to NO2(g) alternatively, while the composition of the 1 nm interfacial liquid layer of the aerosol is instantaneously measured. The ratio of HSO3- to HSO4- is observed to decrease with the concomitant appearance of a strong m/z 62 signal upon NO2(g) exposure. The appearance of m/z 62 indicates the formation of NO3- via the disproportionation of NO2 (2NO2(g) + H2O (l) ⇌ H++NO3-(aq) + HONO(aq)) and thus impacts the ion-ion interactions of NO3- on the ratio of HSO3- to HSO4- in the outermost interfacial layers. Parallel experiments with NO3-(aq) additions are conducted to quantify the impact of NO3- on the the ratio, in order to unravel the contribution of NO2 to the oxidation of S(IV). After accounting for the HNO3 effect, it is concluded: (1) most NO2(g) is converted into NO3- via anion-catalyzed hydrolytic disproportionation; (2) the oxidation of HSO3- by NO2(g) is limited, with a maximum contribution of 10% at pH 4 6. The importance of transition metal catalyzed oxidation of S(IV) for aerosol formation at pH > 6 is also experimentally proved in this work. Overall, our research shows NO2 is not an important oxidant for sulfate aerosol formation during severe Chinese haze aerosol episodes.

B.S. Chemists: Experience and prospects in a changing scientific and technical environment

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

Russell, T.; Burrelli, J.S.

1995-12-31

The men and women who hold a Bachelor`s degree in chemistry as their highest academic degree are an important for chemistry as their highest academic degree are an important for chemistry and science generally. {open_quotes}BS chemists{close_quotes} are the pool of U.S. residents from which future chemistry Ph.D.s (80 percent of them) and MDs (9 percent of the 1990 medical school class) are recruited and the basic pool of scientific and technical manpower for chemical and related industries. BS chemists are the most heterogeneous of all chemist groups and the most mobile: even at graduation, two-thirds of them intend to bemore » something else -- a Ph.D., MD, MBA, etc. -- in the near future. The mobility of many BS chemists is more to other careers, and hence the diffusion of chemical knowledge throughout the occupational spectrum, is primarily an outflow of BS holders utilizing their scientific training in other fields. This talk describes the past and present circumstances of BS chemists and makes some forecasts about these people about these people and those who will be the graduate of four-year chemistry programs in the future. A number of private and federal agencies collect data on chemists, but to chart the situation of the BS graduate, this paper draws on data sets maintained by the National Science Foundation and the National Research Council, both on BS and, for comparison, Ph.D. holders. For clarity, this analysis will not deal with the situation of MS chemists who, on most indicators fall as intuition would tell us, between the BS and Ph.D. groups. We also draw heavily on ACS Comprehensive Member Surveys and the Starting Salary Surveys of new graduates so identified by their academic departments.« less

Variability of the carbonate chemistry in a shallow, seagrass-dominated ecosystem: implications for ocean acidification experiments

USGS Publications Warehouse

Challener, Roberta; Robbins, Lisa L.; Mcclintock, James B.

2016-01-01

Open ocean observations have shown that increasing levels of anthropogenically derived atmospheric CO2 are causing acidification of the world's oceans. Yet little is known about coastal acidification and studies are just beginning to characterise the carbonate chemistry of shallow, nearshore zones where many ecologically and economically important organisms occur. We characterised the carbonate chemistry of seawater within an area dominated by seagrass beds (Saint Joseph Bay, Florida) to determine the extent of variation in pH and pCO2 over monthly and daily timescales. Distinct diel and seasonal fluctuations were observed at daily and monthly timescales respectively, indicating the influence of photosynthetic and respiratory processes on the local carbonate chemistry. Over the course of a year, the range in monthly values of pH (7.36-8.28), aragonite saturation state (0.65-5.63), and calculated pCO2 (195-2537 μatm) were significant. When sampled on a daily basis the range in pH (7.70-8.06), aragonite saturation state (1.86-3.85), and calculated pCO2 (379-1019 μatm) also exhibited significant range and indicated variation between timescales. The results of this study have significant implications for the design of ocean acidification experiments where nearshore species are utilised and indicate that coastal species are experiencing far greater fluctuations in carbonate chemistry than previously thought.

Water quality data at selected sites in the Mississippi Valley-type Zn-Pb ore district of upper Silesia, Poland, 1995-97

USGS Publications Warehouse

Wirt, Laurie; Motyka, Jacek; Leach, David; Sass-Gustkiewicz, Maria; Szuwarzynski, Marek; Adamczyk, Zbigniew; Briggs, Paul; Meiers, Al

2003-01-01

The water chemistry of aquifers and streams in the Upper Silesia Ore District, Poland are affected by their proximity to zinc, lead, and silver ores and by ongoing mining activities that date back to the 11th century. This report presents hydrologic and water-quality data collected as part of a collaborative research effort of the U.S. Geological Survey and the University of Mining and Metallurgy in Cracow, Poland to study Mississippi-Valley-Type lead-zinc deposits. MVT deposits in the Upper Silesia Ore District (Fig. 1) were selected for detailed study because the Polish mining industry allowed access to collect samples from underground mines and mine-land property. Water-quality samples were collected from streams, springs, wells, underground mine seeps and drains; and mine-tailings ponds. Data include field measurements of specific conductance, pH, water temperature, and dissolved oxygen and laboratory analyses of major and minor inorganic constituents and selected trace-element constituents.

Multi-decadal Records of Ocean Acidification and Toxic Heavy Metal Pollution in Coral Cores from Oahu, Hawaii

NASA Astrophysics Data System (ADS)

Stewart, J.; Tolliver, R.; Field, D. B.; Young, C.; Stafford, G.; Day, R. D.

2016-12-01

Monitoring of the physiological/ecological response of marine calcifying organisms to the combination of lower pH and toxic metal pollutants (e.g. Cu and Sn from boat anti-fouling paints) into the oceans requires detailed knowledge of the rates and spatial distribution of ocean acidification (OA) and trace metal composition over time. Yet, measurement of metal concentrations and carbonate system parameters in the modern ocean from seawater bottle data is patchy (e.g. CDIAC/WOCE Carbon Data; http://cdiac.ornl.gov) and there remain few long-term surface water pH monitoring stations; the two longest continuous records of ocean pH extend back less than 30 years (Bermuda - BATS, 31°40'N, 64°10'W; Hawaii - HOTs, 22°45'N, 158°00'W). Much attention has therefore been focused on trace metal and ocean carbonate system proxy development to allow reconstruction of seawater metal content and pH in the past. Of particular promise is the boron isotope (δ11B) pH-proxy measured in marine calcifying organisms such as coral that can be cored enabling multi-decadal, annual-resolution, records of trace element incorporation and seawater pH to be generated. Here we present continuous Cu/Ca and Sn/Ca records in addition to δ11B data from three coral cores of Porites lutea. collected from waters proximal to Oahu, Hawaii. The diagenetic integrity of samples is verified using X-ray diffraction to assess the degree of calcite replacement. These cores reach a maximum depth of 80 cm and represent approximately 80 years of coral growth and seawater chemistry.

Arsenic in ground-water under oxidizing conditions, south-west United States

USGS Publications Warehouse

Robertson, F.N.

1989-01-01

Concentrations of dissolved arsenic in ground-water in alluvial basins of Arizona commonly exceed 50 ??g L-1 and reach values as large as 1,300 ??g L-1. Arsenic speciation analyses show that arsenic occurs in the fully oxidized state of plus 5 (As+5), most likely in the form of HAsO4???2, under existing oxidizing and pH conditions. Arsenic in source areas presumably is oxidized to soluble As before transport into the basin or, if after transport, before burial. Probable sources of arsenic are the sulphide and arsenide deposits in the mineralized areas of the mountains surrounding the basins. Arsenic content of alluvial material ranged from 2 to 88 ppm. Occurrence and removal of arsenic in ground-water are related to the pH and the redox condition of the ground-water, the oxidation state of arsenic, and sorption or exchange. Within basins, dissolved arsenic correlates (P<0.01) with dissolved molybdenum, selenium, vanadium, and fluoride and with pH, suggesting sorption of negative ions. The sorption hypothesis is further supported by enrichment of teachable arsenic in the basin-fill sediments by about tenfold relative to the crustal abundance and by as much as a thousandfold relative to concentrations found in ground-water. Silicate hydrolysis reactions, as defined within the alluvial basins, under closed conditions cause increases in pH basinward and would promote desorption. Within the region, large concentrations of arsenic are commonly associated with the central parts of basins whose chemistries evolve under closed conditions. Arsenic does not correlate with dissolved iron (r = 0.09) but may be partly controlled by iron in the solid phase. High solid-phase arsenic contents were found in red clay beds. Large concentrations of arsenic also were found in water associated with red clay beds. Basins that contain the larger concentrations are bounded primarily by basalt and andesite, suggesting that the iron content as well as the arsenic content of the basin fill may play a role in the occurrence of arsenic in ground-water. Under oxidizing conditions in Arizona, arsenic in ground-water appears to be controlled in part by sorption or desorption of HAsO4???2 on active ferric oxyhydroxide surfaces. ?? 1989 Sciences and Technology Letters.

Feasibility Study on a Process for Electroless Metal Deposition in Pits and Fissures of Teeth for Use in Preventive Dentistry.

DTIC Science & Technology

1980-08-01

been used in topical fluoride solutions applied to prevent caries . The use of SnF 2 . and similar chemical compounds, in the plating process appears to...Methods Tin fluoride solutions are prepared by dissolving SnF 2 in demineralized water at concentrations of 1, 5, 5.7, and 10%. The pH ranges from...saturated FeSO4 with or without 1 gpl thiourea a. .4 34 REFERENCES 1. P. Gron, "Chemistry of Topical Fluorides ", Caries Res. 11 (Suppl. 1): 172-204

Conversion of Azides into Diazo Compounds in Water

PubMed Central

Chou, Ho-Hsuan; Raines, Ronald T.

2013-01-01

Diazo compounds are in widespread use in synthetic organic chemistry, but have untapped potential in chemical biology. We report on the design and optimization of a phosphinoester that mediates the efficient conversion of azides into diazo compounds in phosphate buffer at neutral pH and room temperature. High yields are maintained in the presence of common nucleophilic or electrophilic functional groups, and reaction progress can be monitored by colorimetry. As azido groups are easy to install and maintain in biopolymers or their ligands, this new mode of azide reactivity could have substantial utility in chemical biology. PMID:24053717

Early cements versus pore-water chemical composition in the subsurface of the sabkha of Abu Dhabi

NASA Astrophysics Data System (ADS)

Paul, Andreas; Yuan, Peng; Court, Wesley M.; Lokier, Stephen W.; Dutton, Kirsten E.; Van der Land, Cees; Lessa Andrade, Luiza; Sherry, Angela; Head, Ian M.

2017-04-01

The coastal sabkha of Abu Dhabi is a complex depositional system in an extremely arid climate. This depositional system is marked by the formation of primary carbonate and microbial deposits, and by the development of secondary evaporite and cement phases. A number of earlier studies have assessed the formation of these secondary phases, yet no research has established a relationship between lateral and vertical variations in the chemical composition of pore water and the nature of, in particular, the precipitating pore-filling cements, re-crystallisation features and dissolution. This study aims to establish an understanding of the environmental and sedimentary factors that control early post-depositional changes to sediment composition as a result of sediment - pore water interactions. A particular focus is to characterise changes in the chemistry of the pore water throughout a tidal cycle, aiming at understanding how the influx of 'fresh' lagoonal sea water influences the chemistry of the pore water, and which elements are replenished on a daily basis. The initial data presented here is based upon the relationship between the petrographic analysis of sediment samples and lateral and vertical variations in the chemistry of in-situ sampled pore water. The pore water is characterised with respect to pH, salinity, alkalinity, dissolved organic carbon, and the concentrations of a variety of common metallic and non-metallic elements, including (but not limited to) Ca, Fe, Mg, P, S and Sr. Initial results show that concentrations of Mg, P, and V, and the ratios Mg/Ca and Sr/Ca are highest at the seaward sampling locations. Contrastingly, individual concentrations for Ca, Sr, Fe, Si, and Cu are highest at the most landward locality. In particular the higher concentrations for Ca and Sr might indicate diagenetic processes and are thus enriched as a result of e.g. aragonite dissolution. A striking pattern in Mg concentrations show the highest values for this element within a buried microbial mat. This might point to an enrichment process within this organo-sedimentary layer, that might ultimately contribute to bacterially controlled and/or mediated dolomite formation.

Dynamic Change of Water Quality in Hyporheic Zone at Water Curtain Cultivation Area, Cheongju, Korea

NASA Astrophysics Data System (ADS)

Moon, S. H.; Kim, Y.

2015-12-01

There has been recently growing numbers of facilities for water curtain cultivation of strawberry and lettuce in Korea. These areas are nearly all located in the fluvial deposits near streams which can replenish water resources into exhausted groundwater aquifers during peak season. The purpose of this study is on groundwater chemistry and the change in physical and chemical properties due to stream-groundwater exchange or mixing in the representative agricultural area among the Jurassic granitic terrain of Korea. In the study area, groundwater level continuously decreased from November through March due to intensive use of groundwater, which forced stream water into aquifer. After March, groundwater level was gradually recovered to the original state. To evaluate the extent and its variations of stream water mixing into aquifer, field parameters including T, pH, EC and DO values, concentrations of major ions and oxygen and hydrogen stable isotopic ratios were used. Field measurements and water sample collections were performed several times from 2012 to 2015 mainly during peak time of groundwater use. To compare the temporal variations and areal differences, 21 wells from four cross sections perpendicular to stream line were used. While water temperature, EC values and concentrations of Ca, Mg, Si, HCO3 showed roughly gradual increase from stream line to 150 m distance, pH and DO values showed reverse phenomenon. This can be used to evaluate the extent and limit of stream water introduction into aquifer. However, individual wells showed yearly variations in those parameters and this dynamic and unstable feature indicates that mixing intensity of stream water over groundwater in this hyporheic zone varied year by year according to amounts of groundwater use and decrease of groundwater level.

