NASA Astrophysics Data System (ADS)
Chabot, N. L.
2017-12-01
As planetesimals were heated up in the early Solar System, the formation of Fe-Ni metallic melts was a common occurrence. During planetesimal differentiation, the denser Fe-Ni metallic melts separated from the less dense silicate components, though some meteorites suggest that their parent bodies only experienced partial differentiation. If the Fe-Ni metallic melts did form a central metallic core, the core eventually crystallized to a solid, some of which we sample as iron meteorites. In all of these planetesimal evolution processes, the composition of the Fe-Ni metallic melt influenced the process and the resulting trace element chemical signatures. In particular, the metallic melt's "light element" composition, those elements present in the metallic melt in a significant concentration but with lower atomic masses than Fe, can strongly affect trace element partitioning. Experimental studies have provided critical data to determine the effects of light elements in Fe-Ni metallic melts on trace element partitioning behavior. Here I focus on combining numerous experimental results to identify trace elements that provide unique insight into constraining the light element composition of early Solar System Fe-Ni metallic melts. Experimental studies have been conducted at 1 atm in a variety of Fe-Ni systems to investigate the effects of light elements on trace element partitioning behavior. A frequent experimental examination of the effects of light elements in metallic systems involves producing run products with coexisting solid metal and liquid metal phases. Such solid-metal-liquid-metal experiments have been conducted in the Fe-Ni binary system as well as Fe-Ni systems with S, P, and C. Experiments with O-bearing or Si-bearing Fe-Ni metallic melts do not lend themselves to experiments with coexisting solid metal and liquid metal phases, due to the phase diagrams of these elements, but experiments with two immiscible Fe-Ni metallic melts have provided insight into the qualitative effects of O and Si relative to the well-determined effects of S. Together, these experimental studies provide a robust dataset to identify key elements that are predicted to produce distinct chemical signatures as a function of different Fe-Ni metallic melt compositions during planetesimal evolution processes.
Trace metal concentrations in tropical mangrove sediments, NE Brazil.
Miola, Brígida; Morais, Jáder Onofre de; Pinheiro, Lidriana de Souza
2016-01-15
Sediment cores were taken from the mangroves of the Coreaú River estuary off the northeast coast of Brazil. They were analyzed for grain size, CaCO3, organic matter, and trace metal (Cd, Pb, Zn, Cu, Al, and Fe) contents. Mud texture was the predominant texture. Levels of trace metals in surface sediments indicated strong influence of anthropogenic processes, and diagenetic processes controlled the trace metal enrichment of core sediments of this estuary. The positive relationships between trace metals and Al and Fe indicate that Cu, Zn, Pb, and Cd concentrations are associated mainly with Al and Fe oxy-hydroxides and have natural sources. Copyright © 2015 Elsevier Ltd. All rights reserved.
Ayyamperumal, T; Jonathan, M P; Srinivasalu, S; Armstrong-Altrin, J S; Ram-Mohan, V
2006-09-01
An acid leachable technique is employed in core samples (C1, C2 and C3) to develop a baseline data on the sediment quality for trace metals of River Uppanar, Cuddalore, southeast coast of India. Acid leachable metals (Fe, Mn, Cr, Cu, Ni, Co, Pb, Zn and Cd) indicate peak values at the sulphidic phase and enrichment of metals in the surface layers are due to the anthropogenic activities. Association of trace metals with Fe, Mn indicates their adsorption onto Fe-Mn oxyhydroxides and their correlation with S indicate that they are precipitated as metal sulphides. Factor analysis identified three possible types of geochemical associations and the supremacy of trace metals along with Fe, Mn, S and mud supports their geochemical associations. Factor analysis also signifies that anthropogenic activities have affected both the estuarine and fresh water regions of River Uppanar.
NASA Astrophysics Data System (ADS)
Heal, Mathew R.; Hibbs, Leon R.; Agius, Raymond M.; Beverland, Iain J.
Toxicological studies have implicated trace metals in airborne particles as possible contributors to respiratory and/or cardiovascular inflammation. As part of an epidemiological study, co-located 24 h samples of PM 10, PM 2.5 and black smoke (BS) were collected for 1 year at an urban background site in Edinburgh, and each sample sequentially extracted with ultra-pure water, then concentrated HNO 3/HCl, and analysed for Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, As, Cd and Pb. This yields a comprehensive data set for UK urban airborne trace metal. The median ( n>349) daily water-soluble metal concentration in PM 2.5 ranged from 0.05 ng m -3 for Ti to 5.1 ng m -3 for Pb; and in PM 10 from 0.18 ng m -3 for Ti to 11.7 ng m -3 for Fe. Median daily total (i.e. water+acid-extractable) metal concentration in PM 2.5 ranged from 0.3 ng m -3 for As to 27.6 ng m -3 for Fe; and in PM 10 from 0.37 ng m -3 for As to 183 ng m -3 for Fe. The PM 2.5:PM 10 ratio varied considerably with metal, from <17%, on average, for Ti and Fe, to >70% for V, As, Cd and Pb. The 11 trace metals constituted proportionally more of the PM 10-2.5 fraction than of the PM 2.5 fraction (0.9%). The proportion of water-soluble metal in each size-fraction varied considerably, from <10% water-soluble Fe and Ti in PM 10-2.5, to >50% water-soluble V, Zn, As and Cd in PM 2.5. Although Fe generally dominated the trace metal, water-soluble metal also contained significant Zn, Pb and Cu, and for all size and solubility fractions >90% of trace metal was comprised of Fe, Zn, Pb and Cu. Statistical analyses suggested three main sources: traffic; static combustion; and crustal. The association of metals with traffic (Cu, Fe, Mn, Pb, Zn) was consistent with traffic-induced non-exhaust "resuspension" rather than direct exhaust emission. Meteorology contributed to the wide variation in daily trace metal concentration. The proportion of trace metal in particles varied significantly with the air mass source and was highest on days for trajectories traversing over land. For Mn, Fe, Cu, Zn, As and Pb there was greater correlation of metal concentration with BS mass than with either PM 10 or PM 2.5 mass, suggesting that BS reflectance monitoring could be a cost-effective surrogate measure of particle metal concentration in urban background air.
Trace metal characterization of aerosol particles and cloud water during HCCT 2010
NASA Astrophysics Data System (ADS)
Fomba, K. W.; van Pinxteren, D.; Müller, K.; Iinuma, Y.; Lee, T.; Collett, J. L., Jr.; Herrmann, H.
2015-08-01
Trace metal characterization of bulk and size-resolved aerosol and cloud water samples were performed during the Hill Cap Cloud Thuringia (HCCT) campaign. Cloud water was collected at the top of Mt. Schmücke while aerosol samples were collected at two stations upwind and downwind of Mt. Schmücke. Fourteen trace metals including Ti, V, Fe, Mn, Co, Zn, Ni, Cu, As, Sr, Rb, Pb, Cr, and Se were investigated during four full cloud events (FCEs) that fulfilled the conditions of a continuous air mass flow through the three stations. Aerosol particle trace metal concentrations were found to be lower than those observed in the same region during previous field experiments but were within a similar range to those observed in other rural regions in Europe. Fe and Zn were the most abundant elements with concentration ranges of 0.2-111.6 and 1.1-32.1 ng m-3, respectively. Fe, Mn, and Ti were mainly found in coarse mode aerosols while Zn, Pb, and As were mostly found in the fine mode. Correlation and enrichment factor analysis of trace metals revealed that trace metals such as Ti and Rb were mostly of crustal origin while trace metals such as Zn, Pb, As, Cr, Ni, V, and Cu were of anthropogenic origin. Trace metals such as Fe and Mn were of mixed origins including crustal and combustion sources. Trace metal cloud water concentration decreased from Ti, Mn, Cr, to Co with average concentrations of 9.18, 5.59, 5.54, and 0.46 μg L-1, respectively. A non-uniform distribution of soluble Fe, Cu, and Mn was observed across the cloud drop sizes. Soluble Fe and Cu were found mainly in cloud droplets with diameters between 16 and 22 μm, while Mn was found mostly in larger drops greater than 22 μm. Fe(III) was the main form of soluble Fe especially in the small and larger drops with concentrations ranging from 2.2 to 37.1 μg L-1. In contrast to other studies, Fe(II) was observed mainly in the evening hours, implying its presence was not directly related to photochemical processes. Aerosol-cloud interaction did not lead to a marked increase in soluble trace metal concentrations; rather it led to differences in the chemical composition of the aerosol due to preferential loss of aerosol particles through physical processes including cloud drop deposition to vegetative surfaces.
Trace metal characterization of aerosol particles and cloud water during HCCT 2010
NASA Astrophysics Data System (ADS)
Fomba, K. W.; van Pinxteren, D.; Müller, K.; Iinuma, Y.; Lee, T.; Collet, J., Jr.; Herrmann, H.
2015-04-01
Trace metal characterization of bulk and size resolved aerosol and cloud water samples were performed during the Hill Cap Cloud Thuringia (HCCT) campaign. Cloud water was collected at the top of Mt. Schmücke while aerosol samples were collected at two stations upwind and downwind of Mt. Schmücke. Fourteen trace metals including Ti, V, Fe, Mn, Co, Zn, Ni, Cu, As, Sr, Rb, Pb, Cr, and Se were investigated during four full cloud events (FCE) that fulfilled the conditions of a continuous air mass flow through the three stations. Aerosol particle trace metal concentrations were found to be lower than those observed in the same region during previous field experiments but were within a similar range to those observed in other rural regions in Europe. Fe and Zn were the most abundant elements with concentration ranges of 0.2-111.6 and 1.1-32.1 ng m-3, respectively. Fe, Mn and Ti were mainly found in coarse mode aerosols while Zn, Pb and As were mostly found in the fine mode. Correlation and enrichment factor analysis of trace metals revealed that trace metals such as Ti and Rb were mostly of crustal origin while trace metals such as Zn, Pb, As, Cr, Ni, V, and Cu were of anthropogenic origin. Trace metals such as Fe, Mn, were of mixed origins including crustal and combustion sources. Trace metal cloud water concentration decreased from Ti, Mn, Cr, to Co with average concentrations of 9.18, 5.59, 5.54, and 0.46 μg L-1, respectively. A non-uniform distribution of soluble Fe, Cu and Mn was observed across the cloud drop sizes. Soluble Fe and Cu were found mainly in cloud droplets with diameters between 16 and 22 μm while Mn was found mostly in larger drops greater than 22 μm. Fe (III) was the main form of soluble Fe especially in the small and larger drops with concentrations ranging from 2.2 to 37.1 μg L-1. In contrast to other studies, Fe (II) was observed mainly in the evening hours, implying its presence was not directly related to photochemical processes. Aerosol cloud interaction did not lead to a mark increase in soluble trace metal concentrations, but led to differences in the chemical composition of the aerosol due to preferential loss of aerosol particles through physical processes including cloud drop deposition to vegetative surfaces.
Characterization of typical metal particles during haze episodes in Shanghai, China.
Li, Rui; Yang, Xin; Fu, Hongbo; Hu, Qingqing; Zhang, Liwu; Chen, Jianmin
2017-08-01
Aerosol particles were collected during three heavy haze episodes at Shanghai in the winter of 2013. Transmission electron microscopy (TEM) coupled with energy dispersive X-ray spectroscopy was used to study the morphology and speciation of typical metal particles at a single-particle level. In addition, time-of-flight aerosol mass spectrometry (ATOFMS) was applied to identify the speciation of the Fe-containing particles. TEM analysis indicated that various metal-containing particles were hosted by sulfates, nitrates, and oxides. Fe-bearing particles mainly originated from vehicle emissions and/or steel production. Pb-, Zn-, and Sb-bearing particles were mainly contributed by anthropogenic sources. Fe-bearing particles were clustered into six groups by ATOFMS: Fe-Carbon, Fe-Inorganic, Fe-Trace metal, Fe-CN, Fe-PO 3, and Fe-NO 3 . ATOFMS data suggested that Fe-containing particles corresponded to different origins, including industrial activities, resuspension of dusts, and vehicle emissions. Fe-Carbon and Fe-CN particles displayed significant diurnal variation, and high levels were observed during the morning rush hours. Fe-Inorganic and Fe-Trace metal particle levels peaked at night. Furthermore, Fe-Carbon and Fe-PO 3 were mainly concentrated in the fine particles. Fe-CN, Fe-Inorganic, and Fe-Trace metal exhibited bimodal distribution. The mixing state of the particles revealed that all Fe-bearing particles tended to be mixed with sulfate and nitrate. The data presented herein is essential for elucidating the origin, evolution processes, and health effects of metal-bearing particles. Copyright © 2017 Elsevier Ltd. All rights reserved.
NASA Astrophysics Data System (ADS)
Kumar, A.; Ramanathan, A.; Mathukumalli, B. K. P.; Datta, D. K.
2014-12-01
The distribution, enrichment and ecotoxocity potential of Bangladesh part of Sundarban mangrove was investigated for eight trace metals (As, Cd, Cr, Cu, Fe, Mn, Pb and Zn) using sediment quality assessment indices. The average concentration of trace metals in the sediments exceeded the crustal abundance suggesting sources other than natural in origin. Additionally, the trace metals profile may be a reflection of socio-economic development in the vicinity of Sundarban which further attributes trace metals abundance to the anthropogenic inputs. Geoaccumulation index suggests moderately polluted sediment quality w.r.t. Ni and As and background concentrations for Al, Fe, Mn, Cu, Zn, Pb, Co, As and Cd. Contamination factor analysis suggested low contamination by Zn, Cr, Co and Cd, moderate by Fe, Mn, Cu and Pb while Ni and As show considerable and high contamination, respectively. Enrichment factors for Ni, Pb and As suggests high contamination from either biota or anthropogenic inputs besides natural enrichment. As per the three sediment quality guidelines, Fe, Mn, Cu, Ni, Co and As would be more of a concern with respect to ecotoxicological risk in the Sundarban mangroves. The correlation between various physiochemical variables and trace metals suggested significant role of fine grained particles (clay) in trace metal distribution whereas owing to low organic carbon content in the region the organic complexation may not be playing significant role in trace metal distribution in the Sundarban mangroves.
McKnight, Diane M.; Wershaw, R. L.; Bencala, K.E.; Zellweger, G.W.; Feder, G.L.