Geochemistry and microbiology of iron-related well-screen encrustation and aquifer biofouling in Suffolk County, Long Island, New York

USGS Publications Warehouse

Walter, D.A.

1997-01-01

Iron-related well-screen encrustation and aquifer biofouling has decreased the specific capacity of several production wells in Suffolk County, N.Y., and has forced the Suffolk County Water Authority to adopt a costly well-reconditioning and replacement program. The specific-capacity declines are the result of the precipitation of iron oxyhydroxides and the growth of iron bacteria on the well screens and in the pore spaces of the surrounding formation. Mineralogic and chemical analyses indicate that the inorganic part of the encrusting material consists primarily of amorphous ferric hydroxide (Fe(OH)3 ); minor components of the material include goethite (FeOOH), hematite (Fe2 O 3 ), and quartz (SiO 2 ). The weight percent of ferric hydroxide in the material ranged from 32.3 to 98.6 percent and averaged 64.3 percent. Equilibrium modeling indicated that during pumping the well waters were supersaturated with respect to goethite, hematite, magnetite, and quartz and were under-saturated with respect to ferric hydroxide. Theoretical Eh values computed for the ferrous/ferric-iron redox couple and the oxygen/water redox couple averaged 390 millivolts and 810 millivolts, respectively, indicating that the waters were in a state of redox disequilibrium. The disequilibrium condition arises from the mixing of ground water with a low dissolved-oxygen concentration with oxygenated ground water during operation of the well. The low pH of the ground water contributes to the disequilibrium condition by slowing the rate of iron oxidation after the introduction of oxygen. Chemical and mineralogical data indicate that most of the encrusting material in the wells was deposited while the wells were shut down, probably in response to the use of treated water of higher pH to keep pump turbines wet while the wells were not in operation; the increased pH of water in the static water column increases the rate of ferrous-iron oxidation and causes the well water to become increasingly saturated with respect to ferric hydroxide. The median half-time of oxidation in samples of untreated ground water (pH 4-5) was 4.19 days, whereas the average half-time of oxidation in treated water (pH 7-8) was 11.9 minutes Equilibrium modeling indicated that treated waters generally were supersaturated with respect to ferric hydroxide, whereas untreated well waters were not. Field and laboratory data indicate that iron bacteria play an important role in the encrustation and biofouling process in Suffolk County. Filamentous iron bacteria were common in the affected wells. The most common species was Gallionella ferruginea, an effective biofouling agent that prefers water with low, but detectable, dissolved-oxygen concentrations and high dissolved-iron concentrations; this species was more common in biofilm samples from the Magothy aquifer than in those from the upper glacial aquifer. Iron bacteria also were found in sediment cores from several locations in the aquifer and in drilling water. Lignite could act as a carbon source for heterotrophic iron bacteria, which could accelerate the formation of iron-bacteria biofilms in wells screened in some parts of the Magothy aquifer. Iron-bacteria biofilms alter the chemistry of well water by removing iron, manganese, and sulfate from solution and by increasing the pH. Sulfur-reducing bacteria and iron-sulfide mineral phases were observed in some samples of encrusting material, indicating that these bacteria could contribute to well-screen encrustation in some geochemical environments.

pH responsive label-assisted click chemistry triggered sensitivity amplification for ultrasensitive electrochemical detection of carbohydrate antigen 24-2.

PubMed

Zheng, Yun; Zhao, Lihua; Ma, Zhanfang

2018-05-15

Sensitivity amplification strategy by implementing click chemistry in the construction of biosensing interface can efficiently improve the performance of immunosensor. Herein, we developed a sandwich-type amperometric immunosensor for ultrasensitive detection of carbohydrate antigen 24-2 (CA 242) based on pH responsive label-assisted click chemistry triggered sensitivity amplification strategy. The sensitivity of amperometric immunosensor relies on the current response differences (ΔI) caused by per unit concentration target analyte. The pH responsive Cu 2+ -loaded polydopamine (CuPDA) particles conjugated with detection antibodies were employed as labels, which can release Cu(II) ions by regulating pH. In the presence of ascorbic acid (reductant), Cu(II) ions were reduced to Cu(I) ions. Azide-functionalized double-stranded DNA (dsDNA) as signal enhancer was immobilized on the substrate through Cu + -catalyzed azide/alkyne cycloaddition reaction. With the help of the click reaction, the ΔI caused by target was elevated prominently, resulting in sensitivity amplification of the immunosensor. Under optimal condition, the proposed immunosensor exhibited excellent performance with linear range from 0.0001 to 100 U mL -1 and ultralow detection limit of 20.74 μU mL -1 . This work successfully combines click chemistry with pH-responsive labels in sandwich-type amperometric immunosensor, providing a promising sensitivity amplification strategy to construct immunosensing platform for analysis of other tumor marker. Copyright © 2018 Elsevier B.V. All rights reserved.

Soil chemistry and ground-water quality of the water-table zone of the surficial aquifer, Naval Submarine Base Kings Bay, Camden County, Georgia, 1998 and 1999

USGS Publications Warehouse

Leeth, David C.

2002-01-01

In 1998, the U.S. Geological Survey, in cooperation with the U.S. Department of the Navy, began an investigation to determine background ground-water quality of the water-table zone of the surficial aquifer and soil chemistry at Naval Submarine Base Kings Bay, Camden County, Georgia, and to compare these data to two abandoned solid- waste disposal areas (referred to by the U.S. Navy as Sites 5 and 16). The quality of water in the water-table zone generally is within the U.S. Environmental Protection Agency (USEPA) drinking-water regulation. The pH of ground water in the study area ranged from 4.0 to 7.6 standard units, with a median value of 5.4. Water from 29 wells is above the pH range and 3 wells are within the range of the USEPA secondary drinking-water regulation (formerly known as the Secondary Maximum Contaminant Level or SMCL) of 6.5 to 8.5 standard units. Also, water from one well at Site 5 had a chloride concentration of 570 milligrams per liter (mg/L,), which is above the USEPA secondary drinking-water regulation of 250 mg/L. Sulfate concentrations in water from two wells at Site 5 are above the USEPA secondary drinking-water regulation of 250 mg/L. Of 22 soil-sampling locations for this study, 4 locations had concentrations above the detection limit for either volatile organic compounds (VOCs), base-neutral acids (BNAs), or pesticides. VOCs detected in the study area include toluene in one background sample; and acetone in one background sample and one sample from Site 16--however, detection of these two compounds may be a laboratory artifact. Pesticides detected in soil at the Submarine Base include two degradates of 1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane (DDT): 1,1-dichloro-2,2-bis(p-chlorophenyl)ethane (4,4'-DDD) in one background sample, 1,1-dichloro-2,2-bis(p-chlorophenyl)ethene (4,4'-DDE) in one background sample and one sample from Site 16; and dibenzofuran in one sample from Site 16. BNAs were detected in one background sample and in two samples from Site 16. Hypothesis testing, using the Wilcoxon rank-sum test (also known as the Mann-Whitney test), indicates no statistical difference between ground-water constituent concentrations from Sites 5 and 16, and background concentrations. Hypothesis testing, however, indicates the concentration of barium in background ground-water samples is greater than in ground-water samples collected at Site 16.

Hatching success in salamanders and chorus frogs at two sites in Colorado, USA: Effects of acidic deposition and climate

USGS Publications Warehouse

Muths, E.; Campbell, D.H.; Corn, P.S.

2003-01-01

The snowpack in the vicinity of the Mount Zirkel Wilderness Area is among the most acidic in the western United States. We analyzed water chemistry and examined hatching success in tiger salamanders and chorus frogs at ponds there and at nearby Rabbit Ears Pass (Dumont) to determine whether acid deposition affects amphibians or their breeding habitats at these potentially sensitive locations. We found a wide range of acid neutralizing capacity among ponds within sites; the minimum pH recorded during the experiment was 5.4 at one of 12 ponds with all others at pH ??? 5.7. At Dumont, hatching success for chorus frogs was greater in ponds with low acid neutralizing capacity; however, lowest pHs were >5.8. At current levels of acid deposition, weather and pond characteristics are likely more important than acidity in influencing hatching success in amphibian larvae at these sites.

Influence of corrosive solutions on microhardness and chemistry of magnesium oxide /001/ surfaces

NASA Technical Reports Server (NTRS)

Ishigaki, H.; Miyoshi, K.; Buckley, D. H.

1982-01-01

X-ray photoelectron spectroscopy analyses and hardness experiments were conducted on cleaved magnesium oxide /001/ surfaces. The magnesium oxide bulk crystals were cleaved to specimen size along the /001/ surface, and indentations were made on the cleaved surface in corrosive solutions containing HCl, NaOH, or HNO3 and in water without exposing the specimen to any other environment. The results indicated that chloride (such as MgCl2) and sodium films are formed on the magnesium oxide surface as a result of interactions between an HCl-containing solution and a cleaved magnesium oxide surface. The chloride films soften the magnesium oxide surface. In this case microhardness is strongly influenced by the pH value of the solution. The lower the pH, the lower the microhardness. Sodium films, which are formed on the magnesium oxide surface exposed to an NaOH containing solution, do not soften the magnesium oxide surface.

Fast-growing Acer rubrum differs from slow-growing Quercus alba in leaf, xylem and hydraulic trait coordination responses to simulated acid rain.

PubMed

Medeiros, Juliana S; Tomeo, Nicholas J; Hewins, Charlotte R; Rosenthal, David M

2016-08-01

We investigated the effects of historic soil chemistry changes associated with acid rain, i.e., reduced soil pH and a shift from nitrogen (N)- to phosphorus (P)-limitation, on the coordination of leaf water demand and xylem hydraulic supply traits in two co-occurring temperate tree species differing in growth rate. Using a full-factorial design (N × P × pH), we measured leaf nutrient content, water relations, leaf-level and canopy-level gas exchange, total biomass and allocation, as well as stem xylem anatomy and hydraulic function for greenhouse-grown saplings of fast-growing Acer rubrum (L.) and slow-growing Quercus alba (L.). We used principle component analysis to characterize trait coordination. We found that N-limitation, but not P-limitation, had a significant impact on plant water relations and hydraulic coordination of both species. Fast-growing A. rubrum made hydraulic adjustments in response to N-limitation, but trait coordination was variable within treatments and did not fully compensate for changing allocation across N-availability. For slow-growing Q. alba, N-limitation engendered more strict coordination of leaf and xylem traits, resulting in similar leaf water content and hydraulic function across all treatments. Finally, low pH reduced the propensity of both species to adjust leaf water relations and xylem anatomical traits in response to nutrient manipulations. Our data suggest that a shift from N- to P-limitation has had a negative impact on the water relations and hydraulic function of A. rubrum to a greater extent than for Q. alba We suggest that current expansion of A. rubrum populations could be tempered by acidic N-deposition, which may restrict it to more mesic microsites. The disruption of hydraulic acclimation and coordination at low pH is emphasized as an interesting area of future study. © The Author 2016. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

Move! - a deep Ocean Underwater Robot for Bio-Geochemical Research

NASA Astrophysics Data System (ADS)

Waldmann, C.; Epping, E.; Move! Team

2003-04-01

Within the framework of the binationally funded project MOVE! the partners from the Netherlands and Germany are pursuing the development of a versatile, autonomous vehicle for benthic research. The system acts as a modular platform for different scientific sensors and by moving on the sea floor will allow for taking measurements at defined locations. By combining acoustical navigation methods with other new position tracking devices an accurate positioning can be achieved. Both the vehicle subsystems and the scientific sensors will be powered by a dedicated energy source. The scientific application lies in the area of multidisciplinary studies (physics, chemistry, sedimentology and biology) with an emphasis on element cycling in marine sediments and benthic boundary layer from coastal areas to deep sea. Application of the vehicle should enable timed monitoring and experimentation to study temporal dynamics in forcing and effects, and allow for multiple sites to be studied in a single area to cover spatial variability. Typical experiments would require (1) enclosing an area of sediment and overlying water to monitor the chemical exchange between sediment and water to study the actual base line activities (2) manipulation of the sediment-overlying water by adding dissolved substances or particulate substances (food+ inert tracers) and the subsequent monitoring of overlying water chemistry (oxygen, DIC, pH, nitrate, ammonium, silicate) in order to assess biological responses to chemical disturbances. Sediments should be recovered after the experiment. (3)The monitoring of pore water chemistry by use of microelectrodes and HR-DET probes baseline and after addition in preceding chamber experiment (requires careful repositioning with high accuracy or a combined chamber-profiling unit) (4) Injection of labeled organic and inorganic substrates in the sediment and recovery of sediment cores in order to measure specific activities and to disentangle trophic relationships within sediments. The presentation will explain details of the design concept and how the envisaged scientific goals will be reached.

Chemical characterization of fog and rain water collected at the eastern Andes cordillera

NASA Astrophysics Data System (ADS)

Beiderwieden, E.; Wrzesinsky, T.; Klemm, O.

2005-09-01

During a three month period in 2003 and 2004, the chemistry of fog and rainwater were studied at the "El Tiro" site in a tropical mountain forest ecosystem in Ecuador, South America. The fogwater samples were collected using a passive fog collector, and for the rain water, a standard rain sampler was employed. For all samples, electric conductivity, pH, and the concentrations of NH4+, K+, Na+, Ca2+, Mg2+, Cl-, NO3-, PO43-, and SO42- were measured. For each fog sample, a 5 day back trajectory was calculated by the use of the HYSPLIT model. Two types of trajectories occurred. One type was characterized by advection of air masses from the East over the Amazonian basin, the other trajectory arrived one from the West after significant travel time over the Pacific Ocean. We found considerably higher ion concentrations in fogwater samples than in rain samples. Median pH values are 4.58 for fog water, and 5.26 for the rain samples, respectively. The median electric conductivity was 23 μS cm-1 for the fog and 6 μS cm-1 for the rain. The continent samples exhibit higher concentrations of most ions as compared to the pacific samples, but these differences could not be detected statistically.

Downhole Transformation of the Hydraulic Fracturing Fluid Biocide Glutaraldehyde: Implications for Flowback and Produced Water Quality.

PubMed

Kahrilas, Genevieve A; Blotevogel, Jens; Corrin, Edward R; Borch, Thomas

2016-10-18

Hydraulic fracturing fluid (HFF) additives are used to enhance oil and gas extraction from unconventional shale formations. Several kilometers downhole, these organic chemicals are exposed to temperatures up to 200 °C, pressures above 10 MPa, high salinities, and a pH range from 5-8. Despite this, very little is known about the fate of HFF additives under these extreme conditions. Here, stainless steel reactors are used to simulate the downhole chemistry of the commonly used HFF biocide glutaraldehyde (GA). The results show that GA rapidly (t 1/2 < 1 h) autopolymerizes, forming water-soluble dimers and trimers, and eventually precipitates out at high temperatures (∼140 °C) and/or alkaline pH. Interestingly, salinity was found to significantly inhibit GA transformation. Pressure and shale did not affect GA transformation and/or removal from the bulk fluid. On the basis of experimental pseudo-second-order rate constants, a kinetic model for GA downhole half-life predictions for any combination of these conditions within the limits tested was developed. These findings illustrate that the biocidal GA monomer has limited time to control microbial activity in hot and/or alkaline shales, and may return along with its aqueous transformation products to the surface via flowback and produced water in cooler, more acidic, and saline shales.

Copper-Hydroperoxo Mediated N-Debenzylation Chemistry Mimicking Aspects of Copper Monoxygenases

PubMed Central

Maiti, Debabrata; Narducci Sarjeant, Amy A.; Karlin, Kenneth D.

2008-01-01

Substantial oxidative N-debenzylation reaction along with PhCH=O formation occurs from a hydroperoxo copper(II) complex which has a dibenzylamino substrate (-N(CH2Ph)2 appended as a substituent on one pyridyl group of its tripodal tetradentate TMPA {≡ TPA ≡ tris(2-pyridylmethyl)amine)} ligand framework. During the course of the (LN(CH2Ph)2)CuII(−OOH) reactivity, formation of a substrate and −OOH (an oxygen atom) derived alkoxo CuII(−OR) complex occurs. The observation that the same CuII(−OR) species occurs from CuI/PhIO chemistry suggests the possibility that a copper-oxo (cupryl) reactive intermediate forms during alkoxo species formation, and new ESI-MS data obtained provides some further support for this high-valent intermediate. Net H-atom abstraction chemistry is proposed, based on kinetic isotope effect studies provided here and that previously published for a closely related CuII(−OOH) species incorporating dimethylamine (-N(CH3)2) as the internal substrate (J. Am. Chem. Soc. 2007, 129, 6720-6721); the CuI/PhIO reactivity, with similar isotope effect results, provides further support. The reactivity of these chemical systems closely resembles proposed oxidative N-dealkylation mechanisms effected by the copper-monooxygenases dopamine β-monooxygenase (DβM) or peptidylglycine-α-hydroxylating monooxygenase (PHM). PMID:18783212

Carbonate system parameters of an algal-dominated reef along west Maui

USGS Publications Warehouse

Prouty, Nancy G.; Yates, Kimberly K.; Smiley, Nathan A.; Gallagher, Christopher; Cheriton, Olivia; Storlazzi, Curt

2018-01-01

Constraining coral reef metabolism and carbon chemistry dynamics are fundamental for understanding and predicting reef vulnerability to rising coastal CO2 concentrations and decreasing seawater pH. However, few studies exist along reefs occupying densely inhabited shorelines with known input from land-based sources of pollution. The shallow coral reefs off Kahekili, West Maui, are exposed to nutrient-enriched, low-pH submarine groundwater discharge (SGD) and are particularly vulnerable to the compounding stressors from land-based sources of pollution and lower seawater pH. To constrain the carbonate chemistry system, nutrients and carbonate chemistry were measured along the Kahekili reef flat every 4 h over a 6-d sampling period in March 2016. Abiotic process – primarily SGD fluxes – controlled the carbonate chemistry adjacent to the primary SGD vent site, with nutrient-laden freshwater decreasing pH levels and favoring undersaturated aragonite saturation (Ωarag) conditions. In contrast, diurnal variability in the carbonate chemistry at other sites along the reef flat was driven by reef community metabolism. Superimposed on the diurnal signal was a transition during the second sampling period to a surplus of total alkalinity (TA) and dissolved inorganic carbon (DIC) compared to ocean end-member TA and DIC measurements. A shift from net community production and calcification to net respiration and carbonate dissolution was identified. This transition occurred during a period of increased SGD-driven nutrient loading, lower wave height, and reduced current speeds. This detailed study of carbon chemistry dynamics highlights the need to incorporate local effects of nearshore oceanographic processes into predictions of coral reef vulnerability and resilience.

The pH of chemistry assays plays an important role in monoclonal immunoglobulin interferences.

PubMed

Alberti, Michael O; Drake, Thomas A; Song, Lu

2015-12-01

Immunoglobulin paraproteins can interfere with multiple chemistry assays. We want to investigate the mechanisms of immunoglobulin interference. Serum samples containing paraproteins from the index patient and eight additional patients were used to investigate the interference with the creatinine and total protein assays on the Beckman Coulter AU5400/2700 analyzer, and to determine the effects of pH and ionic strength on the precipitation of different immunoglobulins in these patient samples. The paraprotein interference with the creatinine and total protein assays was caused by the precipitation of IgM paraprotein in the index patient's samples under alkaline assay conditions. At extremely high pH (12-13) and extremely low pH (1-2) and low ionic strength, paraprotein formed large aggregates in samples from the index patient but not from other patients. The pH and ionic strength are the key factors that contribute to protein aggregation and precipitation which interfere with the creatinine and total protein measurements on AU5400/2700. The different amino acid sequence of each monoclonal paraprotein will determine the pH and ionic strength at which the paraprotein will precipitate.

[Aluminum mobilization models of forest yellow earth in South China].

PubMed

Xin, Yan; Zhao, Yu; Duan, Lei

2009-07-15

For the application of acidification models in predicting effects of acid deposition and formulating control strategy in China, it is important selecting regionally applicable models of soil aluminum mobilization and determining their parameters. Based on the long-term monitoring results of soil water chemistry from four forested watersheds in South China, the applicability of a range of equilibriums describing aluminum mobilization was evaluated. The tested equilibriums included those for gibbsite, jurbanite, kaolinite, imogolite, and SOM-Al: Results show that the gibbsite equilibrium commonly used in several acidification models is not suitable for the typical forest soil in South China, while the modified empirical gibbsite equation is applicable with pK = - 2.40, a = 1.65 (for upper layer) and pK = - 2.82, a = 1.66 (for lower layers) at only pH > or = 4. Comparing with the empirical gibbsite equation, the other equilibriums do not perform better. It can also be seen that pAl varies slightly with pH decreases at pH < 4, which is unexplainable by any of these suggested equilibriums.

Nanoscale Titanium Dioxide (nTiO2) Transport in Water-Saturated Natural Sediments: Influence of Soil Organic Matter and Fe/Al Oxyhydroxides

NASA Astrophysics Data System (ADS)

Fisher-Power, L.; Cheng, T.

2017-12-01

Transport of engineered nanoparticles (ENP) in subsurface environments has important implications to water quality and soil contamination. Although extensive research has been conducted to understand the effects of water chemistry on ENP transport, less attention has been paid to influences from the transport medium/matrix. The objective of this research is to investigate the effects of natural organic matter (NOM) and Fe/Al oxyhydroxides in a natural sediment on ENP transport. A sediment was collected and separated into four portions, one of which was unmodified, and the others treated to remove specific components (organic matter, Fe/Al oxyhydroxides, or both organic matter and Fe/Al oxyhydroxides). Transport of nanoscale titanium dioxide (nTiO2) in columns packed with quartz sand and each of the four types of the sediment under water-saturated conditions was studied. Our results showed that nTiO2 transport was strongly influenced by pH and sediment composition. When influent pH = 5, nTiO2 transport in all the sediments was low, as positively-charged nTiO2 was attracted to negatively charged NOM, quartz, and other minerals. nTiO2 transport was slightly enhanced in columns packed with untreated sediment or Fe/Al oxyhydroxides removed sediment due to dissolved organic matter generated by the partial dissolution of NOM, which adsorbed onto nTiO2 surface and reversed its zeta potential to negative. When influent pH = 9, nTiO2 transport was generally high since negatively-charged nTiO2 was repelled by negatively charged transport medium. However, in columns packed with the organic matter removed sediment or the Fe/Al oxyhydroxides removed sediment, nTiO2 transport was low. This was attributable to pH buffering by the sediment, which decreased pore water pH in the column, resulting in zeta potential change and electrostatic attraction between Fe/Al oxyhydroxides and nTiO2. This research demonstrates that electrostatic forces between nTiO2 and mineral/organic components in natural sediments is a key factor that controls nTiO2 retention and transport, and that both NOM and Fe/Al oxyhydroxides may substantially influence nTiO2 transport.

Impacts of episodic acidification on in-stream survival and physiological impairment of Atlantic salmon (Salmo salar) smolts

USGS Publications Warehouse

McCormick, S.D.; Keyes, A.; Nislow, K.H.; Monette, M.Y.

2009-01-01

We conducted field studies to determine the levels of acid and aluminum (Al) that affect survival, smolt development, ion homeostasis, and stress in Atlantic salmon (Salmo salar) smolts in restoration streams of the Connecticut River in southern Vermont, USA. Fish were held in cages in five streams encompassing a wide range of acid and Al levels for two 6-day intervals during the peak of smolt development in late April and early May. Physiological parameters were unchanged from initial sampling at the hatchery and the high water quality reference site (pH > 7.0, inorganic Al < 12 μg·L-1). Mortality, substantial loss of plasma chloride, and gill Na+/K+-ATPase activity, and elevated gill Al occurred at sites with the lowest pH (5.4-5.6) and highest inorganic Al (50-80 μg·L-1). Moderate loss of plasma chloride, increased plasma cortisol and glucose, and moderately elevated gill Al occurred at less severely impacted sites. Gill Al was a better predictor of integrated physiological impacts than water chemistry alone. The results indicate that Al and low pH under field conditions in some New England streams can cause mortality and impair smolt development in juvenile Atlantic salmon and provide direct evidence that episodic acidification is impacting conservation and recovery of Atlantic salmon in the northeastern USA.

Lithologic descriptions of two cores and ground-water-quality data from five counties in the northeastern part of the coastal plain of South Carolina, 1988 and 1991

USGS Publications Warehouse

Falls, W.F.

1994-01-01

This report presents data collected as part of a hydrologic investigation of Darlington, Dillon, Florence, Marion, and Marlboro Counties in the northeastern part of the Coastal Plain of South Carolina. These data include lithologic descriptions of sediment recovered from two continuously cored boreholes and water-quality results for samples collected from 17 existing wells. One continuously cored borehole was drilled near Lake Darpo in the northern part of Darlington County to a total depth of 447 feet below land surface. The other borehole was drilled in Lake City in the south-central part of Florence County to a total depth of 1,090 feet below land surface. Water-quality results presented in this report include specific conductance, dissolved oxygen, temperature, pH, alkalinity, major- and minor-ion chemistry, and hydrogen sulfide.

Rapid releases of metal salts and nutrients following the deposition of volcanic ash into aqueous environments

NASA Astrophysics Data System (ADS)

Jones, Morgan T.; Gislason, Sigurður R.

2008-08-01

Deposition of volcanic ash into aqueous environments leads to dissolution of adsorbed metal salts and aerosols, increasing the bioavailability of key nutrients. Volcanogenic fertilization events could increase marine primary productivity, leading to a drawdown of atmospheric CO 2. Here we conduct flow-through experiments on unhydrated volcanic ash samples from a variety of locations and sources, measuring the concentrations and fluxes of elements into de-ionized water and two contrasting ocean surface waters. Comparisons of element fluxes show that dissolution of adsorbed surface salts and aerosols dominates over glass dissolution, even in sustained low pH conditions. These surface ash-leachates appear unstable, decaying in situ even if kept unhydrated. Volcanic ash from recent eruptions is shown to have a large fertilization potential in both fresh and saline water. Fluorine concentrations are integral to bulk dissolution rates and samples with high F concentrations display elevated fluxes of some nutrients, particularly Fe, Si, and P. Bio-limiting micronutrients are released in large quantities, suggesting that subsequent biological growth will be limited by macronutrient availability. Importantly, acidification of surface waters and high fluxes of toxic elements highlights the potential of volcanic ash-leachates to poison aqueous environments. In particular, large pH changes can cause undersaturation of CaCO 3 polymorphs, damaging populations of calcifying organisms. Deposition of volcanic ash can both fertilize and/or poison aqueous environments, causing significant changes to surface water chemistry and biogeochemical cycles.

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.

Validation of a portable, waterproof blood pH analyser for elasmobranchs

PubMed Central

Bouyoucos, Ian A.; Shipley, Oliver; Rummer, Jodie L.; Mandelman, John W.; Brooks, Edward J.; Grubbs, R. Dean

2017-01-01

Abstract Quantifying changes in blood chemistry in elasmobranchs can provide insights into the physiological insults caused by anthropogenic stress, and can ultimately inform conservation and management strategies. Current methods for analysing elasmobranch blood chemistry in the field are often costly and logistically challenging. We compared blood pH values measured using a portable, waterproof pH meter (Hanna Instruments HI 99161) with blood pH values measured by an i-STAT system (CG4+ cartridges), which was previously validated for teleost and elasmobranch fishes, to gauge the accuracy of the pH meter in determining whole blood pH for the Cuban dogfish (Squalus cubensis) and lemon shark (Negaprion brevirostris). There was a significant linear relationship between values derived via the pH meter and the i-STAT for both species across a wide range of pH values and temperatures (Cuban dogfish: 6.8–7.1 pH 24–30°C; lemon sharks: 7.0–7.45 pH 25–31°C). The relative error in the pH meter's measurements was ~±2.7%. Using this device with appropriate correction factors and consideration of calibration temperatures can result in both a rapid and accurate assessment of whole blood pH, at least for the two elasmobranch species examined here. Additional species should be examined in the future across a wide range of temperatures to determine whether correction factors are universal. PMID:28616238

Forest canopy structural controls over throughfall affect soil microbial community structure in an epiphyte-laden maritime oak stand

NASA Astrophysics Data System (ADS)

Van Stan, J. T., II; Rosier, C. L.; Schrom, J. O.; Wu, T.; Reichard, J. S.; Kan, J.