1992-01-01
Hydrous iron and aluminum oxides are deposited on the streambed in the confluence of the Snake River and Deer Creek, two streams in the Colorado Rocky Mountains. The Snake River is acidic and has high concentrations of dissolved Fe and Al. These metals precipitate at the confluence with the pristine, neutral pH, Deer Creek because of the greater pH (4.5-6.0) in the confluence. The composition of the deposited oxides changes consistently with distance downstream, with the most upstream oxide samples having the greatest Fe and organic carbon content. Fulvic acid accounts for most of the organic content of the oxides. Results indicate that streambed oxides in the confluence are not saturated with respect to their capacity to sorb dissolved humic substances from streamwater. The contents of several trace metals (Mn, Zn, Cu, Pb, Ni and Co) also decrease with distance downstream and are correlated with both the Fe and organic carbon contents. Strong metal-binding sites associated with the sorbed fulvic acid are more than sufficient to account for the trace metal content of the oxides. Complexation of trace metals by sorbed fulvic acid may explain the observed downstream decrease in trace metal content.
Srichandan, Suchismita; Panigrahy, R C; Baliarsingh, S K; Rao B, Srinivasa; Pati, Premalata; Sahu, Biraja K; Sahu, K C
2016-10-15
Concentrations of trace metals such as iron (Fe), copper (Cu), zinc (Zn), cobalt (Co), nickel (Ni), manganese (Mn), lead (Pb), cadmium (Cd), chromium (Cr), arsenic (As), vanadium (V), and selenium (Se) were determined in seawater and zooplankton from the surface waters off Rushikulya estuary, north-western Bay of Bengal. During the study period, the concentration of trace metals in seawater and zooplankton showed significant spatio-temporal variation. Cu and Co levels in seawater mostly remained non-detectable. Other elements were found at higher concentrations and exhibited marked variations. The rank order distribution of trace metals in terms of their average concentration in seawater was observed as Fe>Ni>Mn>Pb>As>Zn>Cr>V>Se>Cd while in zooplankton it was Fe>Mn>Cd>As>Pb>Ni>Cr>Zn>V>Se. The bioaccumulation factor (BAF) of Fe was highest followed by Zn and the lowest value was observed with Ni. Results of correlation analysis discerned positive affinity and good relationship among the majority of the trace metals, both in seawater and zooplankton suggesting their strong affinity and coexistence. Copyright © 2016 Elsevier Ltd. All rights reserved.
Rates of zinc and trace metal release from dissolving sphalerite at pH 2.0-4.0
Stanton, M.R.; Gemery-Hill, P. A.; Shanks, Wayne C.; Taylor, C.D.
2008-01-01
High-Fe and low-Fe sphalerite samples were reacted under controlled pH conditions to determine nonoxidative rates of release of Zn and trace metals from the solid-phase. The release (solubilization) of trace metals from dissolving sphalerite to the aqueous phase can be characterized by a kinetic distribution coefficient, (Dtr), which is defined as [(Rtr/X(tr)Sph)/(RZn/X(Zn) Sph)], where R is the trace metal or Zn release rate, and X is the mole fraction of the trace metal or Zn in sphalerite. This coefficient describes the relationship of the sphalerite dissolution rate to the trace metal mole fraction in the solid and its aqueous concentration. The distribution was used to determine some controls on metal release during the dissolution of sphalerite. Departures from the ideal Dtr of 1.0 suggest that some trace metals may be released via different pathways or that other processes (e.g., adsorption, solubility of trace minerals such as galena) affect the observed concentration of metals. Nonoxidative sphalerite dissolution (mediated by H+) is characterized by a "fast" stage in the first 24-30 h, followed by a "slow" stage for the remainder of the reaction. Over the pH range 2.0-4.0, and for similar extent of reaction (reaction time), sphalerite composition, and surface area, the rates of release of Zn, Fe, Cd, Cu, Mn and Pb from sphalerite generally increase with lower pH. Zinc and Fe exhibit the fastest rates of release, Mn and Pb have intermediate rates of release, and Cd and Cu show the slowest rates of release. The largest variations in metal release rates occur at pH 2.0. At pH 3.0 and 4.0, release rates show less variation and appear less dependent on the metal abundance in the solid. For the same extent of reaction (100 h), rates of Zn release range from 1.53 ?? 10-11 to 5.72 ?? 10-10 mol/m2/s; for Fe, the range is from 4.59 ?? 10-13 to 1.99 ?? 10-10 mol/m2/s. Trace metal release rates are generally 1-5 orders of magnitude slower than the Zn or Fe rates. Results indicate that the distributions of Fe and Cd are directly related to the rate of sphalerite dissolution throughout the reaction at pH 3.0 and 4.0 because these two elements substitute readily into sphalerite. These two metals are likely to be more amenable to usage in predictive acid dissolution models because of this behavior. The Pb distribution shows no strong relation to sphalerite dissolution and appears to be controlled by pH-dependent solubility, most likely related to trace amounts of galena. The distribution of Cu is similar to that of Fe but is the most-dependent of all metals on its mole fraction ratio (Zn:Cu) in sphalerite. The Mn distributions suggest an increase in the rate of Mn release relative to sphalerite dissolution occurs in low Mn samples as pH increases. The Mn distribution in high Mn samples is nearly independent of pH and sphalerite dissolution at pH 2.0 but shows a dependence on these two parameters at higher pH (3.0-4.0).
Atmospheric trace metals measured at a regional background site (Welgegund) in South Africa
NASA Astrophysics Data System (ADS)
Venter, Andrew D.; van Zyl, Pieter G.; Beukes, Johan P.; Josipovic, Micky; Hendriks, Johan; Vakkari, Ville; Laakso, Lauri
2017-03-01
Atmospheric trace metals can cause a variety of health-related and environmental problems. Only a few studies on atmospheric trace metal concentrations have been conducted in South Africa. Therefore the aim of this study was to determine trace metal concentrations in aerosols collected at a regional background site, i.e. Welgegund, South Africa. PM1, PM1-2. 5 and PM2. 5-10 samples were collected for 13 months, and 31 atmospheric trace metal species were detected. Atmospheric iron (Fe) had the highest concentrations in all three size fractions, while calcium (Ca) was the second-most-abundant species. Chromium (Cr) and sodium (Na) concentrations were the third- and fourth-most-abundant species, respectively. The concentrations of the trace metal species in all three size ranges were similar, with the exception of Fe, which had higher concentrations in the PM1 size fraction. With the exception of titanium (Ti), aluminium (Al) and manganese (Mg), 70 % or more of the trace metal species detected were in the smaller size fractions, which indicated the influence of industrial activities. However, the large influence of wind-blown dust was reflected by 30 % or more of trace metals being present in the PM2. 5-10 size fraction. Comparison of trace metals determined at Welgegund to those in the western Bushveld Igneous Complex indicated that at both locations similar species were observed, with Fe being the most abundant. However, concentrations of these trace metal species were significantly higher in the western Bushveld Igneous Complex. Fe concentrations at the Vaal Triangle were similar to levels thereof at Welgegund, while concentrations of species associated with pyrometallurgical smelting were lower. Annual average Ni was 4 times higher, and annual average As was marginally higher than their respective European standard values, which could be attributed to regional influence of pyrometallurgical industries in the western Bushveld Igneous Complex. All three size fractions indicated elevated trace metal concentrations coinciding with the end of the dry season, which could partially be attributed to decreased wet removal and increases in wind generation of particulates. Principal component factor analysis (PCFA) revealed four meaningful factors in the PM1 size fraction, i.e. crustal, pyrometallurgical-related and Au slimes dams. No meaningful factors were determined for the PM1-2. 5 and PM2. 5-10 size fractions, which was attributed to the large influence of wind-blown dust on atmospheric trace metals determined at Welgegund. Pollution roses confirmed the influence of wind-blown dust on trace metal concentrations measured at Welgegund, while the impact of industrial activities was also substantiated.
The Samarco mine tailing disaster: A possible time-bomb for heavy metals contamination?
Queiroz, Hermano M; Nóbrega, Gabriel N; Ferreira, Tiago O; Almeida, Leandro S; Romero, Thais B; Santaella, Sandra T; Bernardino, Angelo F; Otero, Xosé L
2018-05-10
In November 2015, the largest socio-environmental disaster in the history of Brazil occurred when approximately 50 million m 3 of mine tailings were released into the Doce River (SE Brazil), during the greatest failure of a tailings dam worldwide. The mine tailings passed through the Doce River basin, reaching the ecologically important estuary 17 days later. On the arrival of the mine wastes to the coastal area, contamination levels in the estuarine soils were measured to determine the baseline level of contamination and to enable an environmental risk assessment. Soil and tailings samples were collected and analyzed to determine the redox potential (Eh), pH, grain size and mineralogical composition, total metal contents (Fe, Mn, Cr, Zn, Ni, Cu, Pb and Co) and organic matter content. The metals were fractionated to elucidate the mechanisms governing the trace metal dynamics. The mine tailings are mostly composed of Fe (mean values for Fe: 45,200 ± 2850; Mn: 433 ± 110; Cr: 63.9 ± 15.1; Zn: 62.4 ± 28.4; Ni: 24.7 ± 10.4; Cu: 21.3 ± 4.6; Pb: 20.2 ± 4.6 and Co: 10.7 ± 4.8 mg kg -1 ), consisting of Fe-oxyhydroxides (goethite, hematite); kaolinite and quartz. The metal contents of the estuarine soils, especially the surface layers, indicate trace metal enrichment caused by the tailings. However, the metal contents were below threshold levels reported in Brazilian environmental legislation. Despite the fact that only a small fraction (<2%) of the metals identified are readily bioavailable (i.e. soluble and exchangeable fraction), trace metals associated with Fe oxyhydroxides contributed between 69.8 and 87.6% of the total contents. Control of the trace metal dynamics by Fe oxyhydroxides can be ephemeral, especially in wetland soils in which the redox conditions oscillate widely. Indeed, the physicochemical conditions (Eh < 100 mV and circumneutral pH) of estuarine soils favor Fe reduction microbial pathways, which will probably increase the trace metal bioavailability and contamination risk. Copyright © 2018 Elsevier B.V. All rights reserved.
Tembeni, Babalwa; Oyedeji, Adebola O.
2016-01-01
FAAS was used for the analysis of trace metals in fresh and dry plant parts of Cymbopogon validus and Hyparrhenia hirta species with the aim of determining the trace metals concentrations in selected traditional plants consumed in Eastern Cape, South Africa. The trace metal concentration (mg/kg) in the samples of dry Cymbopogon validus leaves (DCVL) showed Cu of 12.40 ± 1.000; Zn of 2.42 ± 0.401; Fe of 2.50 ± 0.410; Mn of 1.31 ± 0.210; Pb of 3.36 ± 0.401 mg/kg, while the samples of fresh Hyparrhenia hirta flowers (FHHF) gave Cu of 9.77 ± 0.610; Zn of 0.70 ± 0.200; Fe of 2.11 ± 0.200; Mn of 1.15 ± 0.080; Pb of 3.15 ± 0.100 mg/kg. Abundance of metal concentrations follows the order: Cu > Fe > Pb > Mn > Zn in the flower samples of Cymbopogon validus and Hyparrhenia hirta species. The concentrations of trace metals in both plant parts were below the permissible limits (PL) set by WHO. It is suggested that pharmacovigilance be carried out periodically to improve the quality, safety, and efficiency of various herbal products. PMID:27795868
Trace metal dynamics in zooplankton from the Bay of Bengal during summer monsoon.
Rejomon, G; Kumar, P K Dinesh; Nair, M; Muraleedharan, K R
2010-12-01
Trace metal (Fe, Co, Ni, Cu, Zn, Cd, and Pb) concentrations in zooplankton from the mixed layer were investigated at 8 coastal and 20 offshore stations in the western Bay of Bengal during the summer monsoon of 2003. The ecotoxicological importance of trace metal uptake was apparent within the Bay of Bengal zooplankton. There was a distinct spatial heterogeneity of metals, with highest concentrations in the upwelling zones of the southeast coast, moderate concentrations in the cyclonic eddy of the northeast coast, and lowest concentrations in the open ocean warm gyre regions. The average trace metal concentrations (μg g⁻¹) in coastal zooplankton (Fe, 44894.1 ± 12198.2; Co, 46.2 ± 4.6; Ni, 62.8 ± 6.5; Cu, 84.9 ± 6.7; Zn, 7546.8 ± 1051.7; Cd, 46.2 ± 5.6; Pb, 19.2 ± 2.6) were higher than in offshore zooplankton (Fe, 3423.4 ± 681.6; Co, 19.5 ± 3.81; Ni, 25.3 ± 7.3; Cu, 29.4 ± 4.2; Zn, 502.3 ± 124.3; Cd, 14.3 ± 2.9; Pb, 3.2 ± 2.0). A comparison of average trace metal concentrations in zooplankton from the Bay of Bengal showed enrichment of Fe, Co, Ni, Cu, Zn, Cd, and Pb in coastal zooplankton may be related to metal absorption from primary producers, and differences in metal concentrations in phytoplankton from coastal waters (upwelling zone and cyclonic eddy) compared with offshore waters (warm gyre). Zooplankton showed a great capacity for accumulations of trace metals, with average concentration factors of 4 867 929 ± 569 971, 246 757 ± 51 321, 337 180 ± 125 725, 43 480 ± 11 212, 1 046 371 ± 110 286, 601 679 ± 213 949, and 15 420 ± 9201 for Fe, Co, Ni, Cu, Zn, Cd, and Pb with respect to dissolved concentrations in coastal and offshore waters of the Bay of Bengal. © 2009 Wiley Periodicals, Inc. Environ Toxicol, 2009. Copyright © 2009 Wiley Periodicals, Inc.
Gao, Yang; Hao, Zhuo; Yang, Tiantian; He, Nianpeng; Tian, Jing; Wen, Xuefa
2016-10-01
In order to better understand air pollution in deve-loping regions, such as China, it is important to investigate the wet deposition behavior of atmospheric trace metals and its sources in the subtropical watershed. This paper studies the seasonal change of trace metal concentrations in precipitation and other potential sources in a typical subtropical watershed (Jiazhuhe watershed) located in the downstream of the Yangtze River of China. The results show that typical crustal elements (Al, Fe) and trace element (Zn) have high seasonal variation patterns and these elements have higher contents in precipitation as compared to other metals in Jiazhuhe watershed. In addition, there is no observed Pb in base flow in this study, and the concentration magnitudes of Al, Ba, Fe, Mn, Sr, and Zn in base flow are significantly higher than that of other metals. During different rainfall events, the dynamic export processes are also different for trace metals. The various trace metals dynamic export processes lead to an inconsistent mass first flush and a significant accumulative variance throughout the rainfall events. It is found that in this region, most of the trace metals in precipitation are from anthropogenic emission and marine aerosols brought by typhoon and monsoon.
Assessment of trace metal levels in size-resolved particulate matter in the area of Leipzig
NASA Astrophysics Data System (ADS)
Fomba, Khanneh Wadinga; van Pinxteren, Dominik; Müller, Konrad; Spindler, Gerald; Herrmann, Hartmut
2018-03-01
Size-resolved trace metal concentrations at four sites in Leipzig (Germany) and its surrounding were assessed between the winter of 2013 and the summer of 2015. The measurements were performed in parallel at; traffic dominated (Leipzig - Mitte, LMI), traffic and residential dominated (Eisenbahnstrasse, EIB), urban background (TROPOS, TRO) and regional background (Melpitz, MEL) sites. In total, 19 trace metals, i.e. K, Ca, Ti, Mn, Fe, Cu, Zn, As, Se, Ba, V, Pb, Ni, Cr, Sr, Sn, Sb, Co and Rb were analysed using total reflection x-ray fluorescence (TXRF). The major metals were Fe, K and Ca with concentrations ranging between; 31-440 ng/m3, 42-153 ng/m3 and 24-322 ng/m3, respectively, while the trace metals with the lowest concentrations were Co, Rb and Se with concentrations of; < 0.3 ng/m3, <0.5 ng/m3 and 0.5-0.7 ng/m3, respectively. PM10 trace metal concentrations during easterly air mass inflow especially at the background sites were in average 70% higher in the winter and 30% higher in the summer in comparison to westerly air mass inflow. Traffic at LMI contributed to about 75% of Cr, Ba, Cu, Sb, Sn, Ca, Co, Mn, Fe and Ti concentrations while regional activities contributed to more than 70% of K, Rb, Pb, Se, As and V concentrations. Traffic dominated trace metals were often observed in the coarse mode while the regional background dominated trace metals were often observed in the fine mode. Trace metal sources were related to crustal matter and road dust re-suspension for metals such as Ca, Fe, Co, Sr, and Ti, brake and tire wear (Cu, Sb, Ba, Fe, Zn, Pb), biomass burning (K, Rb), oil and coal combustion (V, Zn, As, Pb). Crustal matter contributed 5-12% in winter and 8-19% in summer of the PM10 mass. Using Cu and Zn as markers for brake and tire wear, respectively, the estimated brake and tire wear contributions to the PM10 mass were 0.1-0.8% and 1.7-2.9%, respectively. The higher contributions were observed at the traffic sites while the lower contributions were observed at the regional background site. In total, non-exhaust emissions could account for about 10-22% of the PM10 mass in the summer and about 7-15% of the PM10 mass in the winter.
King, Andrew L; Sañudo-Wilhelmy, Sergio A; Leblanc, Karine; Hutchins, David A; Fu, Feixue
2011-08-01
Phytoplankton growth can be limited by numerous inorganic nutrients and organic growth factors. Using the subarctic diatom Attheya sp. in culture studies, we examined how the availability of vitamin B(12) and carbon dioxide partial pressure (pCO(2)) influences growth rate, primary productivity, cellular iron (Fe), cobalt (Co), zinc (Zn) and cadmium (Cd) quotas, and the net use efficiencies (NUEs) of these bioactive trace metals (mol C fixed per mol cellular trace metal per day). Under B(12)-replete conditions, cells grown at high pCO(2) had lower Fe, Zn and Cd quotas, and used those trace metals more efficiently in comparison with cells grown at low pCO(2). At high pCO(2), B(12)-limited cells had ~50% lower specific growth and carbon fixation rates, and used Fe ~15-fold less efficiently, and Zn and Cd ~3-fold less efficiently, in comparison with B(12)-replete cells. The observed higher Fe, Zn and Cd NUE under high pCO(2)/B(12)-replete conditions are consistent with predicted downregulation of carbon-concentrating mechanisms. Co quotas of B(12)-replete cells were ∼5- to 14-fold higher in comparison with B(12)-limited cells, suggesting that >80% of cellular Co of B(12)-limited cells was likely from B(12). Our results demonstrate that CO(2) and vitamin B(12) interactively influence growth, carbon fixation, trace metal requirements and trace metal NUE of this diatom. This suggests the need to consider complex feedback interactions between multiple environmental factors for this biogeochemically critical group of phytoplankton in the last glacial maximum as well as the current and future changing ocean.
Shakeri Yekta, Sepehr; Gustavsson, Jenny; Svensson, Bo H; Skyllberg, Ulf
2012-01-30
The effect of sequential extraction of trace metals on sulfur (S) speciation in anoxic sludge samples from two lab-scale biogas reactors augmented with Fe was investigated. Analyses of sulfur K-edge X-ray absorption near edge structure (S XANES) spectroscopy and acid volatile sulfide (AVS) were conducted on the residues from each step of the sequential extraction. The S speciation in sludge samples after AVS analysis was also determined by S XANES. Sulfur was mainly present as FeS (≈ 60% of total S) and reduced organic S (≈ 30% of total S), such as organic sulfide and thiol groups, in the anoxic solid phase. Sulfur XANES and AVS analyses showed that during first step of the extraction procedure (the removal of exchangeable cations), a part of the FeS fraction corresponding to 20% of total S was transformed to zero-valent S, whereas Fe was not released into the solution during this transformation. After the last extraction step (organic/sulfide fraction) a secondary Fe phase was formed. The change in chemical speciation of S and Fe occurring during sequential extraction procedure suggests indirect effects on trace metals associated to the FeS fraction that may lead to incorrect results. Furthermore, by S XANES it was verified that the AVS analysis effectively removed the FeS fraction. The present results identified critical limitations for the application of sequential extraction for trace metal speciation analysis outside the framework for which the methods were developed. Copyright © 2011 Elsevier B.V. All rights reserved.
Thanh-Nho, Nguyen; Strady, Emilie; Nhu-Trang, Tran-Thi; David, Frank; Marchand, Cyril
2018-04-01
Mangroves can be considered as biogeochemical reactors along (sub)tropical coastlines, acting both as sinks or sources for trace metals depending on environmental factors. In this study, we characterized the role of a mangrove estuary, developing downstream a densely populated megacity (Ho Chi Minh City, Vietnam), on the fate and partitioning of trace metals. Surface water and suspended particulate matter were collected at four sites along the estuarine salinity gradient during 24 h cycling in dry and rainy seasons. Salinity, pH, DO, TSS, POC, DOC, dissolved and particulate Fe, Mn, Cr, As, Cu, Ni, Co and Pb were measured. TSS was the main trace metals carrier during their transit in the estuary. However, TSS variations did not explain the whole variability of metals distribution. Mn, Cr and As were highly reactive metals while the other metals (Fe, Ni, Cu, Co and Pb) presented stable log K D values along the estuary. Organic matter dynamic appeared to play a key role in metals fractioning. Its decomposition during water transit in the estuary induced metal desorption, especially for Cr and As. Conversely, dissolved Mn concentrations decreased along the estuary, which was suggested to result from Mn oxidative precipitation onto solid phase due to oxidation and pH changes. Extra sources as pore-water release, runoff from adjacent soils, or aquaculture effluents were suggested to be involved in trace metal dynamic in this estuary. In addition, the monsoon increased metal loads, notably dissolved and particulate Fe, Cr, Ni and Pb. Copyright © 2018 Elsevier Ltd. All rights reserved.
NASA Astrophysics Data System (ADS)
Mahoney, C.; März, C.; Wagner, T.
2016-12-01
It is well known that for geochemical studies on ancient rocks, outcrop samples can be compromised by present-day weathering. This raises the fundamental question, if only outcrop samples are available, how reliable can paleoenvironmental reconstructions be? To answer this question, shale samples have been gathered from Cretaceous outcrops of the Eastern Cordillera of Colombia, and analysed by XRF and Fe speciation in order to investigate paleo-redox conditions in this margin basin of the Proto-Atlantic. The samples are consistently depleted (relative to average shale) in redox-related trace metals and in total Fe indicating oxic conditions, whereas Fe speciation (highly reactive over total Fe) indicates anoxic conditions. We ask if this depletion in trace metals and total Fe is due to a lack of primary supply from the depositional environment, or if is it caused by modern oxidative outcrop weathering in this tropical mountainous setting? Our results from artificial weathering experiments confirm that certain trace metals U, Zn and Mo are easily leached from the samples, whereas Fe is quantitatively retained in the samples due to conversion of pyrite and siderite to Fe oxides. Pristine samples from wells in the adjacent Middle Magdalena Valley Basin (MMV) also exhibit total Fe depletion, but are up to 2000-fold enriched in Mo. This combined evidence indicates that the depletion of trace metals may be due to contemporary weathering, but there has to be a paleoenvironmental reason behind the low total Fe signature. The Guiana Shield was the probable source of sediment to the Cretaceous basin. The Chemical Index of Alteration suggest the source of detrital material was initially highly weathered (average 83, maximum 95). Ancient laterites have been identified on the Guiana Shield, and retention of Fe in these laterites may explain the low Fe input into the Eastern Cordillera basin. These results confirm that trace metal-based redox proxies may be seriously affected by oxidative weathering in outcrops, and caution should be applied when using such samples. But it also appears that due to the extreme chemical weathering in the provenance area, the Eastern Cordillera basin (and adjacent MMV basin) was unusually Fe-depleted throughout the Cretaceous, and this geochemical signal is preserved even in weathered outcrop samples.
Al-Wabel, Mohammad I; Sallam, Abd El-Azeem S; Usman, Adel R A; Ahmad, Mahtab; El-Naggar, Ahmed Hamdy; El-Saeid, Mohammed Hamza; Al-Faraj, Abdulelah; El-Enazi, Khaled; Al-Romian, Fahad A
2017-06-01
The present study was conducted in one of the most densely cultivated area of Al-Qassim region in Kingdom of Saudi Arabia to (i) monitor trace metal (Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, and Zn) contents in surface and subsurface soils, (ii) assess the pollution and potential ecological risk levels of trace metals, and (iii) identify trace metal sources using enrichment factor (EF), correlation matrix, and principal component analysis (PCA). The pollution levels of the analyzed trace metals calculated by the geoaccumulation index (I geo ) and contamination factor (C f ) suggested that the soils were highly contaminated with Cd and moderately contaminated with Pb. Based on the average values of EF, soil samples were found to present extremely high enrichment for Cd, significant enrichment for Pb, moderate enrichment for Zn, and deficient to minimal enrichment for other trace metals. Among the analyzed trace metals, a very high ecological risk was observed only in the case of Cd at some sampling sites. Meanwhile, other investigated trace metals had a low ecological risk. The results of PCA combined with correlation matrix suggested that Fe, Mn, Zn, Cu, Cr Ni, Cu, and Co represent natural abundance in soil, but Cd, Pb, and Cu are of anthropogenic inputs, mainly due to agrochemical and fertilizer applications. It could be generally concluded that the obtained results can be useful for assessing and conducting a future program for trace metal monitoring in agricultural areas of Saudi Arabia.
Speciations of trace metals in the Danube alluvial sediments within an oil refinery.
Relić, Dubravka; Dordević, Dragana; Popović, Aleksandar; Blagojević, Tamara
2005-07-01
A sequential extraction procedure was applied to identify forms of Ni, Zn, Pb and Cu with Fe- and Mn-oxides associated in alluvial sediments of the River Danube within Pancevo Oil Refinery (Serbia). The five steps of the sequential extraction procedure partitioned metals into: CH(3)COONH(4) extractable (S1); NH(2)OH.HCl carbonate extractable and easily reducible (S2); (NH(4))(2)C(2)O(2)/H(2)C(2)O(2) moderately reducible (S3); H(2)O(2)-HNO(3) organic extractable (S4); and HCl acid soluble residue (S5). Extracted concentrations of trace metals, analyzed after all five steps, were found to be (mg kg(-1)) for Mn: 656, Fe: 26734, Ni: 32.3, Zn: 72.8, Pb: 13.4 and Cu: 27.0. Most of the elements were found in acid soluble residue, characterizing stable compounds in sediments. Non-residual fractions of trace metals (sum of the first four fractions) were analyzed because they are more bioavailable than the residual amount. Correlation analysis and two multivariate analysis methods (principal component and cluster analysis) were used to understand and visualize the associations between the non-residual fractions of trace metals and certain forms, more or less crystalline of Fe- and Mn-oxides within the analyzed sediments, since Fe- and Mn-oxides play an important role in trace metal sorption within aquatic systems, especially within the Danube alluvium where the fluctuations of groundwater are very frequent and the level of groundwater could come close to surface.
Klink, Agnieszka
2017-02-01
The aims of the present investigation were to reveal various trace metal accumulation abilities of two common helophytes Typha latifolia and Phragmites australis and to investigate their potential use in the phytoremediation of environmental metal pollution. The concentrations of Fe, Mn, Zn, Cu, Cd, Pb and Ni were determined in roots, rhizomes, stems and leaves of both species studied as well as in corresponding water and bottom sediments from 19 sites selected within seven lakes in western Poland (Leszczyńskie Lakeland). The principal component and classification analysis showed that P. australis leaves were correlated with the highest Mn, Fe and Cd concentrations, but T. latifolia leaves with the highest Pb, Zn and Cu concentrations. However, roots of the P. australis were correlated with the highest Mn, Fe and Cu concentrations, while T. latifolia roots had the highest Pb, Zn and Cd concentrations. Despite the differences in trace metal accumulation ability between the species studied, Fe, Cu, Zn, Pb and Ni concentrations in the P. australis and T. latifolia exhibited the following accumulation scheme: roots > rhizomes > leaves > stems, while Mn decreased in the following order: root > leaf > rhizome > stem. The high values of bioaccumulation factors and low values of translocation factors for Zn, Mn, Pb and Cu indicated the potential application of T. latifolia and P. australis in the phytostabilisation of contaminated aquatic ecosystems. Due to high biomass of aboveground organs of both species, the amount of trace metals stored in these organs during the vegetation period was considerably high, despite of the small trace metals transport.