2014-12-01

Identifying spatiotemporal influences on soil microbial community (SMC) structure is critical to understanding of patterns in nutrient cycling and related ecological services. Since forest canopy structure alters the spatiotemporal patterning of precipitation water and solute supplies to soils (via the "throughfall" mechanism), is it possible changes in SMC structure variability could arise from modifications in canopy elements? Our study investigates this question by monitoring throughfall water and dissolved ion supply to soils beneath a continuum of canopy structure: from a large gap (0% cover) to heavy Tillandsia usneoides L. (Spanish moss) canopy (>90% cover). Throughfall water supply diminished with increasing canopy cover, yet increased washoff/leaching of Na+, Cl-, PO43-, and SO42- from the canopy to the soils (p < 0.01). Presence of T. usneoides diminished throughfall NO3-, but enhanced NH4+, concentrations supplied to subcanopy soils. The mineral soil horizon (0-10 cm) from canopy gaps, bare canopy, and T. usneoides-laden canopy significantly differed (p < 0.05) in soil chemistry parameters (pH, Ca2+, Mg2+, CEC). PCR-DGGE banding patterns beneath similar canopy covers (experiencing similar throughfall dynamics) also produced high similarities per ANalyses Of SIMilarity (ANO-SIM), and clustered together when analyzed by Nonmetric Multidimensional Scaling (NMDS). Correlation analysis of DGGE banding patterns, throughfall dynamics, and soil chemistry yielded significant correlations (p < 0.05) between fungal communities and soil chemical properties significantly differing between canopy cover types (pH: r2 = 0.50; H+ %-base saturation: r2 = 0.48; Ca2+ %-base saturation: r2 = 0.43). Bacterial community structure correlated with throughfall NO3-, NH4+, and Ca2+ concentrations (r2 = 0.37, p = 0.16). These results suggest that modifications of forest canopy structures are capable of affecting mineral-soil horizon SMC structure via the throughfall mechanism when canopies' biomass distribution is highly heterogeneous.

Temporal and diurnal analysis of trace elements in the Cryospheric water at remote Laohugou basin in northeast Tibetan Plateau.

PubMed

Dong, Zhiwen; Kang, Shichang; Qin, Dahe; Qin, Xiang; Yan, Fangping; Du, Wentao; Wei, Ting

2017-03-01

An evaluation of glacial meltwater chemistry is needed under recent dramatic glacier melting when water resources might be significantly impacted. This study investigated trace elements variation in the meltwater stream, and its related aquatic environmental information, at the Laohugou (LHG) glacier basin (4260 m a.s.l.) at a remote location in northeast Tibetan Plateau. We focused on the spatial, temporal and diurnal change of trace elements during the glacier ablation period. Results showed evident elements spatial difference on the glacier surface meltwater, as most of the elements showed increased concentration at the terminus compared to higher elevations sites. Dominant elements in the meltwater were Ba, Sr and Cr, whereas elements with high enrichment factors (EFs) were Sb, Ni, Mo and Zn. Temporal change of some trace elements concentration (e.g. Sc, Cu, and Rb) indicated increasing trend with accelerated snow-ice melting, whereas others (e.g. Ni, Zn, and Pb) showed decreasing trend. We find that, trace elements showed evident diurnal change and a peak value of concentration was observed each day at about 15:00-17:00, and the diurnal change was influenced by runoff level and pH. Moreover, EFs calculations revealed that heavy metals were partially originated from regional anthropogenic sources. Overall, the accelerated diurnal and temporal snow-ice melting (with high runoff level) were correlated to increased elemental concentration, pH, EC and elemental change mode, and thus this work is of great importance for evaluating the impacts of accelerated glacier melting to meltwater chemistry and downstream ecosystem in the northeast Tibetan Plateau. Copyright © 2016 Elsevier Ltd. All rights reserved.

Societal Production and Careers of PhDs in Chemistry and Biochemistry in France and Japan

ERIC Educational Resources Information Center

Lanciano-Morandat, Caroline; Nohara, Hiroatsu

2013-01-01

Since the late 1980s, the production of PhDs has become a much-discussed political issue, and the reforms and tensions surrounding this category of graduates have gathered momentum. Vocational fields and the contents of PhD education have evolved everywhere, partly because, as academic competition has intensified, the American "graduate…

Salton Sea 1/sup 0/ x 2/sup 0/ NTMS area California and Arizona: data report (abbreviated)

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

Heffner, J.D.

1980-09-01

Surface sediment samples were collected at 997 sites. Ground water samples were collected at 76 sites. Neutron activation analysis results are given for uranium and 16 other elements in sediments, and for uranium and 9 other elements in ground water. Mass spectrometry results are given for helium in ground water. Data from ground water sites include (1) water chemistry measurements (pH, conductivity, and alkalinity) (2) physical measurements (water temperature, well description where applicable, and scintillometer reading) and (3) elemental analyses (U, Al, Br, Cl, Dy, F, He, Mg, Mn, Na and V). Data from sediment sites include (1) stream watermore » chemistry measurements from sites where water was available and (2) elemental analyses (U, Th, Hf, Al, Ce, Dy, Eu, Fe, La, Lu, Mn, Sc, Sm, Na, Ti, V, and Yb). Sample site descriptors are given. Areal distribution maps, histograms, and cumulative frequency plots for the elements listed above; U/Th and U/Hf ratios; and scintillometer readings at sediment sample sites are included. Analyses of the sediment fraction finer than 149..mu..m show high uranium values clustered in the Eagle and Chuckwalla Mountains. High uranium values in the 420 ..mu..m to 1000 ..mu..m fraction are clustered in the McCoy Mountains. Both fractions show groups of high values in the Chocolate Mountains at the Southeastern edge of the Chocolate Mountains Aerial Gunnery Range. Aerial distribution of analytical values shows that high values of many elements in both size fractions are grouped around the Eagle Mountains and the Chuckwalla Mountains. Fe, Mn, Ti, V, Sc, Hf, and the rare earth elements, all of which typically occur in high-density minerals, have higher average (log mean) concentrations in the finer fraction than in the coarser fraction.« less

Hurricane storm surge and amphibian communities in coastal wetlands of northwestern Florida

USGS Publications Warehouse

Gunzburger, M.S.; Hughes, W.B.; Barichivich, W.J.; Staiger, J.S.

2010-01-01

Isolated wetlands in the Southeastern United States are dynamic habitats subject to fluctuating environmental conditions. Wetlands located near marine environments are subject to alterations in water chemistry due to storm surge during hurricanes. The objective of our study was to evaluate the effect of storm surge overwash on wetland amphibian communities. Thirty-two wetlands in northwestern Florida were sampled over a 45-month period to assess amphibian species richness and water chemistry. During this study, seven wetlands were overwashed by storm surge from Hurricane Dennis which made landfall 10 July 2005 in the Florida panhandle. This event allowed us to evaluate the effect of storm surge overwash on water chemistry and amphibian communities of the wetlands. Specific conductance across all wetlands was low pre-storm (<100 ??S/cm), but increased post-storm at the overwashed wetlands (x?? = 7,613 ??S/cm). Increased specific conductance was strongly correlated with increases in chloride concentrations. Amphibian species richness showed no correlation with specific conductance. One month post-storm we observed slightly fewer species in overwashed compared with non-overwashed wetlands, but this trend did not continue in 2006. More species were detected across all wetlands pre-storm, but there was no difference between overwashed and non-overwashed wetlands when considering all amphibian species or adult anurans and larval anurans separately. Amphibian species richness did not appear to be correlated with pH or presence of fish although the amphibian community composition differed between wetlands with and without fish. Our results suggest that amphibian communities in wetlands in the southeastern United States adjacent to marine habitats are resistant to the effects of storm surge overwash. ?? 2010 Springer Science+Business Media B.V.

Groundwater hydrogeochemical characteristics in rehabilitated coalmine spoils

NASA Astrophysics Data System (ADS)

Gomo, M.; Masemola, E.

2016-04-01

The investigation aims to identify and describe hydrogeochemical processes controlling the evolution of groundwater chemistry in rehabilitated coalmine spoils and their overall influence on groundwater quality at a study area located in the Karoo basin of South Africa. A good understanding of the processes that controls the evolution of the mine water quality is vital for the planning, application and management of post-mining remedial actions. The study utilises scatter plots, statistical analysis, PHREEQC hydrogeochemical modelling, stoichiometric reaction ratios analysis, and the expanded Durov diagram as complimentary tools to interpret the groundwater chemistry data collected from monitoring boreholes from 1995 to 2014. Measured pH ranging between 6-8 and arithmetic mean of 7.32 shows that the groundwater system is characterised by circumneutral hydrogeochemical conditions period. Comparison of measured groundwater ion concentrations to theoretical reaction stoichiometry identifies Dolomite-Acid Mine Drainage (AMD) neutralisation as the main hydrogeochemical process controlling the evolution of the groundwater chemistry. Hydrogeochemical modelling shows that, the groundwater has temporal variations of calcite and dolomite saturation indices characterised by alternating cycles of over-saturation and under-saturation that is driven by the release of sulphate, calcium and magnesium ions from the carbonate-AMD neutralization process. Arithmetic mean concentrations of sulphate, calcium and magnesium are in the order of 762 mg/L, 141 mg/L and 108 mg/L. Calcium and magnesium ions contribute to very hard groundwater quality conditions. Classification based on total dissolved solids (TDS), shows the circumneutral water is of poor to unacceptable quality for drinking purposes. Despite its ability to prevent AMD formation and leaching of metals, the dolomite-AMD neutralisation process can still lead to problems of elevated TDS and hardness which mines should be aware of when developing water quality management plans.

Effects of blending of desalinated water with treated surface drinking water on copper and lead release.

PubMed

Liu, Haizhou; Schonberger, Kenneth D; Korshin, Gregory V; Ferguson, John F; Meyerhofer, Paul; Desormeaux, Erik; Luckenbach, Heidi

2010-07-01

This study examined effects of desalinated water on the corrosion of and metal release from copper and lead-containing materials. A jar test protocol was employed to examine metal release from copper and lead-tin coupons exposed to water chemistries with varying blending ratios of desalinated water, alkalinities, pHs and orthophosphate levels. Increasing fractions of desalinated water in the blends resulted in non-monotonic changes of copper and lead release, with generally lower metal concentrations in the presence of desalinated water, especially when its contribution increased from 80% to 100%. SEM examination showed that the increased fractions of desalinated water were associated with pronounced changes of the morphology of the corrosion scales, likely due to the influence of natural organic matter. This hypothesis was corroborated by the existence of correlations between changes of the zeta-potential of representative minerals (malachite and hydrocerussite) and metal release. For practical applications, maintaining pH at 7.8 and adding 1 mg/L orthophosphate as PO(4) were concluded to be adequate to decrease copper and lead release. Lower alkalinity of desalinated water was beneficial for blends containing 50% or more desalinated water. Copyright 2010 Elsevier Ltd. All rights reserved.

Environmental control on water quality; cases studies from Battle Mountain mining district, north-central Nevada. Chapter A.

USGS Publications Warehouse

Tuttle, Michele L.W.; Wanty, Richard B.; Berger, Byron R.; Stillings, Lisa L.

2003-01-01

The environmental controls on water quality were the focus of our study in a portion of the Battle Mountain mining district, north-central Nevada. Samples representing areas outside known mineralized areas, in undisturbed mineralized areas, and in mined areas were chemically and isotopically analyzed. The results are related to geologic, hydrologic, and climatic data. Streams in background areas outside the mineralized zones reflect normal weathering of volcanically derived rocks. The waters are generally dilute, slightly alkaline in pH, and very low in metals. As these streams flow into mineralized zones, their character changes. In undisturbed mineralized areas, discharge into streams of ground water through hydrologically conductive fractures can be traced with chemistry and, even more effectively, with sulfur isotopic composition of dissolved sulfate. Generally, these tracers are much more subtle than in those areas where mining has produced adits and mine-waste piles. The influence of drainage from these mining relicts on water quality is often dramatic, especially in unusually wet conditions. In one heavily mined area, we were able to show that the unusually wet weather in the winter and spring greatly degraded water quality. Addition of calcite to the acid, metalrich mine drainage raised the stream pH and nearly quantitatively removed the metals through coprecipitation and (or) adsorption onto oxyhydroxides. This paper is divided into four case studies used to demonstrate our results. Each addresses the role of geology, hydrology, mining activity and (or) local climate on water quality. Collectively, they provide a comprehensive look at the important factors affecting water quality in this portion of the Battle Mountain mining district.

The effects of salinity, pH, and dissolved organic matter on acute copper toxicity to the rotifer, Brachionus plicatilis ("L" strain).