Controls on Fe(II)-Activated Trace Element Release from Goethite and Hematite
DOE Office of Scientific and Technical Information (OSTI.GOV)
Frierdich, Andrew J.; Catalano, Jeffrey G.
2012-03-26
Electron transfer and atom exchange (ETAE) between aqueous Fe(II) and Fe(III) oxides induces surface growth and dissolution that affects trace element fate and transport. We have recently demonstrated Ni(II) cycling through goethite and hematite (adsorbed Ni incorporates into the mineral structure and preincorporated Ni releases to solution) during Fe(II)-Fe(III) ETAE. However, the chemical parameters affecting net trace element release remain unknown. Here, we examine the chemical controls on Ni(II) and Zn(II) release from Ni- and Zn-substituted goethite and hematite during reaction with Fe(II). Release follows a rate law consistent with surface reaction limited mineral dissolution and suggests that release occursmore » near sites of Fe(III) reductive dissolution during Fe(II)-Fe(III) ETAE. Metal substituent type affects reactivity; Zn release is more pronounced from hematite than goethite, whereas the opposite trend occurs for Ni. Buildup of Ni or Zn in solution inhibits further release but this resumes upon fluid exchange, suggesting that sustained release is possible under flow conditions. Mineral and aqueous Fe(II) concentrations as well as pH strongly affect sorbed Fe(II) concentrations, which directly control the reaction rates and final metal concentrations. Our results demonstrate that structurally incorporated trace elements are mobilized from iron oxides into fluids without abiotic or microbial net iron reduction. Such release may affect micronutrient availability, contaminant transport, and the distribution of redox-inactive trace elements in natural and engineered systems.« less
Kalnejais, Linda H.; Martin, W. R.; Bothner, Michael H.
2015-01-01
To determine the conditions that lead to a diffusive release of dissolved metals from coastal sediments, porewater profiles of Ag, Cu, and Pb have been collected over seven years at two contrasting coastal sites in Massachusetts, USA. The Hingham Bay (HB) site is a contaminated location in Boston Harbor, while the Massachusetts Bay (MB) site is 11 km offshore and less impacted. At both sites, the biogeochemical cycles include scavenging by Fe-oxyhydroxides and release of dissolved metals when Fe-oxyhydroxides are reduced. Important differences in the metal cycles at the two sites, however, result from different redox conditions. Porewater sulfide and seasonal variation in redox zone depth is observed at HB, but not at MB. In summer, as the conditions become more reducing at HB, trace metals are precipitated as sulfides and are no longer associated with Fe-oxyhydroxides. Sulfide precipitation close to the sediment–water interface limits the trace metal flux in summer and autumn at HB, while in winter, oxidation of the sulfide phases drives high benthic fluxes of Cu and Ag, as oxic conditions return. The annual diffusive flux of Cu at HB is found to be significant and contributes to the higher than expected water column Cu concentrations observed in Boston Harbor. At MB, due to the lower sulfide concentrations, the association of trace metals with Fe-oxyhydroxides occurs throughout the year, leading to more stable fluxes. A surface enrichment of solid phase trace metals was found at MB and is attributed to the persistent scavenging by Fe-oxyhydroxides. This process is important, particularly at sites that are less reducing, because it maintains elevated metal concentrations at the surface despite the effects of bioturbation and sediment accumulation, and because it may increase the persistence of metal contamination in surface sediments.
Laser-Induced Breakdown Spectroscopy of Trace Metals
NASA Technical Reports Server (NTRS)
Simons, Stephen (Technical Monitor); VanderWal, Randall L.; Ticich, Thomas M.; West, Joseph R., Jr.
2004-01-01
An alternative approach for laser-induced breakdown spectroscopy (LIBS) determination of trace metal determination in liquids is demonstrated. The limits of detection (LOD) for the technique ranged from 10 ppb to 10 ppm for 15 metals metals (Mg, Al, Si, Ca, Ti, Cr, Fe, Co, Ni, Cu, Zn, As, Cd, Hg, Pb) tested.
Palazzolo, Dominic L.; Crow, Andrew P.; Nelson, John M.; Johnson, Robert A.
2017-01-01
Introduction: ECIGs are currently under scrutiny concerning their safety, particularly in reference to the impact ECIG liquids (E-liquids) have on human health. One concern is that aerosolized E-liquids contain trace metals that could become trapped in respiratory tissues and induce pathology. Methods: To mimic this trapping, peristaltic pumps were used to generate and transport aerosol onto mixed cellulose ester (MCE) membranes where aluminum (Al), arsenic (As), cadmium (Cd), copper (Cu), iron (Fe), manganese (Mn), nickel (Ni), lead (Pb), and zinc (Zn) were subsequently captured and quantified. The presence of trace metals on unexposed MCE membranes and on MCE membranes exposed to mainstream smoke served as control and comparison, respectively. The presence of these metals was also determined from the E-liquid before aerosolization and untouched by the ECIG device. All metals were quantified using ICP-MS. The ECIG core assembly was analyzed using scanning electron microscopy with elemental analysis capability. Results: The contents (μg) of Al, As, Cd, Cu, Fe, Mn, Ni, Pb, and Zn on control MCE membranes were 1.2 ± 0.2, 0.050 ± 0.002, 0.047 ± 0.003, 0.05 ± 0.01, 0.001 ± 0.001, 0.16 ± 0.04, 0.005 ± 0.003, 0.014 ± 0.006, and 0.09 ± 0.02, respectively. The contents of all trace metals on MCE membranes exposed to aerosol were similar to controls, except Ni which was significantly (p < 0.01) higher (0.024 ± 0.004 μg). In contrast, contents of Al, As, Fe, Mn, and Zn on MCE membranes exposed to smoke were significantly higher (p < 0.05) than controls. The contents of Al, As, Cu, Fe, and Mn on smoke-exposed MCE membranes were also significantly higher (p < 0.05) than their content on aerosol-exposed membranes. The contents per cigarette equivalent of metals in E-liquid before aerosolization were negligible compared to amounts of aerosolized E-liquid, except for Fe (0.002 μg before and 0.001 μg after). Elemental analysis of the core assembly reveals the presence of several of these trace metals, especially Al, Fe, Ni, and Zn. Conclusions: In general, from the single ECIG-device/E-liquid combination used, the amount of trace metals from ECIG-generated aerosol are lower than in traditional mainstream smoke, Only Ni in the ECIG-generated aerosol was higher than control. The most probable source of Ni in this aerosol is the core assembly. PMID:28119618
Zhang, Wanli; Zhang, Lei; Li, Aimin
2015-11-01
This study aimed at investigating the effects of trace metals on methane production from food waste and examining the feasibility of reducing metals dosage by ethylenediamine-N,N'-disuccinic acid (EDDS) via improving metals bioavailability. The results indicated that the effects of metal elements highly depended on the supplemental concentrations. Trace metals supplemented under moderate concentrations greatly enhanced the methane yield. However, the excessive supplementation of Fe (1000 mg/L) and Ni (50 mg/L) exhibited the obvious toxicity to methanogens. The combinations of trace metals exhibited remarkable synergistic effects. The supplementation of Fe (100 mg/L) + Co (1 mg/L) + Mo (5 mg/L) + Ni (5 mg/L) obtained the greatest methane yield of 504 mL/g VSadded and the highest increment of 35.5% compared to the reactor without metals supplementation (372 mL/g VSadded). The changes of metals speciation showed the reduction of metals bioavailability during anaerobic digestion, which might weaken the stimulative effects of trace metals. However, the addition of EDDS improved metals bioavailability for microbial uptake and stimulated the activity of methanogens, and therefore, strengthened the stimulative effects of metals on anaerobic digestion of food waste. The batch and semi-continuous experiments confirmed that the addition of EDDS (20 mg/L) bonded to trace metals prior to their supplementation could obtain a 50% reduction of optimal metals dosage. This study provided a feasible method to reduce trace metals dosage without the degeneration of process performance of anaerobic digestion. Copyright © 2015 Elsevier Ltd. All rights reserved.
2012-01-01
We propose a tripartite biochemical mechanism for memory. Three physiologic components are involved, namely, the neuron (individual and circuit), the surrounding neural extracellular matrix, and the various trace metals distributed within the matrix. The binding of a metal cation affects a corresponding nanostructure (shrinking, twisting, expansion) and dielectric sensibility of the chelating node (address) within the matrix lattice, sensed by the neuron. The neural extracellular matrix serves as an electro-elastic lattice, wherein neurons manipulate multiple trace metals (n > 10) to encode, store, and decode coginive information. The proposed mechanism explains brains low energy requirements and high rates of storage capacity described in multiples of Avogadro number (NA = 6 × 1023). Supportive evidence correlates memory loss to trace metal toxicity or deficiency, or breakdown in the delivery/transport of metals to the matrix, or its degradation. Inherited diseases revolving around dysfunctional trace metal metabolism and memory dysfunction, include Alzheimer's disease (Al, Zn, Fe), Wilson’s disease (Cu), thalassemia (Fe), and autism (metallothionein). The tripartite mechanism points to the electro-elastic interactions of neurons with trace metals distributed within the neural extracellular matrix, as the molecular underpinning of “synaptic plasticity” affecting short-term memory, long-term memory, and forgetting. PMID:23050060
NASA Astrophysics Data System (ADS)
Rapp, I.; Schlosser, C.; Gledhill, M.; Achterberg, E. P.
2016-02-01
Fe availability in surface waters determines primary production, N2 fixation and microbial community structure and thus plays an important role in ocean carbon and nitrogen cycles. Eastern boundary upwelling areas with oxygen minimum zones, such as the Mauritanian shelf region, are typically associated with elevated Fe concentrations with shelf sediments as key source of Fe to bottom and surface waters. The magnitude of vertical and horizontal Fe fluxes from shelf sediments to onshore and offshore surface waters are not well constrained and there are still large uncertainties concerning the stabilisation of Fe once released from sediments into suboxic and oxic waters. Supportive data of other trace metals can be used as an indicator of sediment release, scavenging processes and biological utilisation. Here we present soluble (<0.02 µm), dissolved (<0.2 µm) and total dissolvable (unfiltered) trace metal data collected at 10 stations on a 90 nautical mile transect across the Mauritanian shelf region in June 2014 (cruise Meteor 107). The samples were pre-concentrated using an automated off-line pre-concentration device and analysed simultaneously for Cd, Pb, Fe, Ni, Cu, Zn, Mn and Co using a high resolution inductively coupled plasma mass spectrometer (HR-ICP-MS). First results indicate the importance of benthic sources to the overall Fe budget in this region. Both dissolved Fe and Mn showed enhanced concentrations close to the shelf at depths between 40 and 180 m corresponding with low oxygen concentrations (<50 µmol L-1). Elevated soluble, dissolved, and total dissolvable Fe and Mn concentrations at an offshore station coincided with the location of a cyclonic Eddie that was characterised by an oxygen depleted water body. To further assess the accuracy of vertical and horizontal fluxes of Fe and other trace metals, we compare diffusivity estimates determined by a microstructure profiler and the scale length method (de Jong et al. 2012) with observed isotopic Ra data.
Influence of Oxalate on Ni Fate during Fe(II)-Catalyzed Recrystallization of Hematite and Goethite.
Flynn, Elaine D; Catalano, Jeffrey G
2018-06-05
During biogeochemical iron cycling at redox interfaces, dissolved Fe(II) induces the recrystallization of Fe(III) oxides. Oxalate and other organic acids promote dissolution of these minerals and may also induce recrystallization. These processes may redistribute trace metals among the mineral bulk, mineral surface, and aqueous solution. However, the impact of interactions among organic acids, dissolved Fe(II), and iron oxide minerals on trace metal fate in such systems is unclear. The present study thus explores the effect of oxalate on Ni release from and incorporation into hematite and goethite in the absence and presence of Fe(II). When Ni is initially structurally incorporated into the iron oxides, both oxalate and dissolved Fe(II) promote the release of Ni to aqueous solution. When both species are present, their effects on Ni release are synergistic at pH 7 but inhibitory at pH 4, indicating that cooperative and competitive interactions vary with pH. In contrast, oxalate suppresses Ni incorporation into goethite and hematite during Fe(II)-induced recrystallization, decreasing the proportion of Ni substituting in a mineral structure by up to 36%. These observations suggest that at redox interfaces oxalate largely enhances trace metal mobility. In such settings, oxalate, and likely other organic acids, may thus enhance micronutrient availability and inhibit contaminant sequestration.
Bioremoval of trace metals from rhizosediment by mangrove plants in Indian Sundarban Wetland.
Chowdhury, Ranju; Favas, Paulo J C; Jonathan, M P; Venkatachalam, Perumal; Raja, P; Sarkar, Santosh Kumar
2017-11-30
The study accentuated the trace metal accumulation and distribution pattern in individual organs of 13 native mangrove plants along with rhizosediments in the Indian Sundarban Wetland. Enrichment of the essential micronutrients (Mn, Fe, Zn, Cu, Co, Ni) was recorded in all plant organs in comparison to non-essential ones, such as Cr, As, Pb, Cd, Hg. Trunk bark and root/pneumatophore showed maximum metal accumulation efficiency. Rhizosediment recorded manifold increase for most of the trace metals than plant tissue, with the following descending order: Fe>Mn>Zn>Cu>Pb>Ni>Cr>Co>As>Cd>Hg. Concentrations of Cu, Ni, Pb and Hg were found to exceed prescribed sediment quality guidelines (SQGs) indicating adverse effect on adjacent biota. Both index of geoaccumulation (I geo ) and enrichment factor (EF) also indicated anthropogenic contamination. Based on high (>1) translocation factor (TF) and bioconcentration factor (BCF) values Sonneratiaapetala and Avicenniaofficinalis could be considered as potential accumulators, of trace metals. Copyright © 2017 Elsevier Ltd. All rights reserved.