PubMed

Arnold, W R; Diamond, R L; Smith, D S

2010-08-01

This paper presents data from original research for use in the development of a marine biotic ligand model and, ultimately, copper criteria for the protection of estuarine and marine organisms and their uses. Ten 48-h static acute (unfed) copper toxicity tests using the euryhaline rotifer Brachionus plicatilis ("L" strain) were performed to assess the effects of salinity, pH, and dissolved organic matter (measured as dissolved organic carbon; DOC) on median lethal dissolved copper concentrations (LC50). Reconstituted and natural saltwater samples were tested at seven salinities (6, 11, 13, 15, 20, 24, and 29 g/L), over a pH range of 6.8-8.6 and a range of dissolved organic carbon of <0.5-4.1 mg C/L. Water chemistry analyses (alkalinity, calcium, chloride, DOC, hardness, magnesium, potassium, sodium, salinity, and temperature) are presented for input parameters to the biotic ligand model. In stepwise multiple regression analysis of experimental results where salinity, pH, and DOC concentrations varied, copper toxicity was significantly related only to the dissolved organic matter content (pH and salinity not statistically retained; alpha=0.05). The relationship of the 48-h dissolved copper LC50 values and dissolved organic carbon concentrations was LC50 (microg Cu/L)=27.1xDOC (mg C/L)1.25; r2=0.94.

Degradation of dichlorvos using hydrodynamic cavitation based treatment strategies.

PubMed

Joshi, Ravi K; Gogate, Parag R

2012-05-01

The degradation of an aqueous solution of dichlorvos, a commonly used pesticide in India, has been systematically investigated using hydrodynamic cavitation reactor. All the experiments have been carried out using a 20 ppm solution of commercially available dichlorvos. The effect of important operating parameters such as inlet pressure (over a range 3-6 bar), temperature (31 °C, 36 °C and 39 °C) and pH (natural pH = 5.7 and acidic pH = 3) on the extent of degradation has been investigated initially. It has been observed that an optimum value of pressure gives maximum degradation whereas low temperature and pH of 3 are favorable. Intensification studies have been carried out using different additives such as hydrogen peroxide, carbon tetrachloride, and Fenton's reagent. Use of hydrogen peroxide and carbon tetrachloride resulted in the enhancement of the extent of degradation at optimized conditions but significant enhancement was obtained with the combined use of hydrodynamic cavitation and Fenton's chemistry. The maximum extent of degradation as obtained by using a combination of hydrodynamic cavitation and Fenton's chemistry was 91.5% in 1h of treatment time. The present work has conclusively established that hydrodynamic cavitation in combination with Fenton's chemistry can be effectively used for the degradation of dichlorvos. Copyright © 2011 Elsevier B.V. All rights reserved.

Natural weathering in dry disposed ash dump: Insight from chemical, mineralogical and geochemical analysis of fresh and unsaturated drilled cores.

PubMed

Akinyemi, S A; Akinlua, A; Gitari, W M; Khuse, N; Eze, P; Akinyeye, R O; Petrik, L F

2012-07-15

Some existing alternative applications of coal fly ash such as cement manufacturing; road construction; landfill; and concrete and waste stabilisation use fresh ash directly collected from coal-fired power generating stations. Thus, if the rate of usage continues, the demand for fresh ash for various applications will exceed supply and use of weathered dry disposed ash will become necessary alternative. As a result it's imperative to understand the chemistry and pH behaviour of some metals inherent in dry disposed fly ash. The bulk chemical composition as determined by XRF analysis showed that SiO2, Al2O3 and Fe2O3 were the major oxides in fresh ash and unsaturated weathered ashes. The unsaturated weathered ashes are relatively depleted in CaO, Fe2O3, TiO2, SiO2, Na2O and P2O5 due to dissolution and hydrolysis caused by chemical interaction with ingressing CO2 from the atmosphere and infiltrating rain water. Observed accumulations of Fe2O3, TiO2, CaO, K2O, Na2O and SO3 and Zn, Zr, Sr, Pb, Ni, Cr and Co in the lower layers indicate progressive downward movement through the ash dump though at a slow rate. The bulk mineralogy of unsaturated weathered dry disposed ash, as determined by XRD analysis, revealed quartz and mullite as the major crystalline phases; while anorthite, hematite, enstatite, lime, calcite, and mica were present as minor mineral phases. Pore water chemistry revealed a low concentration of readily soluble metals in unsaturated weathered ashes in comparison with fresh ash, which shows high leachability. This suggests that over time the precipitation of transient minor secondary mineral phases; such as calcite and mica might retard residual metal release from unsaturated weathered ash. Chloride and sulphate species of the water soluble extracts of weathered ash are at equilibrium with Na+ and K+; these demonstrate progressive leaching over time and become supersaturated at the base of unsaturated weathered ash. This suggests that the ash dump does not encapsulate the salt or act as a sustainable salt sink due to over time reduction in pore water pH. The leaching behaviours of Ca, Mg, Na+, K+, Se, Cr and Sr are controlled by the pH of the leachant in both fresh and unsaturated weathered ash. Other trace metals like As, Mo and Pb showed amphoteric behaviour with respect to the pH of the leachant. The precipitation of minor quantities of secondary mineral phases in the unsaturated weathered ash has significant effects on the acid susceptibility and leaching patterns of chemical species in comparison with fresh ash. The unsaturated weathered ash had lower buffering capacity at neutral pH (7.94-8.00) compared to fresh (unweathered) ash. This may be due to the initial high leaching/flushing of soluble basic buffering constituents from fly ash after disposal. The overall results of the acid susceptibility tests suggest that both fresh ash and unsaturated weathered ash would release a large percentage of their chemical species when in contact with slightly acidified rain. Proper management of ash dumps is therefore essential to safeguard the environmental risks of water percolation in different fly ashes behaviour. Copyright © 2012 Elsevier Ltd. All rights reserved.

The pH of water from various sources: an overview for recommendation for patients with atopic dermatitis.

PubMed

Kulthanan, Kanokvalai; Nuchkull, Piyavadee; Varothai, Supenya

2013-07-01

Patients with atopic dermatitis (AD) have increased susceptibility to irritants. Some patients have questions about types of water for bathing or skin cleansing. We studied the pH of water from various sources to give an overview for physicians to recommend patients with AD. Water from various sources was collected for measurement of the pH using a pH meter and pH-indicator strips. Bottled drinking still water had pH between 6.9 and 7.5 while the sparkling type had pH between 4.9 and 5.5. Water derived from home water filters had an approximate pH of 7.5 as same as tap water. Swimming pool water had had pH between 7.2 and 7.5 while seawater had a pH of 8. Normal saline and distilled water had pH of 5.4 and 5.7, respectively. Facial mineral water had pH between 7.5 and 8, while facial makeup removing water had an acidic pH. Normal saline, distilled water, bottled sparkling water and facial makeup removing water had similar pH to that of normal skin of normal people. However, other factors including benefits of mineral substances in the water in terms of bacteriostatic and anti-inflammation should be considered in the selection of cleansing water.

The pH of water from various sources: an overview for recommendation for patients with atopic dermatitis

PubMed Central

Kulthanan, Kanokvalai; Varothai, Supenya

2013-01-01

Background Patients with atopic dermatitis (AD) have increased susceptibility to irritants. Some patients have questions about types of water for bathing or skin cleansing. Objective We studied the pH of water from various sources to give an overview for physicians to recommend patients with AD. Methods Water from various sources was collected for measurement of the pH using a pH meter and pH-indicator strips. Results Bottled drinking still water had pH between 6.9 and 7.5 while the sparkling type had pH between 4.9 and 5.5. Water derived from home water filters had an approximate pH of 7.5 as same as tap water. Swimming pool water had had pH between 7.2 and 7.5 while seawater had a pH of 8. Normal saline and distilled water had pH of 5.4 and 5.7, respectively. Facial mineral water had pH between 7.5 and 8, while facial makeup removing water had an acidic pH. Conclusion Normal saline, distilled water, bottled sparkling water and facial makeup removing water had similar pH to that of normal skin of normal people. However, other factors including benefits of mineral substances in the water in terms of bacteriostatic and anti-inflammation should be considered in the selection of cleansing water. PMID:23956962

Sludge-Derived Biochar for Arsenic(III) Immobilization: Effects of Solution Chemistry on Sorption Behavior.

PubMed

Zhang, Weihua; Zheng, Juan; Zheng, Pingping; Tsang, Daniel C W; Qiu, Rongliang

2015-07-01

Recycling sewage sludge by pyrolysis has attracted increasing attention for pollutant removal from wastewater and soils. This study scrutinized As(III) sorption behavior on sludge-derived biochar (SDBC) under different pyrolysis conditions and solution chemistry. The SDBC pyrolyzed at a higher temperature showed a lower As(III) sorption capacity and increasingly nonlinear isotherm due to loss of surface sites and deoxygenation-dehydrogenation. The Langmuir sorption capacity on SDBC (3.08-6.04 mg g) was comparable to other waste-derived sorbents, with the highest As(III) sorption on SDBC pyrolyzed at 400°C for 2 h. The As(III) sorption kinetics best fit with the pseudo-second-order equation, thus suggesting the significance of the availability of surface sites and initial concentration. Sorption of As(III) was faster than that of Cr(VI) but slower than that of Pb(II), which was attributed to their differences in molar volume (correlated to diffusion coefficients) and sorption mechanisms. The X-ray photoelectron spectra revealed an increase of oxide oxygen (O) with a decrease of sorbed water, indicative of ligand exchange with hydroxyl groups on SDBC surfaces. The As(III) sorption was not pH dependent in acidic-neutral range (pH < 8) due to the buffering capacity and surface characteristics of the SDBC; however, sorption was promoted by increasing pH in the alkaline range (pH > 8) because of As(III) speciation in solution. An increasing ionic strength (0.001-0.1 mol L) facilitated As(III) sorption, indicating the predominance of ligand exchange over electrostatic interactions, while high concentrations (0.1 mol L) of competing anions (fluoride, sulfate, carbonate, and phosphate) inhibited As(III) sorption. These results suggest that SDBC is applicable for As(III) immobilization in most environmentally relevant conditions. Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.

Evaluating remedial alternatives for an acid mine drainage stream: Application of a reactive transport model

USGS Publications Warehouse

Runkel, R.L.; Kimball, B.A.

2002-01-01

A reactive transport model based on one-dimensional transport and equilibrium chemistry is applied to synoptic data from an acid mine drainage stream. Model inputs include streamflow estimates based on tracer dilution, inflow chemistry based on synoptic sampling, and equilibrium constants describing acid/base, complexation, precipitation/dissolution, and sorption reactions. The dominant features of observed spatial profiles in pH and metal concentration are reproduced along the 3.5-km study reach by simulating the precipitation of Fe(III) and Al solid phases and the sorption of Cu, As, and Pb onto freshly precipitated iron-(III) oxides. Given this quantitative description of existing conditions, additional simulations are conducted to estimate the streamwater quality that could result from two hypothetical remediation plans. Both remediation plans involve the addition of CaCO3 to raise the pH of a small, acidic inflow from ???2.4 to ???7.0. This pH increase results in a reduced metal load that is routed downstream by the reactive transport model, thereby providing an estimate of post-remediation water quality. The first remediation plan assumes a closed system wherein inflow Fe(II) is not oxidized by the treatment system; under the second remediation plan, an open system is assumed, and Fe(II) is oxidized within the treatment system. Both plans increase instream pH and substantially reduce total and dissolved concentrations of Al, As, Cu, and Fe(II+III) at the terminus of the study reach. Dissolved Pb concentrations are reduced by ???18% under the first remediation plan due to sorption onto iron-(III) oxides within the treatment system and stream channel. In contrast, iron(III) oxides are limiting under the second remediation plan, and removal of dissolved Pb occurs primarily within the treatment system. This limitation results in an increase in dissolved Pb concentrations over existing conditions as additional downstream sources of Pb are not attenuated by sorption.

Sensitivity of Ocean Chemistry and Oxygen Change to the Uncertainty in Climate Change

NASA Astrophysics Data System (ADS)

Cao, L.; Wang, S.; Zheng, M.; Zhang, H.

2014-12-01

With increasing atmospheric CO2 and climate change, global ocean is undergoing substantial physical and biogeochemical changes. In particular, changes in ocean oxygen and carbonate chemistry have great implication for marine biota. There is considerable uncertainty in the projections of future climate change, and it is unclear how the uncertainty in climate change would affect the projection of ocean oxygen and carbonate chemistry. To examine the effect of climate change on ocean oxygen and carbonate chemistry, we used an Earth system model of intermediate complexity to perform simulations that are driven by atmospheric CO2 concentration pathway of RCP 8.5 with climate sensitivity varying from 0.0°C to 4.5 °C. Climate change affects carbonate chemistry and oxygen mainly through its impact on ocean temperature, ocean ventilation, and concentration of dissolved inorganic carbon and alkalinity. Our simulations show that climate change mitigates the decrease of carbonate ions at the ocean surface but has negligible effect on surface ocean pH. Averaged over the whole ocean, climate change acts to decrease oxygen concentration but mitigates the CO2-induced reduction of carbonate ion and pH. In our simulations, by year 2500, every degree increase of climate sensitivity warms the ocean by 0.8 °C and reduces ocean-mean dissolved oxygen concentration by 5.0%. Meanwhile, every degree increase of climate sensitivity buffers CO2-induced reduction in ocean-mean carbonate ion concentration and pH by 3.4% and 0.02 units, respectively. Our study demonstrates different sensitivities of ocean temperature, carbonate chemistry, and oxygen, in terms of both the sign and magnitude, to the amount of climate change, which have great implications for understanding the response of ocean biota to climate change.

Carbonate system parameters of an algal-dominated reef along West Maui

NASA Astrophysics Data System (ADS)

Prouty, Nancy G.; Yates, Kimberly K.; Smiley, Nathan; Gallagher, Chris; Cheriton, Olivia; Storlazzi, Curt D.