Akortia, Eric; Olukunle, Olubiyi I; Daso, Adegbenro P; Okonkwo, Jonathan O
2017-03-01
Unregulated electronic waste (e-waste) recycling operations have become a significant environmental issue as well as human health risk in developing countries across the world. The present study evaluated the extent of pollution in Agbogbloshie e-waste recycling site in Accra, Ghana. The concentrations of polybrominated diphenyl ethers (PBDEs) and some selected trace metals were determined using gas chromatography electron impact ionization mass spectrometry and flame atomic absorption spectrophotometry, respectively. The concentrations of ∑ PBDEs ranged from 15.6 to 96.8ngg -1 dry weight, with an overall mean of 54.8ngg -1 dw. BDE-28 was the dominant congener followed by BDE-209 and BDE-47. The order of mean concentrations of the abundant trace metals was Fe>Cu>Pb≫Mn, with a mean range of .531-289mgkg -1 . Geoaccumulation index suggested that the surface soils deteriorated from moderate to high metal pollution, particularly for Cu, Pb and Fe. Of the trace metals analysed, Fe exhibited the highest concentration ranging from 3.97 to 918mgkg -1 . Correlation and principal component analyses suggested possible interactions between PBDEs and the trace metals analysed, while source assessment suggested that PBDEs and trace metals were mostly derived from inputs from the e-waste recycling activities. Average daily dose (ADD) was estimated using concentrations corresponding to 5th percentile, median and 95th percentile. Hazard quotients of 380 and 862 were obtained for adults and children respectively, for Cu and Pb which is a cause for concern especially for local children. Copyright © 2016. Published by Elsevier Inc.
NASA Astrophysics Data System (ADS)
Suresh Babu, S.
2016-12-01
Forty two samples were acquired from the surface and bottom water profiles along 5 transects spread over Bahia Magdalena lagoon, Baja California Sur to assess the behavior of trace metals in a high influenced upwelling region on the Pacific coast. To elaborate the fate of metals, also the physico-chemical parameters (pH, temperature, salinity, conductivity, dissolved oxygen). Determination of the concentrations of trace metals (Fe, Mn, Cr, Cu, Co, Pb, Ni, Zn, Cd As, Hg) were measured using Atomic absorption spectrometry. The results demonstrated high values of As, Ni and Co which is attributed to the local geology and phosphate deposits. Low values of Fe and Mn are attested to the oxic conditions of the lagoon which are responsible for the oxidation of Fe and Mn. The region witnesses raised temperatures (28.92ºC) and salinities of 35.2 PSU for its arid climatic conditions and high rates of evaporation. In general, the region presented minor quantities of dissolved trace metals due to dispersion and high intense interaction with the open sea. The results were also compared with other studies to understand the enrichment pattern in this side of the pacific coast which experiences various geothermal activities and upwelling phenomenon.
Sun, Huifang; Shi, Baoyou; Yang, Fan; Wang, Dongsheng
2017-05-01
Trace heavy metals accumulated in iron corrosion scales within a drinking water distribution system (DWDS) could potentially be released to bulk water and consequently deteriorate the tap water quality. The objective of this study was to identify and evaluate the release of trace heavy metals in DWDS under changing source water conditions. Experimental pipe loops with different iron corrosion scales were set up to simulate the actual DWDS. The effects of sulfate levels on heavy metal release were systemically investigated. Heavy metal releases of Mn, Ni, Cu, Pb, Cr and As could be rapidly triggered by sulfate addition but the releases slowly decreased over time. Heavy metal release was more severe in pipes transporting groundwater (GW) than in pipes transporting surface water (SW). There were strong positive correlations (R 2 > 0.8) between the releases of Fe and Mn, Fe and Ni, Fe and Cu, and Fe and Pb. When switching to higher sulfate water, iron corrosion scales in all pipe loops tended to be more stable (especially in pipes transporting GW), with a larger proportion of stable constituents (mainly Fe 3 O 4 ) and fewer unstable compounds (β-FeOOH, γ-FeOOH, FeCO 3 and amorphous iron oxides). The main functional iron reducing bacteria (IRB) communities were favorable for the formation of Fe 3 O 4 . The transformation of corrosion scales and the growth of sulfate reducing bacteria (SRB) accounted for the gradually reduced heavy metal release with time. The higher metal release in pipes transporting GW could be due to increased Fe 6 (OH) 12 CO 3 content under higher sulfate concentrations. Copyright © 2017 Elsevier Ltd. All rights reserved.
Experimental Constraints on Iron Mobilization into Biomass Burning Aerosols
NASA Astrophysics Data System (ADS)
Sherry, A. M.; Romaniello, S. J.; Herckes, P.; Anbar, A. D.
2017-12-01
Atmospheric deposition of iron (Fe) can limit marine primary productivity and, therefore, carbon dioxide uptake. Recent modeling studies suggest that biomass burning aerosols may contribute a significant amount of soluble Fe to the surface ocean. To address this hypothesis, we collected foliage samples from species representative of several biomes impacted by severe fire events. Existing studies of burn-induced trace element mobilization have often collected both entrained soil particles along with material from burning biomass, making it difficult to determine the actual source of aerosolized trace metals. In order to better constrain the importance of biomass vs. entrained soil as a source of trace metals in burn aerosols, we conducted burn experiments using soil-free foliage representative of a variety of fire-impacted ecosystems. The resulting burn aerosols were collected in two stages (PM > 2.5 μm and PM < 2.5 μm) on cellulose filters using a high-volume air sampler equipped an all-Teflon impactor. Unburned foliage and burn aerosols were analyzed for Fe and other trace metals using inductively coupled plasma mass spectrometry (ICP-MS). Our results show that 0.06-0.86 % of Fe in plant biomass is likely mobilized as atmospheric aerosols during biomass burning events, depending on the type of foliage. We used these results and estimates of annual global wildfire area to estimate the impact of biomass burning aerosols on total atmospheric Fe flux to the ocean. We estimate that biomass-derived Fe likely contributes 3% of the total soluble Fe flux from aerosols. Prior studies, which implicitly included both biomass and soil-derived Fe, concluded that biomass burning contributed as much as 7% of the total marine soluble Fe flux from aerosols. Together, these studies suggest that biomass and fire-entrained soil probably contribute equally to the total fire-derived Fe aerosol flux. Further study of solubility differences between plant- and soil-derived Fe is needed to improve estimates of the soluble Fe contribution from biomass burning to the marine soluble Fe flux.
NASA Astrophysics Data System (ADS)
Johnston, Scott G.; Rose, Andrew L.; Burton, Edward D.; Webster-Brown, Jenny
2015-01-01
Large alpine landslides that entrain substantial organic material below the water table and create suspended floodplains may have long-term consequences for the mobilisation of redox sensitive elements, such as Fe, into streamwaters. In turn, the cycling of iron in aquatic systems can influence the fate of nutrients, alter primary productivity, enhance accumulation of trace metals and induce fractionation of rare earth elements (REE). In this study we examine a reach of a pristine oligotrophic alpine stream bracketing a 30 year-old landslide and explore the consequences of landslide-induced Fe mobilisation for aqueous geochemistry and the composition of benthic stream cobble biofilm. Elevated Fe2+ and Mn in landslide zone stream waters reflect inputs of circumneutral groundwater from the landslide debris-zone floodplain. Geochemical characteristics are consistent with reductive dissolution being a primary mechanism of Fe2+ and Mn mobilisation. Stream cobble biofilm in the landslide zone is significantly (P < 0.01) enriched in poorly crystalline Fe(III) (∼10-400 times background) and Mn (∼15-150 times background) (1 M HCl extractable; Fe(III)Ab). While the landslide zone accounts for less than ∼9% of the total stream length, we estimate it is responsible for approximately 60-80% of the stream's benthic biofilm load of poorly crystalline Fe(III) and Mn. Biofilm Fe(III) precipitates are comprised mainly of ferrihydrite, lepidocrocite and an organic-Fe species, while precipitate samples collected proximal to hyporheic seeps contain abundant sheath structures characteristic of the neutrophilic Fe(II)-oxidising bacteria Leptothrix spp. Stream-cobble Fe(III)-rich biofilm is accumulating PO43- (∼3-30 times background) and behaving as a preferential substrate for photosynthetic periphyton, with benthic PO43-, chlorophyll a, organic carbonHCl and total N all significantly positively correlated with Fe(III)Ab and significantly elevated within the landslide zone (P < 0.01). P K-edge XANES indicates P is associated with both ferric and Ca-phosphate minerals, while SEM-EDX elemental mapping of Fe(III) precipitates reveal strong spatial associations between P, Ca and Fe. Cobble Fe(III)-rich biofilm is also sorbing and accumulating multiple trace metals and REE. Within the landslide zone there are significant (P < 0.01) enrichments (up to ∼10-100 times background) for most trace metals examined here and metals display significant positive linear correlations with Fe(III)Ab on a log transformed basis. Stream cobble biofilm also exhibits distinct REE fractionation along the flow path, with light REE (La, Ce, Nd, Pr) preferentially partitioning to the Fe(III) and Mn-rich biofilm within the landslide zone. Accumulation of PO43- and trace metals in this relatively environmentally labile form may have implications for their bioavailability and downstream transport, but further research is required to assess possible ecological consequences. This study demonstrates the potential for large alpine landslides to encourage reach-scale circumneutral Fe mobilisation in adjacent streams, thereby shaping multiple aspects of benthic stream geochemistry for many years after the landslide event itself.
Preda, Micaela; Cox, Malcolm E
2002-11-01
The Pumicestone region is a unique catchment in northern Moreton Bay, southeast Queensland. The region supports a wide range of land-use activities as well as attractions such as nature conservation areas. One environmental aspect that has not previously been addressed in this area is the occurrence of minor and trace metals in estuarine sediments associated with the main estuaries of the region. The trace metals included in this investigation are: vanadium, chromium, molybdenum, cobalt, nickel, copper, zinc, cadmium, lead and arsenic. To determine and evaluate the occurrence and distribution of metals in the area, several components have been analysed: bedrock material, pre-industrial settings, recent estuarine sediments, soils of estuarine origin and mangrove pneumatophores. The 40 sites chosen for sediment and soil samples cover a variety of estuarine settings and represent a range of natural conditions in terms of channel and bank morphology, tidal energy, vegetation cover, relationship to bedrock, water salinity and land disturbance. The chemical, mineralogical and statistical analyses employed in this study enabled (a) establishment of background values for the area, (b) determination of relationships between metals and (c) identification of sites with anomalous metal concentrations. All the metals found in the sediments of the area are sourced from the geological bedrock. The dominant trace elements identified in sediments are Zn, V and Cr. The remaining metals are highly variable spatially. All trace metals are controlled by the presence of Fe and Mn oxides, and by the grainsize of the sediment. Typically, fine-grained Fe-rich materials tend to adsorb more trace metals than sandy sediments. In soils that have developed from estuarine muds, some metals such as Cr, Mo, Pb and As tend to be in larger quantities than in the estuarine counterparts. Some of the elements, which occur in significant amounts in the sediment, have been detected in mangrove tissue (Avicenniamarina) such as V, Cr, Zn, Fe and Mn. Of particular note is Cu, which is present in mangrove tissue in quantities many times exceeding the sediment concentration. The comparative analysis of pre-industrial settings and recent sediments and soils highlighted some areas of metal enrichment such as acid-affected sites where oxidation of pyrite has mobilised metals from sediments; these metals are then redistributed in Fe-rich surficial layers. Disturbed banks within the estuaries are also likely to have low levels of metal enrichment due to boating activities.
Rainbow, P.S.; Poirier, L.; Smith, B.D.; Brix, K.V.; Luoma, S.N.
2006-01-01
Diet is an important exposure route for the uptake of trace metals by aquatic invertebrates, with trace metal trophic transfer depending on 2 stages - assimilation and subsequent accumulation by the predator. This study investigated the trophic transfer of trace metals from the sediment-dwelling polychaete worm Nereis diversicolor from metal-rich estuarine sediments in southwestern UK to 2 predators - another polychaete N. virens (Cu, Zn, Pb, Cd, Fe) and the decapod crustacean Palaemonetes varians (Cu, Zn, Pb, Cd, Fe, Ag, As, Mn). N. virens showed net accumulation of Cu, Zn, Pb and Cd from the prey; accumulation increased with increasing prey concentration, but a coefficient of trophic transfer decreased with increasing prey concentration, probably because a higher proportion of accumulated metal in the prey is bound in less trophically available (insoluble) detoxified forms. The trace metal accumulation patterns of P. varians apparently restricted significant net accumulation of metals from the diet of N. diversicolor to just Cd. There was significant mortality of the decapods fed on the diets of metal-rich worms. Metal-rich invertebrates that have accumulated metals from the rich historical store in the sediments of particular SW England estuaries can potentially pass these metals along food chains, with accumulation and total food chain transfer depending on the metal assimilation efficiencies and accumulation patterns of the animal at each trophic level. This trophic transfer may be significant enough to have ecotoxicological effects. ?? Inter-Research 2006.
The Dart estuary, Devon, UK: a case study of chemical dynamics and pollutant mobility
NASA Astrophysics Data System (ADS)
Schuwerack, P.-M. M.; Neal, M.; Neal, C.
2007-01-01
Water, sediments and gill and digestive gland tissues of adult common shore crab (Carcinus maenas), collected at Noss Marina, Sandquay (Britannia Royal Naval College), the Dartmouth Pier, Warfleet Cove and Sugary Cove in the Dart estuary, Devon, UK, were analysed for major, minor and trace elements in spring 2004. Total acid-available measurements analysed included the truly dissolved component and acid-available sediments. Trace metal concentrations are associated largely with particulate and micro-particulate/colloidal phases, the latter being able to pass through standard filter papers. Wide ranges of chemical concentrations were found in the water, sediments and tissues at all the locations. In the water column, 48% of the variance is linked to the sea-salt component (Cl, Na, K, Ca, Mg, B, Li and Sr) and the sediment-associated acid-available fractions are linked to Fe-rich lithogenous materials (Ba, Co, Cu, Fe, Mn, V and Zn). In the sediments, trace elements of Cd, Co, Cr, Fe, Pb, Mn, Ni and V are correlated with the sea salts and associated with the fraction of fine sediments within the total sediment. In the gills and the digestive gland tissues of crabs, high concentrations of Al, Cu and Fe are found and there are correlations between acid-available trace metals of Cu, Cr, Fe, Mn, Ni, Sr and Zn. The relationships between trace metal contaminants, their site-specific concentrations, their temporal and spatial variability and the effects of human activities, such as moorland/agriculture with historic mining and recreational activities in the lower Dart estuary, are discussed.