2018-04-01

Constraining coral reef metabolism and carbon chemistry dynamics are fundamental for understanding and predicting reef vulnerability to rising coastal CO2 concentrations and decreasing seawater pH. However, few studies exist along reefs occupying densely inhabited shorelines with known input from land-based sources of pollution. The shallow coral reefs off Kahekili, West Maui, are exposed to nutrient-enriched, low-pH submarine groundwater discharge (SGD) and are particularly vulnerable to the compounding stressors from land-based sources of pollution and lower seawater pH. To constrain the carbonate chemistry system, nutrients and carbonate chemistry were measured along the Kahekili reef flat every 4 h over a 6-day sampling period in March 2016. Abiotic process - primarily SGD fluxes - controlled the carbonate chemistry adjacent to the primary SGD vent site, with nutrient-laden freshwater decreasing pH levels and favoring undersaturated aragonite saturation (Ωarag) conditions. In contrast, diurnal variability in the carbonate chemistry at other sites along the reef flat was driven by reef community metabolism. Superimposed on the diurnal signal was a transition during the second sampling period to a surplus of total alkalinity (TA) and dissolved inorganic carbon (DIC) compared to ocean endmember TA and DIC measurements. A shift from positive net community production and positive net community calcification to negative net community production and negative net community calcification was identified. This transition occurred during a period of increased SGD-driven nutrient loading, lower wave height, and reduced current speeds. This detailed study of carbon chemistry dynamics highlights the need to incorporate local effects of nearshore oceanographic processes into predictions of coral reef vulnerability and resilience.

Sensitivity to acidification of subalpine ponds and lakes in north-western Colorado

USGS Publications Warehouse

Campbell, D.H.; Muths, E.; Turk, J.T.; Corn, P.S.

2004-01-01

Although acidifying deposition in western North America is lower than in many parts of the world, many high-elevation ecosystems there are extremely sensitive to acidification. Previous studies determined that the Mount Zirkel Wilderness Area (MZWA) has the most acidic snowpack and aquatic ecosystems that are among the most sensitive in the region. In this study, spatial and temporal variability of ponds and lakes in and near the MZWA were examined to determine their sensitivity to acidification and the effects of acidic deposition during and after snowmelt. Within the areas identified as sensitive to acidification based on bedrock types, there was substantial variability in acid-neutralizing capacity (ANC), which was related to differences in hydrological flowpaths that control delivery of weathering products to surface waters. Geological and topographic maps were of limited use in predicting acid sensitivity because their spatial resolution was not fine enough to capture the variability of these attributes for lakes and ponds with small catchment areas. Many of the lakes are sensitive to acidification (summer and autumn ANC < 100 µeq L−1), but none of them appeared to be threatened immediately by episodic or chronic acidification. In contrast, 22 ponds had minimum ANC < 30 µeq L−1, indicating that they are extremely sensitive to acidic deposition and could be damaged by episodic acidification, although net acidity (ANC < 0) was not measured in any of the ponds during the study. The lowest measured pH value was 5·4, and pH generally remained less than 6·0 throughout early summer in the most sensitive ponds, indicating that biological effects of acidification are possible at levels of atmospheric deposition that occurred during the study. The aquatic chemistry of lakes was dominated by atmospheric deposition and biogeochemical processes in soils and shallow ground water, whereas the aquatic chemistry of ponds was also affected by organic acids and biogeochemical processes in the water column and at the sediment–water interface. These results indicate that conceptual and mechanistic acidification models that have been developed for lakes and streams may be inadequate for predicting acidification in less-understood systems such as ponds.

Adventures in STEM: Lessons in Water Chemistry From Elementary School to Graduate School

NASA Astrophysics Data System (ADS)

Dittrich, T. M.

2014-12-01

I will present the accumulation of over 10 years of experience teaching STEM subjects to students ranging from 1st grade to graduate school. I was fortunate to gain a lot of valuable teaching experience while in graduate school in Boulder, CO and so many of my experiences center on opportunities for connecting with students in the field in CO. 3rd-5th grade field hikes - While helping at Jamestown Elementary School, I led hikes with a 3-5th grade class to an abandoned flourospar mine where the students were able to pick up beautiful purple fluorite crystals from the ground while discussing how mining works. During the hike back, we used field meters to measure the pH and conductivity of the stream and discussed the need to balance society's need for metals with the harmful effects of acid mine drainage. 9th, 10th grade STEM Academy at Skyline High School - During an NSF-sponsored fellowship, I had the opportunity to teach a STEM class to 9th and 10th graders where we used the engineering design process to a) design a tool to help a handicapped 3rd grader use the drinking fountain by herself and b) design a treatment system for cleaning up acid mine drainage. Undergraduate and Graduate Environmental Water Chemistry Field Trip - Students had the opportunity to tour two local mine sites to collect contaminated water that would be used in class for alkalinity titrations and pH, sulfate, and hardness measurements. They also collected water samples upstream and at multiple points downstream of a wastewater treatment plan and measured and graphed the dissolved oxygen "sag" in the river. My main teaching philosophy has two parts: 1) assume the students know nothing and 2) assume the students are even smarter than you think you are. This informs my approach to field trips by always starting from the beginning, but also not oversimplifying the topic. 1st graders on their best day can be very similar to graduate students on their worst.

Formation of aqueous-phase sulfate during the haze period in China: Kinetics and atmospheric implications

NASA Astrophysics Data System (ADS)

Zhang, Haijie; Chen, Shilu; Zhong, Jie; Zhang, Shaowen; Zhang, Yunhong; Zhang, Xiuhui; Li, Zesheng; Zeng, Xiao Cheng

2018-03-01

Sulfate is one of the most important components in the aerosol due to its key role in air pollution and global climate change. Recent work has suggested that reactive nitrogen chemistry in aqueous water can explain the missing source of sulfate in the aqueous water. Herein, we have mapped out the energy profile of the oxidization process of SO2 leading from NO2 and two feasible three-step mechanisms have been proposed. For the oxidation of HOSO2- and HSO3- by the dissolved NO2 in weakly acidic and neutral aerosol (pH ≤ 7), the main contribution to the missing sulfate production comes from the oxidation of HOSO2-. The whole process is a self-sustaining process. For the oxidation of SO32- in alkaline aerosol (pH > 7), the third step - decomposition step of H2O or hydrolysis of SO3 step which are two parallel processes are the rate-limiting steps. The present results are of avail to better understand the missing source of sulfate in the aerosol and hence may lead to better science-based solutions for resolving the severe haze problems in China.

Effect of water chemistry on the aggregation and photoluminescence behavior of carbon dots.

PubMed

Bayati, Mohamed; Dai, Jingjing; Zambrana, Austin; Rees, Chloe; Fidalgo de Cortalezzi, Maria

2018-03-01

Carbon dots are rapidly emerging carbon-based nanomaterials that, due to their growing applications, will inevitable find their way to natural waters; however, their environmental fate is mostly unknown. Carbon dots with different surface functionality were fabricated and characterized by TEM and FT-IR. Their surface charge, given by the zeta potential, and their hydrodynamic diameter in suspension were investigated under a variety of environmentally relevant conditions. The effect of ionic strength was studied in the presence of monovalent (NaCl) and divalent (CaCl 2 ) cations, for pH levels from 3 to 11; humic acid was used as a model for dissolved natural organic matter. Total potential energies of interactions were modeled by classical DLVO theory. The experimental results showed that water chemistry altered the surface charge of the nanomaterials, but their hydrodynamic size could not be correlated to those changes. Evidence of specific interactions was found for the amino functionalized particles in most cases, as well as the plain carbon dots in the presence of Ca 2+ and humic acid. Nanoparticles remained largely stable in suspension, with some exception at the highest ionic strength considered. DLVO theory did not adequately capture the aggregation behavior of the system. Moreover, cation and/or humic acid adsorption negatively affected the emission intensity of the particles, suggesting limitations to their use in natural water sensing applications. The particular stability shown by the carbon dots results in exposure to organisms in the water column and the possibility of contamination transported to significant distances from their source. Copyright © 2017. Published by Elsevier B.V.

Assessment of typical natural processes and human activities' impact on the quality of drinking water.

PubMed

Kurilić, Sanja Mrazovac; Ulniković, Vladanka Presburger; Marić, Nenad; Vasiljević, Milenko

2015-11-01

This paper provides insight into the quality of groundwater used for public water supply on the territory of Temerin municipality (Vojvodina, Serbia). The following parameters were measured: color, turbidity, pH, KMnO4 consumption, total dissolved solids (TDS), EC, NH4+, Cl-, NO2-, NO3-, Fe, Mn, As, Ca2+, Mg2+, SO4(2-), HCO3-, K+, and Na+. The correlations and ratios among parameters that define the chemical composition were determined aiming to identify main processes that control the formation of the chemical composition of the analyzed waters. Groundwater from three analyzed sources is Na-HCO3 type. Elevated organic matter content, ammonium ion content, and arsene content are characteristic for these waters. The importance of organic matter decay is assumed by positive correlation between organic matter content and TDS, and HCO3- content. There is no evidence that groundwater chemistry is determined by the depth of captured aquifer interval. The main natural processes that control the chemistry of all analyzed water are cation exchange and feldspar weathering. The dominant cause of As concentration in groundwater is the use of mineral fertilizers and of KMnO4 in urban area. The concentration of As and KMnO4 in the observed sources is inversely proportional to the distance from agricultural land and urban area. 2D model of distribution of As and KMnO4 is done, and it is applicable in detecting sources of pollution. By using this model, we can quantify the impact of certain pollutants on unfavorable content of some parameters in groundwater.

77 FR 66625 - National Institute of General Medical Sciences; Notice of Closed Meetings

Federal Register 2010, 2011, 2012, 2013, 2014

2012-11-06

...: Helen R. Sunshine, Ph.D., Chief, Office of Scientific Review, National Institute of General Medical...: Robert Horowits, Ph.D., Senior Investigator, National Institute of General Medical Sciences, National... Chemistry Research; 93.862, Genetics and [[Page 66626

Sol-gel method for encapsulating molecules

DOEpatents

Brinker, C. Jeffrey; Ashley, Carol S.; Bhatia, Rimple; Singh, Anup K.

2002-01-01

A method for encapsulating organic molecules, and in particular, biomolecules using sol-gel chemistry. A silica sol is prepared from an aqueous alkali metal silicate solution, such as a mixture of silicon dioxide and sodium or potassium oxide in water. The pH is adjusted to a suitably low value to stabilize the sol by minimizing the rate of siloxane condensation, thereby allowing storage stability of the sol prior to gelation. The organic molecules, generally in solution, is then added with the organic molecules being encapsulated in the sol matrix. After aging, either a thin film can be prepared or a gel can be formed with the encapsulated molecules. Depending upon the acid used, pH, and other processing conditions, the gelation time can be from one minute up to several days. In the method of the present invention, no alcohols are generated as by-products during the sol-gel and encapsulation steps. The organic molecules can be added at any desired pH value, where the pH value is generally chosen to achieve the desired reactivity of the organic molecules. The method of the present invention thereby presents a sufficiently mild encapsulation method to retain a significant portion of the activity of the biomolecules, compared with the activity of the biomolecules in free solution.

Dispersion of phyllosilicates in aqueous suspensions: role of the nature and amount of surfactant.

PubMed

Houta, Nadia; Lecomte-Nana, Gisèle-Laure; Tessier-Doyen, Nicolas; Peyratout, Claire

2014-07-01

The present work aims at investigating the effect of pH values and additives on the dispersion of two 1:1 dioctahedral phyllosilicates in the presence of water. Two model clays are used for this purpose, BIP kaolin and NZCC halloysite, presenting the same surface chemistry but different morphologies. The effect of sodium hexametaphosphate, sodium silicate and sodium carbonate is discussed. Kaolin and halloysite powders were first characterized using X-ray diffraction, thermogravimetric analysis and scanning electron microscopy. Subsequently, suspensions containing 8 mass% of each clay were prepared with or without additives. Experimental measurements regarding the pH values, the zeta potential and the rheological behavior were performed to determine the most suitable additive. Results show that the conformation of halloysite particles changes regarding pH values of suspensions and is strongly related to the surface charges of these particles. At their natural pH values, halloysite and kaolin suspensions exhibit zeta potentials equal to -50 and -20 mV respectively. This trend indicates that halloysite-based suspensions are well dispersed compared to kaolin-based suspensions. Sodium hexametaphosphate is the most suitable dispersant for both clays. The rheological characterization regarding further applications in casting process indicates a shear-thinning behavior for all studied compositions. Copyright © 2014 Elsevier Inc. All rights reserved.

Impact of Long-Range Transported African Dust Events on Cloud Composition and Physical Properties at a Caribbean Tropical Montane Cloud Forest

NASA Astrophysics Data System (ADS)

Valle-Diaz, C. J.; Torres-Delgado, E.; Lee, T.; Collett, J. L.; Cuadra-Rodriguez, L. A.; Prather, K. A.; Spiegel, J.; Eugster, W.

2012-12-01

We studied the impact of long-range transported African Dust (LRTAD) on cloud composition and properties at the Caribbean tropical montane cloud forest (TMCF) of Pico del Este (PE), as part of the Puerto Rico African Dust and Clouds Study (PRADACS). Here we present results from measurements performed in July 2011. Bulk chemical analysis of cloud water and rainwater showed pH and conductivity higher in the presence of dust. pH and conductivity were also higher for larger cloud droplets (size cut of 17 μm at 50% efficiency) suggesting a higher content of dust in this fraction. The concentration of the water-soluble ions in rainwater was found to be lower than for cloud water. This in turn translates to higher pH and lower conductivity. African dust influence at PE was confirmed by the presence of nss-Ca, Fe, Mg, Na, and Al in cloud/rain water, and inferred by HYSPLIT trajectories and the satellite images from the Saharan Air Layer (SAL). Interstitial single-particle size and chemistry measured using aerosol time-of-flight mass spectrometry revealed mostly sea-salt particles (Na, Cl, Ca) and dust particles (Fe, Ti, Mg, nss-Ca). Anthropogenic influence detected as the presence of EC, a tracer for combustion processes, was found to be fairly small according to ATOFMS measurements. An increase of total organic carbon, total nitrogen, and dissolved organic carbon was observed during LRTAD events. Cloud droplet distributions revealed that LRTAD can lead to more numerous, but smaller cloud droplets (around 8 μm in average) at PE. However, total liquid water content appeared to be unaffected by this shift of droplet sizes. Overall, differences in the studied physicochemical properties of aerosols and clouds during dust and non-dust events were observed. Our results show that during LRTAD events, aerosol-cloud-precipitation interactions are altered at PE. Detailed results will be presented at the meeting.

Evaluating the impacts of membrane type, coating, fouling, chemical properties and water chemistry on reverse osmosis rejection of seven nitrosoalklyamines, including NDMA.

PubMed

Steinle-Darling, Eva; Zedda, Marco; Plumlee, Megan H; Ridgway, Harry F; Reinhard, Martin

2007-09-01

Reverse osmosis (RO) treatment has been found to be effective for a wide range of organics but generally small, polar, uncharged molecules such as N-nitrosodimethylamine (NDMA) can be poorly rejected. The rejection of seven N-nitrosoalkylamines with molecular masses in the range of 78-158Da, including NDMA, N-nitrosodiethylamine (NDEA), N-nitrosomethylethylamine (NMEA), N-nitrosodipropylamine (NDPA), N-nitrosodibutylamine (NDBA), N-nitrosopyrrolidine (NPyr), N-nitrosopiperidine (NPip) by three commercial brackish-water reverse osmosis membranes was studied in flat-sheet cells under cross-flow conditions. The membranes used were ESPA3 (Hydranautics), LFC3 (Hydranautics) and BW-30 (Dow/Filmtec), commonly used in water reuse applications. The effects of varying ionic strength and pH, dip-coating membranes with PEBAX 1657, a hydrophilic polymer, and artificial fouling with alginate on nitrosamine rejection were quantified. Rejection in deionized (DI) water increased with molecular mass from 56 to 70% for NDMA, to 80-91% for NMEA, 89-97% for NPyr, 92-98% for NDEA, and to beyond the detection limits for NPip, NDPA and NDBA. For the nitrosamines with quantifiable transmission, linear correlations (r(2)>0.97) were found between the number of methyl groups and the log(transmission), with factor 0.35 to 0.55 decreases in transmission per added methyl group. A PEBAX coating lowered the ESPA3 rejection of NDMA by 11% but increased the LFC3 and BW30 rejection by 6% and 15%, respectively. Artificially fouling ESPA3 membrane coupons with 170g/m(2) alginate decreased the rejection of NDMA by 18%. A feed concentration of 100mM NaCl decreased rejection of NDMA by 15% and acidifying the DI water feed to pH=3 decreased the rejection by 5%, whereas increasing the pH to 10 did not have a significant (p<0.05) effect.

McMurdo Dry Valleys, Antarctica - A Mars Phoenix Mission Analog

NASA Technical Reports Server (NTRS)

Tamppari, L. K.; Anderson, R. M.; Archer, D.; Douglas, S.; Kounaves, S. P.; McKay, C. P.; Ming, Douglas W.; Moore, Q.; Quinn, J. E.; Smith, P. H.;

The effect of acidification on the bioavailability and electrochemical lability of zinc in seawater.

PubMed

Kim, Ja-Myung; Baars, Oliver; Morel, François M M

2016-11-28

A poorly studied but potentially important consequence of the CO 2 -induced acidification of the surface ocean is a possible change in the bioavailability of trace metals, which play a critical role in the productivity and population dynamics of marine ecosystems. We report laboratory and field experiments designed to compare quantitatively the effects of acidification on the bioavailability of Zn, a metal essential to the growth of phytoplankton and on the extent of its complexation by model and natural ligands. We observed a good correspondence between the effects of pH on the rate of Zn uptake by a model diatom and the chemical lability of Zn measured by anodic stripping voltammetry (ASV). In model laboratory systems, the chemical lability and the bioavailability of Zn could either increase or decrease at low pH depending on the mix of complexing ligands. In a sample of coastal surface water, we observed similar increases in the ASV-labile and bioavailable Zn concentrations upon acidification, a result contrary to previous observations. These results, which can likely be generalized to other bioactive trace metals, mutatis mutandis , demonstrate the intricacy of the effects of ocean acidification on the chemistry and the ecology of surface seawater.This article is part of the themed issue 'Biological and climatic impacts of ocean trace element chemistry'. © 2016 The Author(s).

Seasonal variation of carcass decomposition and gravesoil chemistry in a cold (Dfa) climate.

PubMed

Meyer, Jessica; Anderson, Brianna; Carter, David O

2013-09-01

It is well known that temperature significantly affects corpse decomposition. Yet relatively few taphonomy studies investigate the effects of seasonality on decomposition. Here, we propose the use of the Köppen-Geiger climate classification system and describe the decomposition of swine (Sus scrofa domesticus) carcasses during the summer and winter near Lincoln, Nebraska, USA. Decomposition was scored, and gravesoil chemistry (total carbon, total nitrogen, ninhydrin-reactive nitrogen, ammonium, nitrate, and soil pH) was assessed. Gross carcass decomposition in summer was three to seven times greater than in winter. Initial significant changes in gravesoil chemistry occurred following approximately 320 accumulated degree days, regardless of season. Furthermore, significant (p < 0.05) correlations were observed between ammonium and pH (positive correlation) and between nitrate and pH (negative correlation). We hope that future decomposition studies employ the Köppen-Geiger climate classification system to understand the seasonality of corpse decomposition, to validate taphonomic methods, and to facilitate cross-climate comparisons of carcass decomposition. © 2013 American Academy of Forensic Sciences.

Uncertainties in water chemistry in disks: An application to TW Hydrae

NASA Astrophysics Data System (ADS)

Kamp, I.; Thi, W.-F.; Meeus, G.; Woitke, P.; Pinte, C.; Meijerink, R.; Spaans, M.; Pascucci, I.; Aresu, G.; Dent, W. R. F.

2013-11-01

Context. This paper discusses the sensitivity of water lines to chemical processes and radiative transfer for the protoplanetary disk around TW Hya. The study focuses on the Herschel spectral range in the context of new line detections with the PACS instrument from the Gas in Protoplanetary Systems project (GASPS). Aims: The paper presents an overview of the chemistry in the main water reservoirs in the disk around TW Hya. It discusses the limitations in the interpretation of observed water line fluxes. Methods: We use a previously published thermo-chemical Protoplanetary Disk Model (ProDiMo) of the disk around TW Hya and study a range of chemical modeling uncertainties: metallicity, C/O ratio, and reaction pathways and rates leading to the formation of water. We provide results for the simplified assumption of Tgas = Tdust to quantify uncertainties arising for the complex heating/cooling processes of the gas and elaborate on limitations due to water line radiative transfer. Results: We report new line detections of p-H2O (322-211) at 89.99 μm and CO J = 18-17 at 144.78 μm for the disk around TW Hya. Disk modeling shows that the far-IR fine structure lines ([O i], [C ii]) and molecular submm lines are very robust to uncertainties in the chemistry, while the water line fluxes can change by factors of a few. The water lines are optically thick, sub-thermally excited and can couple to the background continuum radiation field. The low-excitation water lines are also sensitive to uncertainties in the collision rates, e.g. with neutral hydrogen. The gas temperature plays an important role for the [O i] fine structure line fluxes, the water line fluxes originating from the inner disk as well as the high excitation CO, CH+ and OH lines. Conclusions: Due to their sensitivity on chemical input data and radiative transfer, water lines have to be used cautiously for understanding details of the disk structure. Water lines covering a wide range of excitation energies provide access to the various gas phase water reservoirs (inside and outside the snow line) in protoplanetary disks and thus provide important information on where gas-phase water is potentially located. Experimental and/or theoretical collision rates for H2O with atomic hydrogen are needed to diminish uncertainties from water line radiative transfer. Herschel is an ESA space observatory with science instruments provided by European-led Principal Investigator consortia and with important participation from NASA.Appendices are available in electronic form at http://www.aanda.org

The Conjugate Acid-Base Chart.

ERIC Educational Resources Information Center

Treptow, Richard S.

1986-01-01

Discusses the difficulties that beginning chemistry students have in understanding acid-base chemistry. Describes the use of conjugate acid-base charts in helping students visualize the conjugate relationship. Addresses chart construction, metal ions, buffers and pH titrations, and the organic functional groups and nonaqueous solvents. (TW)

Synthesis of Some "Cobaloxime" Derivatives: A Demonstration of "Umpolung" in the Reactivity of an Organometallic Complex

NASA Astrophysics Data System (ADS)

Jameson, Donald L.; Grzybowski, Joseph J.; Hammels, Deb E.; Castellano, Ronald K.; Hoke, Molly E.; Freed, Kimberly; Basquill, Sean; Mendel, Angela; Shoemaker, William J.

1998-04-01

This article describes a four-reaction sequence for the synthesis of two organometallic "cobaloxime" derivatives. The concept of "Umpolung" or reversal of reactivity is demonstrated in the preparation of complexes. The complex Co(dmgH)2(4-t-BuPy)Et is formed by the reaction of a cobalt (I) intermediate (cobalt in the role of nucleophile) with ethyl iodide. The complex Co(dmgH)2(4-t-BuPy)Ph is formed by the reaction of PhMgBr with a cobalt (III) intermediate (cobalt in the role of electrophile). All the products contain cobalt in the diamagnetic +3 oxidation state and are readily characterized by proton and carbon NMR. The four reaction sequence may be completed in two 4-hour lab periods. Cobaloximes are well known as model complexes for Vitamin B-12 and the experiment exposes students to aspects of classical coordination chemistry, organometallic chemistry and bioinorganic chemistry. The experiment also illustrates an important reactivity parallel between organic and organometallic chemistry.

Impact of seawater acidification on pH at the tissue–skeleton interface and calcification in reef corals

PubMed Central

Venn, Alexander A.; Tambutté, Eric; Holcomb, Michael; Laurent, Julien; Allemand, Denis; Tambutté, Sylvie

2013-01-01

Insight into the response of reef corals and other major marine calcifiers to ocean acidification is limited by a lack of knowledge about how seawater pH and carbonate chemistry impact the physiological processes that drive biomineralization. Ocean acidification is proposed to reduce calcification rates in corals by causing declines in internal pH at the calcifying tissue–skeleton interface where biomineralization takes place. Here, we performed an in vivo study on how partial-pressure CO2-driven seawater acidification impacts intracellular pH in coral calcifying cells and extracellular pH in the fluid at the tissue–skeleton interface [subcalicoblastic medium (SCM)] in the coral Stylophora pistillata. We also measured calcification in corals grown under the same conditions of seawater acidification by measuring lateral growth of colonies and growth of aragonite crystals under the calcifying tissue. Our findings confirm that seawater acidification decreases pH of the SCM, but this decrease is gradual relative to the surrounding seawater, leading to an increasing pH gradient between the SCM and seawater. Reductions in calcification rate, both at the level of crystals and whole colonies, were only observed in our lowest pH treatment when pH was significantly depressed in the calcifying cells in addition to the SCM. Overall, our findings suggest that reef corals may mitigate the effects of seawater acidification by regulating pH in the SCM, but they also highlight the role of calcifying cell pH homeostasis in determining the response of reef corals to changes in external seawater pH and carbonate chemistry. PMID:23277567

Impact of seawater acidification on pH at the tissue-skeleton interface and calcification in reef corals.

PubMed

Venn, Alexander A; Tambutté, Eric; Holcomb, Michael; Laurent, Julien; Allemand, Denis; Tambutté, Sylvie

2013-01-29

Insight into the response of reef corals and other major marine calcifiers to ocean acidification is limited by a lack of knowledge about how seawater pH and carbonate chemistry impact the physiological processes that drive biomineralization. Ocean acidification is proposed to reduce calcification rates in corals by causing declines in internal pH at the calcifying tissue-skeleton interface where biomineralization takes place. Here, we performed an in vivo study on how partial-pressure CO(2)-driven seawater acidification impacts intracellular pH in coral calcifying cells and extracellular pH in the fluid at the tissue-skeleton interface [subcalicoblastic medium (SCM)] in the coral Stylophora pistillata. We also measured calcification in corals grown under the same conditions of seawater acidification by measuring lateral growth of colonies and growth of aragonite crystals under the calcifying tissue. Our findings confirm that seawater acidification decreases pH of the SCM, but this decrease is gradual relative to the surrounding seawater, leading to an increasing pH gradient between the SCM and seawater. Reductions in calcification rate, both at the level of crystals and whole colonies, were only observed in our lowest pH treatment when pH was significantly depressed in the calcifying cells in addition to the SCM. Overall, our findings suggest that reef corals may mitigate the effects of seawater acidification by regulating pH in the SCM, but they also highlight the role of calcifying cell pH homeostasis in determining the response of reef corals to changes in external seawater pH and carbonate chemistry.

The history and character of acid precipitation in eastern North America

Treesearch

Charles V. Cogbill

1976-01-01

The history and present distribution of precipitation acidity in eastern North America is reviewed. Precipitation chemistry from the 1920's indicates heavy ionic deposition, but low acidity (calculated) in Tennessee (pH 7.4) and New York (pH 6.15). However, high acidity was apparently widespread over northeast North America by 1955-56 and measured pH's below...

Silicon concentrations in UK surface waters

NASA Astrophysics Data System (ADS)

Neal, Colin; Neal, Margaret; Reynolds, Brian; Maberly, Stephen C.; May, Linda; Ferrier, Robert C.; Smith, Jennifer; Parker, Julie E.