NASA Astrophysics Data System (ADS)
Steinmann, M.; Floch, A. L.; Lucot, E.; Badot, P. M.
2014-12-01
The oxyhydroxides of iron are common soil minerals and known to control the availability of various major and trace elements essential for biogeochemical processes. We present a study from acidic natural forest soils, where reducing redox conditions due to seasonal waterlogging lead to the dissolution of Fe-oxyhydroxides, and to the release of Fe to soil water. In order to study in detail the mechanism of redox cycling of Fe, we used Rare Earth Element (REE) distribution patterns, because an earlier study has shown that they are a suitable tool to identify trace metal sources during soil reduction in wetland soils (Davranche et al., 2011). The REE patterns of soil leachates obtained with the modified 3-step BCR extraction scheme of Rauret et al., (1999) were compared with those of natural soil water. The adsorbed fractions (F1 leach), the reducible fraction of the deepest soil horizon H4 (F2 leach, 50-120 cm), and the oxidizable fractions of horizons H2 to H4 (F3 leachs, 24-120 cm) yielded REE patterns almost identical to soil water (see figure), showing that the REE and trace metal content of soil water was mainly derived from the F1 pool, and from the F2 and F3 pools of the clay mineral-rich deep soil horizons. In contrast, the F2 leach mobilized mainly Fe-oxyhydroxides associated with organic matter of the surface soil and yielded REE patterns significantly different from those of soil water. These results suggest that the trace metal content of soil water in hydromorphic soils is primarily controlled by the clay fraction of the deeper soil horizons and not by organic matter and related Fe-oxyhydroxides of the surface soil. Additional analyses are in progress in order to verify whether the REE and trace metals of the deeper soil horizons were directly derived from clay minerals or from associated Fe-oxyhydroxide coatings. Refs cited: Davranche et al. (2011), Chem. Geol. 284; Rauret et al. (1999), J. Environ. Monit. 1.
LaBar, Julie A; Nairn, Robert W
2018-05-01
A passive treatment system (PTS), including two parallel vertical flow bioreactors (VFBR), was constructed in 2008 for the treatment of unabated net-alkaline ferruginous mine drainage in the Tar Creek Superfund Site in northeastern Oklahoma. Water quality data collected since the PTS began operation indicate significant removal of trace metals in the VFBR. Results of a sequential extraction procedure (SEP) performed on substrate samples showed that the majority of Cd, Co, Fe, Ni, Pb, and Zn were retained in the refractory organic/sulfide fraction. Subsequent acid volatile sulfide/simultaneously extracted metals (AVS/SEM) analyses confirmed the retention of Cd, Fe, Pb, and Zn as sulfides, but Co and Ni results were less certain. The majority of trace metals were retained as insoluble products in the VFBR, while up to 20% of most of the trace metals were retained in soluble, bioavailable fractions. Nearly 70% of Mn was retained in the soluble and bioavailable exchangeable, carbonate, and labile organic fractions. Copyright © 2018 Elsevier Ltd. All rights reserved.
ThomasArrigo, Laurel K; Mikutta, Christian; Byrne, James; Kappler, Andreas; Kretzschmar, Ruben
2017-06-20
In freshwater wetlands, organic flocs are often found enriched in trace metal(loid)s associated with poorly crystalline Fe(III)-(oxyhydr)oxides. Under reducing conditions, flocs may become exposed to aqueous Fe(II), triggering Fe(II)-catalyzed mineral transformations and trace metal(loid) release. In this study, pure ferrihydrite, a synthetic ferrihydrite-polygalacturonic acid coprecipitate (16.7 wt % C), and As- (1280 and 1230 mg/kg) and organic matter (OM)-rich (18.1 and 21.8 wt % C) freshwater flocs dominated by ferrihydrite and nanocrystalline lepidocrocite were reacted with an isotopically enriched 57 Fe(II) solution (0.1 or 1.0 mM Fe(II)) at pH 5.5 and 7. Using a combination of wet chemistry, Fe isotope analysis, X-ray absorption spectroscopy (XAS), 57 Fe Mössbauer spectroscopy and X-ray diffraction, we followed the Fe atom exchange kinetics and secondary mineral formation over 1 week. When reacted with Fe(II) at pH 7, pure ferrihydrite exhibited rapid Fe atom exchange at both Fe(II) concentrations, reaching 76 and 89% atom exchange in experiments with 0.1 and 1 mM Fe(II), respectively. XAS data revealed that it transformed into goethite (21%) at the lower Fe(II) concentration and into lepidocrocite (73%) and goethite (27%) at the higher Fe(II) concentration. Despite smaller Fe mineral particles in the coprecipitate and flocs as compared to pure ferrihydrite (inferred from Mössbauer-derived blocking temperatures), these samples showed reduced Fe atom exchange (9-30% at pH 7) and inhibited secondary mineral formation. No release of As was recorded for Fe(II)-reacted flocs. Our findings indicate that carbohydrate-rich OM in flocs stabilizes poorly crystalline Fe minerals against Fe(II)-catalyzed transformation by surface-site blockage and/or organic Fe(II) complexation. This hinders the extent of Fe atom exchange at mineral surfaces and secondary mineral formation, which may consequently impair Fe(II)-activated trace metal(loid) release. Thus, under short-term Fe(III)-reducing conditions facilitating the fast attainment of solid-solution equilibria (e.g., in stagnant waters), Fe-rich freshwater flocs are expected to remain an effective sink for trace elements.
Klink, Agnieszka; Polechońska, Ludmiła; Dambiec, Małgorzata; Białas, Kamila
2018-01-01
Trees are widely used for biomonitoring and filtering air in industrial, urban, and rural areas. This research was undertaken to examine accumulation capacities of macroelements (Ca, K, Mg, Na) and trace metals (As, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, Zn) in needles and bark of Pinus sylvestris and leaves and bark of Quercus petraea growing in the vicinity of the chlor-alkali plant PCC Rokita in Brzeg Dolny (Lower Silesia, SW Poland). Because Scots pine is well studied and considered a useful bioindicator, we have used this species as a base for comparison of the accumulation ability of sessile oak that shows some features of good bioindicator, but whose biogeochemistry was scarcely studied. Results showed that for both species leaves contained more macroelements (Ca, K, Mg), whereas the bark was richer in most trace metals (Cd, Cr, Cu, Fe, and Pb). However, trees studied differed with respect to element content. Oak bark and leaves were more effective in accumulating macro- and trace elements (bark Cd, Co, Cr, Cu, K, Mg, Mn, Na, Ni, Pb and leaves Ca, Cr, Cu, Fe, K, Mg, Na, Ni) than Scots pine tissues. Nevertheless, foliar metal accumulation index of these species was similar, suggesting that their overall ability to accumulate trace metals was similar.
Microbial Influences on Trace Metal Cycling in a Meromictic Lake, Fayetteville Green Lake, NY
NASA Astrophysics Data System (ADS)
Zerkle, A. L.; House, C.; Kump, L.
2002-12-01
Microorganisms can exist in aquatic environments at very high cell densities of up to 1011 cells/L, and can accumulate significant quantities of trace metals. Bacteria actively take up bioactive trace metals, including Fe, Zn, Mn, Co, Ni, Cu, and Mo, which function as catalytic centers in metalloproteins and metal-activated enzymes involved in virtually all cellular functions. In addition, bacteria may catalyze the release of trace metals from inorganic substrates by processes such as the reduction of iron and manganese oxides, suggesting that trace metal distributions within a natural environment dominated by microbial processes may be controlled primarily by microbial ecology. Fayetteville Green Lake (FGL), NY, is a permanently stratified meromictic lake that has a well-oxygenated surface water mass (mixolimnion) overlying a relatively stagnant, anoxic deep water mass (monimolimnion). A chemocline separates the water masses at around 20m depth, where oxygen concentrations decrease and sulfate and methane concentrations increase. In addition, previous studies have indicated that trace metals such as V, Cr, Co, Mn, and Fe reach elevated concentrations at the chemocline. Using fluorescent in situ hybridization (FISH) of FGL samples from depths of up to 40m with bacterial and archaeal probes, we have shown that fluctuating redox conditions within the FGL water column correlate with significant variations in the composition and distribution of microbial populations with depth. The mixolimnion is dominated by Eubacteria, with increasing concentrations of Archaea in the lower anoxic zone. Increases in microbial cell densities coincide with increases in trace metals at the chemocline, suggesting microbial activity may be responsible for trace metal release at this boundary. 16S rRNA PCR cloning techniques are currently being used to identify dominant microbial populations at various levels within the FGL water column. Future studies will focus on the potential for these dominant microorganisms to influence trace metal cycling and bioavailability in the FGL water column.
Airborne mineral components and trace metals in Paris region: spatial and temporal variability.
Poulakis, E; Theodosi, C; Bressi, M; Sciare, J; Ghersi, V; Mihalopoulos, N
2015-10-01
A variety of mineral components (Al, Fe) and trace metals (V, Cr, Mn, Ni, Cu, Zn, Cd, Pb) were simultaneously measured in PM2.5 and PM10 fractions at three different locations (traffic, urban, and suburban) in the Greater Paris Area (GPA) on a daily basis throughout a year. Mineral species and trace metal levels measured in both fractions are in agreement with those reported in the literature and below the thresholds defined by the European guidelines for toxic metals (Cd, Ni, Pb). Size distribution between PM2.5 and PM10 fractions revealed that mineral components prevail in the coarse mode, while trace metals are mainly confined in the fine one. Enrichment factor analysis, statistical analysis, and seasonal variability suggest that elements such as Mn, Cr, Zn, Fe, and Cu are attributed to traffic, V and Ni to oil combustion while Cd and Pb to industrial activities with regional origin. Meteorological parameters such as rain, boundary layer height (BLH), and air mass origin were found to significantly influence element concentrations. Periods with high frequency of northern and eastern air masses (from high populated and industrialized areas) are characterized by high metal concentrations. Finally, inner city and traffic emissions were also evaluated in PM2.5 fraction. Significant contributions (>50 %) were measured in the traffic site for Mn, Fe, Cr, Zn, and Cu, confirming that vehicle emissions contribute significantly to their levels, while in the urban site, the lower contributions (18 to 33 %) for all measured metals highlight the influence of regional sources on their levels.
Trace metals in the Ob and Yenisei Rivers' Estuaries (the Kara Sea).
NASA Astrophysics Data System (ADS)
Demina, L. L.
2014-12-01
Behavior of some trace metals (Al, As, Cd, Co, Cr, Cu, Fe, Mn, Ni and Pb) in water column (soluble <0.45 µm and particulate fractions) and bottom sediments (surface and cores) along the two transects from the Ob River and Yenisei River Estuaries to the Kara Sea was studied. The length of both transects was about 700 km. Water depth was 12-63 m, O2 dissolved :5.36-9.55 ml l-1. Along the transects salinity increased from 0.07 to 34.2 psu, while the SPM' concentration decreased from 10.31 to 0.31 mg/l. Total suspended particulate matter load is more than one order of magnitude higher in the Ob River Estuary comparing to that of the Yenisei River. It has led to a significant difference between the suspended trace metals' concentrations (µg/l) in water of the two estuaries. With salinity increase along transects Fe susp., Mn susp. and Zn susp. decreased by a factor of 100-500, that has led to a growth of a relative portion of dissolved trace metals followed by their bioaccumulation (Demina et al., 2010). A strong direct correlation between suspended Cu, Fe and SPM mass concentration was found. For the first time along the Yenisei River' Estuary -the Kara Sea transect a direct positive correlation between Cu suspended and volume concentration of SPM (mg/ml3) was found, that was attributed to contribution of phytoplankton aggregates in the SPM composition. A trend of relationship between content of suspended As and pelitic fraction (2-10 µm) of SPM was firstly found in theses basins also. Study of trace metal speciation in the bottom sediments (adsorbed, associated with Fe-Mn (oxyhydr)oxides, organic matter and fixed in the mineral lattice or refractory) has revealed the refractory fraction to be prevailing (70-95% total content) for Fe, Zn, Cu, Co, Ni, Cr, Cd and Pb. That means that toxic heavy metals were not available for bottom fauna. Mn was predominantly found in the adsorbed and (oxyhydr)oxides geochemically labile forms, reflecting the redox condition change along both transects and within the sedimentary cores. References. Demina L.L., Gordeev V.V., Galkin S.V., Kravchishina M.D. Biogeochemistry of some heavy metals and metalloids along the transect the Ob River Estuary - the Kara Sea. Oceanology, 2010, vo. 50, No 5, pp. 729- 742.
Bjørklund, Geir; Aaseth, Jan; Skalny, Anatoly V; Suliburska, Joanna; Skalnaya, Margarita G; Nikonorov, Alexandr A; Tinkov, Alexey A
2017-05-01
Iron (Fe) deficiency is considered as the most common nutritional deficiency. Iron deficiency is usually associated with low Fe intake, blood loss, diseases, poor absorption, gastrointestinal parasites, or increased physiological demands as in pregnancy. Nutritional Fe deficiency is usually treated with Fe tablets, sometimes with Fe-containing multimineral tablets. Trace element interactions may have a significant impact on Fe status. Existing data demonstrate a tight interaction between manganese (Mn) and Fe, especially in Fe-deficient state. The influence of Mn on Fe homeostasis may be mediated through its influence on Fe absorption, circulating transporters like transferrin, and regulatory proteins. The existing data demonstrate that the influence of zinc (Zn) on Fe status may be related to their competition for metal transporters. Moreover, Zn may be involved in regulation of hepcidin production. At the same time, human data on the interplay between Fe and Zn especially in terms of Fe-deficiency and supplementation are contradictory, demonstrating both positive and negative influence of Zn on Fe status. Numerous data also demonstrate the possibility of competition between Fe and chromium (Cr) for transferrin binding. At the same time, human data on the interaction between these metals are contradictory. Therefore, while managing hypoferremia and Fe-deficiency anemia, it is recommended to assess the level of other trace elements in parallel with indices of Fe homeostasis. It is supposed that simultaneous correction of trace element status in Fe deficiency may help to decrease possible antagonistic or increase synergistic interactions. Copyright © 2017 Elsevier GmbH. All rights reserved.
The influence of carbon, sulfur, and silicon on trace element partitioning in iron alloys
NASA Astrophysics Data System (ADS)
Han, J.; Van Orman, J. A.; Crispin, K. L.; Ash, R. D.