2005-03-01

This paper describes the variations in silicon concentrations in UK waters for a wide range of catchment systems (near pristine, rural, and agricultural and urban impacted systems). The paper largely concerns silicon levels in streams, rivers and lakes based on extensive data collected as part of several research and monitoring initiatives of national and international standing. For a detailed study of an upland catchment in mid-Wales, information on atmospheric inputs and groundwater chemistries is provided to supply background information to cross link to the surface water chemistry. Several hundred streams/rivers and lakes are dealt with within the study, dealing with the main types of freshwater riverine and lacustrine environments. The streams/rivers vary from small ephemeral runoff to the major rivers of the UK. The geographical location of sites vary from local sites in mid-Wales, to regional studies across Scotland, to the major eastern UK rivers entering the North Sea and to acid sensitive upland sites across Wales, the English Lake District, Scotland and Northern Ireland. The surface waters range in silicon concentration from 0 to 19 mg-Si l -1 (average for individual sites vary between 0.7 and 7.6 mg-Si l -1) and there are some clear variations which link to two primary processes (1) the relative inputs of groundwaters enriched in silicon and near surface waters more depleted in silicon and (2) plankton uptake of silicon during the summer months under baseflow conditions. Thermodynamic analysis reveals that the waters are approximately saturated with respect to either quartz or chalcedony except for two circumstances when undersaturation occurs. Firstly, undersaturation occurs at pH less than 5.5 in the upland areas and this is because the waters are mainly sourced from the acidic organic soils which are depleted in inorganic minerals. Secondly, undersaturation occurs in the lowland rivers when biological activity is at its highest and this leads to silicon removal from the water column. Quartz equilibrium can be approached (at pH>5.5) mainly within the upland systems which are not aquifer recharge dominated. However, for the lowland systems that are groundwater recharge dominated, it is chalcedony saturation which is approached, and such saturation is often observed within groundwaters. Similar patterns of undersaturation in response to biological uptake are seen in lakes and the extent of silicon depletion increases with biological productivity. Chalcedony oversaturation can occur for some UK rivers under baseflow conditions and this probably links to a higher rate of weathering.

Urban and Suburban Influences on Water Chemistry in Washington DC: Impervious Surfaces and Urban Stream Syndrome

NASA Astrophysics Data System (ADS)

MacAvoy, S. E.; Petersen, E.

2015-12-01

Among the challenges facing urban rivers are water stormwater runoff problems and changing water chemistry, not only from air and water pollution sources, but also from altered geology with the development of "urban karst". Seventy five percent of the Anacostia River in Washington, D.C. is urban or impervious. The Anacostia River experiences environmental challenges similar to those of other urban industrial rivers (heavy metal, PCB and PAH contamination). It also has Ca/Sr ratios above 200, and Na concentrations higher than Ca, and elevated ionic strength, all associated with extended chemical interaction with concrete. While these chemical characteristics have been documented in the urban areas within DC, they have not been examined in the largely suburban/mixed development tributaries of the Anacostia. Here we examine the base-flow geochemistry of the Anacostia River and its suburban tributaries (6 locations) over a year (November 2014- August 2015), concentrating on the following water chemistry variables: pH, hardness, SAR, alkalinity, Ca, Mg, Na, K, Fe, Mn, Zn, Al, Ba, Ni, total P, S, Sr, NO3-, NH4+, PO43-. NO3- and NH4+ were generally lowest in at all sites in January, but rose to between 0.5 and 2.4 mg/L in June, with highest NO3- concentrations in suburban areas. Na and Cl concentrations were 5x higher in suburban areas than urban areas during the winter months. Ca/Sr concentration ratios, were between 120 and 200 for suburban sites but increased as the sites became more urban (to a high of 240 for the most urban site). These trends have been observed in other urban streams, and correlate with percent impervious area. The data follow patterns expected for "urban stream syndrome" and dissolution of concrete. Suburban areas, with their relatively small streams, show greater winter salting effects than more urban areas down stream. Suburban areas also show higher NO3- (and occasionally higher NH4+) than urban areas except in winter. The data presented here demonstrates that the geochemistry of highly urbanized systems may be significantly altered and should be better understood in order to assess urban impacts on water quality.

Influence of atmospheric deposition on Okefenokee National Wildlife Refuge

USGS Publications Warehouse

Winger, P.V.; Lasier, P.J.; Jackson, B.P.

1995-01-01

Designation of Okefenokee National Wildlife Refuge (Georgia) as a Class I Air Quality Area affords mandatory protection of the airshed through permit-review processes for planned developments. Rainfall is the major source of water to the swamp, and potential impacts from developments in the airshed are high. To meet management needs for baseline information, chemical contributions from atmospheric deposition and partitioning of anions and cations in various matrices of the swamp, with emphasis on mercury and lead, were determined during this study. Chemistry of rainfall was measured on an event basis from one site and quarterly on surface water, pore water, floc, and sediment from four locations. A sediment core collected from the Refuge interior was sectioned, aged, and analyzed for mercury. Rainfall was acidic (pH 4.7-4.9), with average total and methyl mercury concentrations of 9 ng/L and 0.1 ng/L, respectively. Surface waters were acidic (pH 3.8-4.1), dilute (specific conductance 35-60 pS), and highly organic (dissolved organic carbon 35-50 mg/L). Total mercury was 1-3.5 ng/L in surface and pore water, and methyl mercury was 0.02-0.20 ng/L. Total mercury in sediments and floc was 100-200 ng/g dry weight, and methyl mercury was 4-16 ng/g. Lead was 0-1.7 pg/L in rainfall, not detectable in surface water, 3.4-5.4 pg/L in pore water, and 3.9-4.9 mg/kg in floc and sediment. Historical patterns of mercury deposition showed an increase in total mercury from pre-1800 concentrations of 250 ng/g to 500 ng/g in 1950, with concentrations declining thereafter to present.

WATER CHEMISTRY ASSESSMENT METHODS

EPA Science Inventory

This section summarizes and evaluates the surfce water column chemistry assessment methods for USEPA/EMAP-SW, USGS-NAQA, USEPA-RBP, Oho EPA, and MDNR-MBSS. The basic objective of surface water column chemistry assessment is to characterize surface water quality by measuring a sui...

Alterations in seawater pH and CO 2 affect calcification and photosynthesis in the tropical coralline alga, Hydrolithon sp. (Rhodophyta)

NASA Astrophysics Data System (ADS)

Semesi, I. Sware; Kangwe, Juma; Björk, Mats

2009-09-01

Calcification in the marine environment is the basis for the accretion of carbonate in structures such as coral reefs, algal ridges and carbonate sands. Among the organisms responsible for such calcification are the Corallinaceae (Rhodophyta), recognised as major contributors to the process world-wide. Hydrolithon sp. is a coralline alga that often forms rhodoliths in the Western Indian Ocean. In Zanzibar, it is commonly found in shallow lagoons, where it often grows within seagrass beds and/or surrounded by green algae such as Ulva sp. Since seagrasses in Zanzibar have recently been shown to raise the pH of the surrounding seawater during the day, and since calcification rates are sensitive to pH, which changes the saturation state of calcium carbonate, we measured the effects of pH on photosynthetic and calcification rates of this alga. It was found that pH had significant effects on both calcification and photosynthesis. While increased pH enhanced calcification rates both in the light and in the dark at pH >8.6, photosynthetic rates decreased. On the other hand, an increase in dissolved CO 2 concentration to ˜26 μmol kg -1 (by bubbling with air containing 0.9 mbar CO 2) caused a decrease in seawater pH which resulted in 20% less calcification after 5 days of exposure, while enhancing photosynthetic rates by 13%. The ecological implications of these findings is that photosynthetically driven changes in water chemistry by surrounding plants can affect calcification rates of coralline algae, as may future ocean acidification resulting from elevated atmospheric CO 2.

A Head for Chemistry.

ERIC Educational Resources Information Center

Hanshumaker, William

1987-01-01

Discusses some of the ways that a cabbage can be used to produce a universal indicator of pH. Describes the methods for producing the indicator, experiments students can do on ordinary household chemicals, and a student take-home assignment for producing pH indicators. (TW)

Radical Chemistry and Structural Relationships of PPCP Degradation by UV/Chlorine Treatment in Simulated Drinking Water.

PubMed

Guo, Kaiheng; Wu, Zihao; Shang, Chii; Yao, Bo; Hou, Shaodong; Yang, Xin; Song, Weihua; Fang, Jingyun

2017-09-19

The UV/chlorine process is an emerging advanced oxidation process (AOP) used for the degradation of micropollutants. However, the radical chemistry of this AOP is largely unknown for the degradation of numerous structurally diverse micropollutants in water matrices of varying quality. These issues were addressed by grouping 34 pharmaceuticals and personal care products (PPCPs) according to the radical chemistry of their degradation in the UV/chlorine process at practical PPCP concentrations (1 μg L -1 ) and in different water matrices. The contributions of HO • and reactive chlorine species (RCS), including Cl • , Cl 2 •- , and ClO • , to the degradation of different PPCPs were compound specific. RCS showed considerable reactivity with olefins and benzene derivatives, such as phenols, anilines, and alkyl-/alkoxybenzenes. A good linear relationship was found between the RCS reactivity and negative values of the Hammett ∑σ p + constant for aromatic PPCPs, indicating that electron-donating groups promote the attack of benzene derivatives by RCS. The contribution of HO • , but not necessarily RCS, to PPCP removal decreased with increasing pH. ClO • showed high reactivity with some PPCPs, such as carbamazepine, caffeine, and gemfibrozil, with second-order rate constants of 9.2 × 10 7 , 1.03 × 10 8 , and 4.16 × 10 8 M -1 s -1 , respectively, which contributed to their degradation. Natural organic matter (NOM) induced significant scavenging of ClO • and greatly decreased the degradation of PPCPs that was attributable to ClO • , with a second-order rate constant of 4.5 × 10 4 (mg L -1 ) -1 s -1 . Alkalinity inhibited the degradation of PPCPs that was primarily attacked by HO • and Cl • but had negligible effects on the degradation of PPCPs by ClO • . This is the first study on the reactivity of RCS, particularly ClO • , with structurally diverse PPCPs under simulated drinking water condition.

Impact of physical and chemical characteristics of breeding sites on mosquito larval abundance at Ismailia Governorate, Egypt.

PubMed

Bahgat, Iman Mohamed

2013-08-01

The distribution and monthly abundance of mosquito larvae in released water, drainage canals and sewage water tanks in Ismailia governorate were investigated. The results obtained indicated the presence of five culicine (Culex. pipiens, Cx. pusillus, Cx. perexiguus, Cx. theleri and Ochlerotatus. caspius) and two anopheline (Anopheles. multicolor and An. pharoensis) mosquito species. Significantly higher larval density was recorded in sewage water (n= 5534; 46.08%) as compared with released water (n = 2903; 24.17%) and drainage water (n= 3573; 29.75%). Culex pipiens was the most dominant mosquito species in the three habitats. The effects of environmental parameters including pH, biological and chemical oxygen demands, day time water temperature, plant growth, salinity, total organic matter and concentrations of heavy metals on larval population density were investigated. The positive correlations observed between heavy metals concentrations in the three habitats suggested relative uniformity of the sources of metal pollutants. Culex pipiens larvae demonstrated high tolerance to elevated levels of heavy metals in sewage water and compensatory effects of high nutrient levels generally associated with sewage or domestic waste. High densities of culicine larvae were accompanied by low density of anopheline larvae. This was attributed to water chemistry & competitive interactions.

Aquatic and terrestrial organic matter in the diet of stream consumers: implications for mercury bioaccumulation.

PubMed

Jardine, Timothy D; Kidd, Karen A; Rasmussen, Joseph B

2012-04-01

The relative contribution of aquatic vs. terrestrial organic matter to the diet of consumers in fluvial environments and its effects on bioaccumulation of contaminants such as mercury (Hg) remain poorly understood. We used stable isotopes of carbon and nitrogen in a gradient approach (consumer isotope ratio vs. periphyton isotope ratio) across temperate streams that range in their pH to assess consumer reliance on aquatic (periphyton) vs. terrestrial (riparian vegetation) organic matter, and whether Hg concentrations in fish and their prey were related to these energy sources. Taxa varied in their use of the two sources, with grazing mayflies (Heptageniidae), predatory stoneflies (Perlidae), one species of water strider (Metrobates hesperius), and the fish blacknose dace (Rhinichthys atratulus) showing strong connections to aquatic sources, while Aquarius remigis water striders and brook trout (Salvelinus fontinalis) showed a weak link to in-stream production. The aquatic food source for consumers, periphyton, had higher Hg concentrations in low-pH waters, and pH was a much better predictor of Hg in predatory invertebrates that relied mainly on this food source vs. those that used terrestrial C. These findings suggest that stream biota relying mainly on dietary inputs from the riparian zone will be partially insulated from the effects of water chemistry on Hg availability. This has implications for the development of a whole-system understanding of nutrient and material cycling in streams, the choice of taxa in contaminant monitoring studies, and in understanding the fate of Hg in stream food webs.

Partial Characterization of a Novel Amphibian Hemoglobin as a Model for Graduate Student Investigation on Peptide Chemistry, Mass Spectrometry, and Atomic Force Microscopy

ERIC Educational Resources Information Center

Bemquerer, Marcelo P.; Macedo, Jessica K. A.; Ribeiro, Ana Carolina J.; Carvalho, Andrea C.; Silva, Debora O. C.; Braz, Juliana M.; Medeiros, Kelliane A.; Sallet, Lunalva A. P.; Campos, Pollyanna F.; Prates, Maura V.; Silva, Luciano P.

2012-01-01

Graduate students in chemistry, and in biological and biomedical fields must learn the fundamentals and practices of peptide and protein chemistry as early as possible. A project-oriented approach was conducted by first-year M.Sc and Ph.D students in biological sciences. A blind glass slide containing a cellular smear and an aqueous cellular…

Structural and Synthetic Organosilicon Chemistry.

DTIC Science & Technology

1984-07-23

yields of benzanilide and acetanilide , 58ab, respectively. Curiously, the 0 Ph me SitI R OH PhNH R 57a R = Ph 75% 58a R = Ph 57b R = Me 55% 58b R...CO Bond of Amides: We obtained some encouraging preliminary results in this area. Formation of the t-butyldimethylsilyl imino ether from acetanilide ...followed by mild acidic hydrolysis produced aniline in 40% yield. Control studies have shown that the hydrolysis conditions do not cleave acetanilide