2014-12-01
Non-metallic light elements are important constituents of planetary cores and have a strong influence on the partitioning behavior of trace elements. Planetary cores may contain a wide range of non-metallic light elements, including H, N, S, P, Si, and C. Under highly reducing conditions, such as those that are thought to have pertained during the formation of Mercury's core, Si and C, in addition to sulfur, may be particularly important constituents. Each of these elements may strongly effect and have a different impact on the partitioning behavior of trace elements but their combined effects on trace element partitioning have not been quantified. We investigated the partitioning behavior of more than 25 siderophile trace elements within the Fe-S-C-Si system with varying concentrations of C, S, and Si. The experiments were performed under pressures varying from 1 atm to 2 GPa and temperatures ranging from 1200˚C to 1450˚C. All experiments produced immiscible liquids, one enriched in Si and C, and the other predominantly FeS. We found some highly siderophile elements including Os, Ru, Ir, and Re are much more enriched in Fe-Si-C phase than in Fe-S phase, whereas other trace elements like V, Co, Ag, Hf, and Pb are enriched in S-rich phase. However, not all the trace elements enriched in Fe-Si-C phase are repelled by sulfur. Elements like Re and Ru could have different partitioning trends if sulfur concentration in S-rich phase rises. The partitioning behavior of these trace elements could enhance our understanding of the differentiation of Mercury's core under oxygen-poor conditions.
Mo & Fe Influences on Nitrate Assimilation in Lake Ontario and the St Lawrence River
NASA Astrophysics Data System (ADS)
Twiss, M. R.; Salk, K.; Avolio, L. N.; Chappaz, A.; Ostrom, N. E.
2013-12-01
Lake Ontario has undergone a steady increase in nitrate since the early 1970s, a phenomenon also occurring in other large lakes. Possible causes of this increase include rising urban and agricultural runoff, atmospheric deposition, less demand for N due to effective point source P control, and trace metal-N co-limitation as observed in Lake Erie. Despite the abundance of nitrate in Lake Ontario, heterocystous cyanobacteria have been detected here setting up the paradoxical situation wherein some cyanobacteria are investing in the more costly diazotrophy whilst surrounded by a form of N that requires less energy and metal quota to assimilate. Mo and Fe are involved in reductive nitrate assimilation making it possible that reductive nitrate assimilation in Lake Ontario is limited in phytoplankton by low trace metal bioavailability. To test this hypothesis, 1-d enrcihment experiments were conducted using trace metal clean techniques in June 2013 at two coastal sites in Lake Ontario, and 4-d enrichment experiments were conducted in July 2013 on main channel waters of the St. Lawrence River, the outflow of Lake Ontario. Water was sampled from the metalimnion of Lake Ontario and from surface water of the main channel of the river. Water was enriched with the the following treatments in triplicate: control, 100 nM KH2PO4, 50 nM FeCl3, 50 nM Na2MoO4, and a mix of P, Fe & Mo. Experiments in the river showed significant effects due to P (increase in Chl-a, NO3 and SiO2 drawdown, changes in phytoplankton community, increase in photosynthetic efficiency [Fv/Fm]) but less impact of trace metals relative to control, presumably due to greater ambient trace metal bioavailability. As measured using FluoroProbe, the phytoplankton community changed very little (over 1 d) in lake waters; there was no significant change in total chl-a. However, as in the river, Fv/Fm revealed significant metal and P effects with the P, Fe & Mo mix being significantly greater than control (Fig. 1; we will present data relating to the response of PON and POC pools to the enrichment experiments). The results suggest that P was limiting phytoplankton growth and that Mo and Fe were more co-limiting in the lake than in the river. This information builds on prior work demonstrating Fe/N co-limitation and is the first study to investigate the role of Mo in the N cycle in the Laurentian Great Lakes. Figure 1. Photosynthetic efficiency in experimental treatments measured using fast repetition rate fluorimetry after 1 d (Lake Ontario) and 4 d (St. Lawrence River); * = P < 0.05.
Trace metals in Bermuda rainwater
DOE Office of Scientific and Technical Information (OSTI.GOV)
Jickells, T.D.; Knap, A.H.; Church, T.M.
1984-02-20
The concentration of Cd, Cu, Fe, Mn, Ni, Pb, and Zn have been measured in Bermuda rainwater. Factor analysis indicates that Fe, Mn, and Pb have similar to acidic components derived from North America. The other metals all behave simiarly but differently to the acides. Sea salt, even after allowances for fractionation, apparently contributes minor amounts of Cu, Pb, and Zn and uncertain amounts of Fe, Mn, and Cd to Atlantic Ocean precipitation. Wash out ratios, calculated from this data along with earlier measurements of atmospheric trace metal concentration on Bermuda, are of the same order as those reported frommore » other remote ocean areas. The wet depositional fluxes of Cu, Ni, Pb, and Zn to the western Atlantic Ocean are significant compared to measured oceanic flux rates. However, the wet depositional fluxes of Fe and Mn to this area are relatively small, suggesting additional inputs, while an excess wet depositional flux of Cd suggests large-scale atmospheric recycling of this element.« less
Metal concentrations in water and sediments from tourist beaches of Acapulco, Mexico.
Jonathan, M P; Roy, P D; Thangadurai, N; Srinivasalu, S; Rodríguez-Espinosa, P F; Sarkar, S K; Lakshumanan, C; Navarrete-López, M; Muñoz-Sevilla, N P
2011-04-01
A survey on the metal concentrations (As, Ba, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, Sr, V, Zn) in beach water and sediments is reported from the tourist destination of Acapulco city on the Pacific coast of Mexico. The concentration of dissolved trace metals (DTMs) in beach water and acid leachable trace metals (ALTMs) in sediments indicated that they are anthropogenic in nature due to the increased tourist activities in the crowded beach locations. The statistical analysis indicates Fe and Mn play a major role as metal scavengers in both the medium (water and sediment) and the higher value of other metals is site specific in the study area, indicating that they are transported from the local area. Comparison results suggest that the beach water quality has deteriorated more than the sediments and special care needs to be taken to restore the beach quality. Copyright © 2011 Elsevier Ltd. All rights reserved.
Strontium and Trace Metals in the Mississippi River Mixing Zone
NASA Astrophysics Data System (ADS)
Xu, Y.; Marcantonio, F.
2001-12-01
Strontium is generally believed to be a conservative element, i.e., it is assumed that dissolved Sr moves directly from rivers through estuaries to the ocean. More recently, however, detailed sampling of rivers suggests a weak non-conservative behavior for Sr. Here, we present dissolved and suspended load Sr and trace metal data for samples retrieved along salinity transects in the estuarine mixing zone of the Mississippi River. Our cruises took place during times representing high, falling, and low Mississippi River discharge. Sr concentration and isotopic composition were analyzed for both dissolved particulate loads. Selected particle-reactive or redox-sensitive trace metals (Mn, Fe, U, V, Mo, Ti, and Pb) were analyzed simultaneously. In the dissolved load, Sr showed conservative behavior in both high- and low- discharge periods. Non-conservative behavior of Sr predominated during falling discharge in the summer. Significant positive correlations were found between Sr, Mo and Ti. U and V distributions were found to be essentially controlled by mixing of river water and seawater, but with significantly lower riverine concentrations during high-flow stage. Particulate element concentrations can be quite variable and heterogeneous. In this study, strong correlations were found between particulate Mn (and Fe) concentrations and particulate concentrations of Ti, U, V, and Pb. No such correlations with Mn (or Fe) were found for particulate Sr and Mo. There is a vast hypoxic zone along the coast of Louisiana in the Gulf of Mexico that exists during the summer months. Based on the Sr isotope systematics and the relationships between Sr and trace metals, we believe that this eutrophication may contribute to the non-conservative behaviors of Sr and other trace metals. We discuss the potential implications of this hypothesis on the Sr mass balance of present-day and past seawater.
Li, Zhenhua; Chang, Xijun; Zou, Xiaojun; Zhu, Xiangbing; Nie, Rong; Hu, Zheng; Li, Ruijun
2009-01-26
A new method that utilizes ethylenediamine-modified activated carbon (AC-EDA) as a solid-phase extractant has been developed for simultaneous preconcentration of trace Cr(III), Fe(III), Hg(II) and Pb(II) prior to the measurement by inductively coupled plasma optical emission spectrometry (ICP-OES). The new sorbent was prepared by oxidative surface modification. Experimental conditions for effective adsorption of trace levels of Cr(III), Fe(III), Hg(II) and Pb(II) were optimized with respect to different experimental parameters using batch and column procedures in detail. The optimum pH value for the separation of metal ions simultaneously on the new sorbent was 4.0. Complete elution of absorbed metal ions from the sorbent surface was carried out using 3.0 mL of 2% (%w/w) thiourea and 0.5 mol L(-1) HCl solution. Common coexisting ions did not interfere with the separation and determination of target metal ions. The maximum static adsorption capacity of the sorbent at optimum conditions was found to be 39.4, 28.9, 60.5 and 49.9 mg g(-1) for Cr(III), Fe(III), Hg(II) and Pb(II), respectively. The time for 94% adsorption of target metal ions was less than 2 min. The detection limits of the method was found to be 0.28, 0.22, 0.09 and 0.17 ng mL(-1) for Cr(III), Fe(III), Hg(II) and Pb(II), respectively. The precision (R.S.D.) of the method was lower 4.0% (n=8). The prepared sorbent as solid-phase extractant was successfully applied for the preconcentration of trace Cr(III), Fe(III), Hg(II) and Pb(II) in natural and certified samples with satisfactory results.
Diverse stoichiometry of dissolved trace metals in the Indian Ocean
Thi Dieu Vu, Huong; Sohrin, Yoshiki
2013-01-01
Trace metals in seawater are essential to organisms and important as tracers of various processes in the ocean. However, we do not have a good understanding of the global distribution and cycling of trace metals, especially in the Indian Ocean. Here we report the first simultaneous, full-depth, and basin-scale section-distribution of dissolved (D) Al, Mn, Fe, Co, Ni, Cu, Zn, Cd, and Pb in the Indian Ocean. Our data reveal widespread co-limitation for phytoplankton production by DFe and occurrence of redox-related processes. The stoichiometry of the DM/phosphorus ratio agrees within a factor of 5 between deep waters in the Indian and Pacific, whereas it shows variability up to a factor of 300 among water masses within the Indian Ocean. This indicates that a consistent mechanism controls the stoichiometry in the deep waters, which are significantly depleted in Mn, Fe, and Co compared to requirements for phytoplankton.
Dredging-related mobilisation of trace metals: a case study in The Netherlands.
van den Berg, G A; Meijers, G G; van der Heijdt, L M; Zwolsman, J J
2001-06-01
Mobilisation of contaminants is an important issue in environmental risk assessment of dredging projects. This study has aimed at identifying the effects of dredging on mobilisation of trace metals (Zn, Cu, Cd and Pb). The intensities and time scales of trace metal mobilisation were investigated during an experimental dredging project conducted under field conditions. The loss of contaminated dredge spoil is mainly reflected by increasing levels of trace metals in the suspended matter, dissolved trace metal concentrations in the water column are not significantly influenced by the dredging activities. This indicates a strong binding mechanism of trace metals to the solid phase or a fast redistribution over sorptive phases in response to oxidation of e.g. trace metal sulphides. Given the differences in levels of reactive phases (Mn, Fe, sulphides and organic matter) between the riverine suspended matter and the sediments, changes in the levels of these parameters in the suspended matter upon dredging may give information on the processes influencing the behaviour of trace metals and on the potential loss of sediment during dredging operations. Therefore, we recommend to routinely measure these parameters in studies on contaminant behaviour related to dredging activities.
Tu, Zhifeng; He, Qun; Chang, Xijun; Hu, Zheng; Gao, Ru; Zhang, Lina; Li, Zhenhua
2009-09-07
A novel method that utilizes 1-(2-formamidoethyl)-3-phenylurea-modified activated carbon (AC-1-(2-formamidoethyl)-3-phenylurea) as a solid-phase extractant has been developed for simultaneous preconcentration of trace Cr(III), Cu(II), Fe(III) and Pb(II) prior to the measurement by inductively coupled plasma atomic emission spectrometry (ICP-AES). Experimental conditions for effective adsorption of trace levels of Cr(III), Cu(II), Fe(III) and Pb(II) were optimized using batch and column procedures in detail. The optimum pH value for the separation of metal ions simultaneously on the new sorbent was 4. And the adsorbed metal ions could be completely eluted by using 2.0 mL 2.0 mol L(-1) HCl solution. Common coexisting ions did not interfere with the separation and determination of target metal ions. The maximum static adsorption capacity of the sorbent at optimum conditions was found to be 39.8, 39.9, 77.8 and 17.3 mg g(-1) for Cr(III), Cu(II), Fe(III) and Pb(II), respectively. The detection limits of the method were found to be 0.15, 0.41, 0.27 and 0.36 ng mL(-1) for Cr(III), Cu(II), Fe(III) and Pb(II), respectively. The relative standard deviation (RSD) of the method was lower than 4.0% (n=8). The method was successfully applied for the preconcentration of trace Cr(III), Cu(II), Fe(III) and Pb(II) in natural and certified samples with satisfactory results.
Effect of Ocean Acidification on Organic and Inorganic Speciation of Trace Metals.
Stockdale, Anthony; Tipping, Edward; Lofts, Stephen; Mortimer, Robert J G
2016-02-16
Rising concentrations of atmospheric carbon dioxide are causing acidification of the oceans. This results in changes to the concentrations of key chemical species such as hydroxide, carbonate and bicarbonate ions. These changes will affect the distribution of different forms of trace metals. Using IPCC data for pCO2 and pH under four future emissions scenarios (to the year 2100) we use a chemical speciation model to predict changes in the distribution of organic and inorganic forms of trace metals. Under a scenario where emissions peak after the year 2100, predicted free ion Al, Fe, Cu, and Pb concentrations increase by factors of up to approximately 21, 2.4, 1.5, and 2.0 respectively. Concentrations of organically complexed metal typically have a lower sensitivity to ocean acidification induced changes. Concentrations of organically complexed Mn, Cu, Zn, and Cd fall by up to 10%, while those of organically complexed Fe, Co, and Ni rise by up to 14%. Although modest, these changes may have significance for the biological availability of metals given the close adaptation of marine microorganisms to their environment.
Baines, Stephen B.; Chen, Xi; Vogt, Stefan; Fisher, Nicholas S.; Twining, Benjamin S.; Landry, Michael R.
2016-01-01
Mesozooplankton production in high-nutrient low-chlorophyll regions of the ocean may be reduced if the trace element concentrations in their food are insufficient to meet growth and metabolic demands. We used elemental microanalysis (SXRF) of single-celled plankton to determine their trace metal contents during a series of semi-Lagrangian drift studies in an HNLC upwelling region, the Costa Rica Dome (CRD). Cells from the surface mixed layer had lower Fe:S but higher Zn:S and Ni:S than those from the subsurface chlorophyll maximum at 22–30 m. Diatom Fe:S values were typically 3-fold higher than those in flagellated cells. The ratios of Zn:C in flagellates and diatoms were generally similar to each other, and to co-occurring mesozooplankton. Estimated Fe:C ratios in flagellates were lower than those in co-occurring mesozooplankton, sometimes by more than 3-fold. In contrast, Fe:C in diatoms was typically similar to that in zooplankton. RNA:DNA ratios in the CRD were low compared with other regions, and were related to total autotrophic biomass and weakly to the discrepancy between Zn:C in flagellated cells and mesozooplankton tissues. Mesozooplankton may have been affected by the trace element content of their food, even though trace metal limitation of phytoplankton was modest at best. PMID:27275029
Pan, Yunyu; Koopmans, Gerwin F; Bonten, Luc T C; Song, Jing; Luo, Yongming; Temminghoff, Erwin J M; Comans, Rob N J
2016-12-01
Alternating flooding and drainage conditions have a strong influence on redox chemistry and the solubility of trace metals in paddy soils. However, current knowledge of how the effects of water management on trace metal solubility are linked to trace metal uptake by rice plants over time is still limited. Here, a field-contaminated paddy soil was subjected to two flooding and drainage cycles in a pot experiment with two rice plant cultivars, exhibiting either high or low Cd accumulation characteristics. Flooding led to a strong vertical gradient in the redox potential (Eh). The pH and Mn, Fe, and dissolved organic carbon concentrations increased with decreasing Eh and vice versa. During flooding, trace metal solubility decreased markedly, probably due to sulfide mineral precipitation. Despite its low solubility, the Cd content in rice grains exceeded the food quality standards for both cultivars. Trace metal contents in different rice plant tissues (roots, stem, and leaves) increased at a constant rate during the first flooding and drainage cycle but decreased after reaching a maximum during the second cycle. As such, the high temporal variability in trace metal solubility was not reflected in trace metal uptake by rice plants over time. This might be due to the presence of aerobic conditions and a consequent higher trace metal solubility near the root surface, even during flooding. Trace metal solubility in the rhizosphere should be considered when linking water management to trace metal uptake by rice over time.
Poikāne, Rita; Carstensen, Jacob; Dahllöf, Ingela; Aigars, Juris
2005-07-01
The dynamics (fate) of trace metals in suspended particulate matter within the Gulf of Riga has not yet been adequately addressed in the scientific literature. Therefore, during a two year period (2001-2002) samples of suspended particulate matter and surface sediments for trace metal analysis were collected in the Gulf of Riga and the Daugava river, and these data were combined with background information from the national marine monitoring program in Latvia. This paper presents a descriptive study of solid phase trace metals (aluminium, iron, cadmium, chromium, copper, manganese, nickel, lead and zinc) dynamics and their spatial distribution within the Gulf of Riga based on Principal Component Analysis and Cluster analysis. Fluvial particulate matter and particulate Al, Fe, Cr and Ni were brought into the Gulf of Riga mainly during spring flood and thereafter quickly diluted by the water masses of the Gulf of Riga. Fine-grained suspended material and particulate Al and Fe were well mixed and evenly distributed through all deepwater basins of the Gulf of Riga. The increase of particulate Mn below the thermocline in August and a strong negative correlation with dissolved oxygen concentrations suggested that particulate Mn in the water column and the sediments were regulated mainly by changing oxic-anoxic conditions in the sediments of the Gulf of Riga. The observed correlation between Al and Fe in the water column is in contrast to that observed in the nepheloid layer where Fe correlated with Mn, obviously due to fast diagenetic processes on sediment surface. The observed negative correlation of Cd and Zn with total carbon and total nitrogen in the nepheloid layer might indicate different sedimentation mechanisms of these elements, however, this assumption is still inconclusive.
Trace Metals in Urban Stormwater Runoff and their Management
NASA Astrophysics Data System (ADS)
Li, T.; Hall, K.; Li, L. Y.; Schreier, H.
2009-04-01
In past decades, due to the rapid urbanization, land development has replaced forests, fields and meadows with impervious surfaces such as roofs, parking lots and roads, significantly affecting watershed quality and having an impact on aquatic systems. In this study, non-point source pollution from a diesel bus loop was assessed for the extent of trace metal contamination of Cu, Mn, Fe, and Zn in the storm water runoff. The study was carried out at the University of British Columbia (UBC) in the Greater Vancouver Regional District (GVRD) of British Columbia, Canada. Fifteen storm events were monitored at 3 sites from the diesel bus loop to determine spatial and temporal variations of dissolved and total metal concentrations in the storm water runoff. The dissolved metal concentrations were compared with the provincial government discharge criteria and the bus loop storm water quality was also compared with previous studies conducted across the GVRD urban area. To prevent storm water with hazardous levels of contaminants from being discharged into the urban drainage system, a storm water catch basin filter was installed and evaluated for its efficiency of contaminants removal. The perlite filter media adsorption capacities for the trace metals, oil and grease were studied for better maintenance of the catch basin filter. Dissolved copper exceeded the discharge criteria limit in 2 out of 15 cases, whereas dissolved zinc exceeded the criteria in 4 out of 15 cases, and dissolved manganese was below the criteria in all of the events sampled. Dissolved Cu and Zn accounted for 36 and 45% of the total concentration, whereas Mn and Fe only accounted for 20 and 4% of their total concentration, respectively. Since they are more mobile and have higher bioaccumulation potentials, Zn and Cu are considered to be more hazardous to the aquatic environment than Fe and Mn. With high imperviousness (100%) and intensive traffic at the UBC diesel bus loop, trace metal concentrations were 3, 0.7, 9, and 3.2 times higher than the GVRD urban area limits for Cu, Mn, Fe, and Zn, respectively. The filter showed high and stable capture efficiencies in total metals (Cu 62%, Mn 75%, Fe 83%, Zn 62%), dissolved metals (Cu 39%, Mn 37%, Fe 47%, Zn 32%), turbidity (72%), and suspended solids (74%) removal during the first month of operation. After that, there was gradual degradation. The catch basin filter performance improved significantly for the suspended solids and total metal removal after cleaning. However, the perlite filter medium showed poor performance for dissolved metal removal in the second study period. Based on the findings, a catch basin filter is effective in storm water management to control suspended solids loading from storm water runoff.
Nworie, Obinna Elijah; Qin, Junhao; Lin, Chuxia
2017-08-21
A batch experiment was conducted to examine the effects of six low-molecular-weight organic acids on the mobilization of arsenic and trace metals from a range of contaminated soils. The results showed that the organic acids behaved differently when reacting with soil-borne As and trace metals. Oxalic acid and acetic acid had the strongest and weakest capacity to mobilize the investigated elements, respectively. The solubilisation of iron oxides by the organic acids appears to play a critical role in mobilizing other trace metals and As. Apart from acidification and complexation, reductive dissolution played a dominant role in the dissolution of iron oxides in the presence of oxalic acid, while acidification tended to be more important for dissolving iron oxides in the presence of other organic acids. The unique capacity of oxalic acid to solubilize iron oxides tended to affect the mobilization of other elements in different ways. For Cu, Mn, and Zn, acidification-driven mobilization was likely to be dominant while complexation might play a major role in Pb mobilization. The formation of soluble Fe and Pb oxalate complexes could effectively prevent arsenate or arsenite from combining with these metals to form solid phases of Fe or Pb arsenate or arsenite.
Trace metal partitioning in Thalassia testudinum and sediments in the Lower Laguna Madre, Texas.
Whelan, Thomas; Espinoza, Jorge; Villarreal, Xiomara; Cottagoma, Maria
2005-01-01
Seagrass communities dominate the Laguna Madre, which accounts for 25% of the coastal region of Texas. Seagrasses are essential to the health of the Laguna Madre (LM) and have experienced an overall decline in coverage in the Lower Laguna Madre (LLM) since 1967. Little is known on the existing environmental status of the LLM. This study focuses on the trace metal chemistry of four micronutrient metals, Fe, Mn, Cu, and Zn, and two non-essential metals, Pb and As, in the globally important seagrass Thalassia testudinum. Seasonal trends show that concentrations of most essential trace metals increase in the tissue during the summer months. With the exception of (1) Cu in the vertical shoot and root, and (2) Mn in the roots, no significant positive correlation exists between the rhizosphere sediment and T. testudinum tissue. Iron indicates a negative correlation between the morphological units and the rhizosphere sediments. No other significant relationship was found between the sediments and the T. testudinum tissue. Mn was enriched up to 10-fold in the leaf tissue relative to the other morphological units and also enriched relative to the rhizosphere sediments. Both Cu and Mn appear to be enriched in leaf tissue compared to other morphological units and also enriched relative to the Cu and Mn in the rhizoshpere sediments. Sediments cores taken in barren areas were slightly elevated in Zn relative to the rhizosphere sediments, whereas no other metals showed statistical differences between barren sediment cores and rhizosphere sediments. However, no correlation was measured in T. testudinum tissue and Zn in rhizosphere sediments. Previous studies suggested that Fe/Mn ratios could indicate differences between seagrass environments. Our results indicate that there is an influence from the Rio Grande in the Fe/Mn signature in sediments, and that ratio is not reflected in the T. testudinum tissue. The results from this study show that the LLM contains trace metal concentrations less than or equal to values for uncontaminated locations worldwide. In addition, there appears to be a complex partitioning in the trace metals in the morphological units of T. testudinum tissue and that analysis only of the leaf may not be indicative of the trace metal levels in this important seagrass species.
Serrano, A; Pinto-Ibieta, F; Braga, A F M; Jeison, D; Borja, R; Fermoso, F G
2017-12-01
Low concentrations of trace elements in many organic wastes recommend their supplementation in order to avoid potential limitations. Different chelating agents have been used to ensure an adequate trace metal pool in the soluble fraction, by forming dissolved complexes. Ethylenediaminetetraacetic acid (EDTA) is probably the most common, although several negative effects could be associated with its usage. Biomethane potential tests were performed using Olive Mill Solid Waste as the substrate, supplementing different combinations of Fe, Co, Ni, Ba, always under the presence of EDTA. Results show that Ni and Co slightly recovered biodegradability. However, Ba supplementation resulted in worsening the methane yield coefficient in all cases. High concentration of EDTA led to decrease in the activity of anaerobic digestion. High availability of EDTA induces the capture of trace metals like Co or Ni, key trace metals for anaerobic biomass activity. While supplementing trace metals, the addition of Ba and/or EDTA must be carefully considered.
Jayaprakash, M; Kumar, R Senthil; Giridharan, L; Sujitha, S B; Sarkar, S K; Jonathan, M P
2015-10-01
Accumulation of trace metals (Fe, Mn, Cr, Cu, Ni, Co, Pb, Zn, Cd) were investigated in water, sediment (n=20) along with six fish of diverse feeding guilds (Sillago sihama, Liza parsia, Etroplus suratensis, Oreochromis mossambicus, Arius parkii and Gerres oyena) from the Ennore creek, northern part of Chennai metropolitan megacity, southeast coast of India. Dissolved trace metals (DTMs) in surface water samples and total trace metals (TTMs) in surface sediments (top 0-10cm) indicate that concentration pattern of metals was higher in the discharge point of the river/channels entering the main creek. The maximum mean values of DTMs exhibited the following decreasing order (expressed in µg/L): Fe (1698)>Mn (24)>Zn (14.50)>Pb (13.89)>Ni (6.73)>Cu (3.53)>Co (3.04)>Cr (2.01) whereas the trend is somewhat different in sediments (µgg(-1)): Fe (4300)>Mn (640)>Cr (383)>Zn (155)>Cu (102)>Ni (35)>Pb (32)>Cd (0.51) are mainly due to the industrial complexes right on the banks of the river/channels. Species-specific heterogeneous patterns of tissue metal loads were apparent and the overall metal enrichment exhibited the following decreasing order (expressed in µgg(-1)): Cu (7.33)>Fe (6.53)>Zn (4.91)>Cr (1.67)>Pb (1.33)>Ni (0.44)>Mn (0.43)>Co (0.36)>Cd (0.11). This indicates that metals are absorbed onto the different organs, which is also endorsed by the calculated values of bioaccumulation factor (BAFs) (avg. muscle 117, gill 126, liver 123, intestine 118) in fishes. The high calculated biota sediment accumulation factor (BSAF) (0.437) for the species Arius parkii is considered to be a potential bioindicator in this region. The enrichment of trace metals is also supported by the association of metals in water, sediments and different body organs (muscle, gill, liver, intestine) of fish samples. Comparative studies with other coastal regions indicate considerable enrichment of DTMs & TTMs in sediments as well as in various organs of fish samples. Holistic spatial, temporal monitoring and comprehensive regional strategies are required to prevent health risks and ensure nutritional safety conditions. Copyright © 2015 Elsevier Inc. All rights reserved.
Effect of silicon on trace element partitioning in iron-bearing metallic melts
NASA Astrophysics Data System (ADS)
Chabot, Nancy L.; Safko, Trevor M.; McDonough, William F.
2010-08-01
Despite the fact that Si is considered a potentially important metalloid in planetary systems, little is known about the effect of Si in metallic melts on trace element partitioning behavior. Previous studies have established the effects of S, C, and P, nonmetals, through solid metal/liquid metal experiments in the corresponding Fe binary systems, but the Fe-Si system is not appropriate for similar experiments because of the high solubility of Si in solid metal. In this work, we present the results from 0.1MPa experiments with two coexisting immiscible metallic liquids in the Fe-S-Si system. By leveraging the extensive available knowledge about the effect of S on trace element partitioning behavior, we explore the effect of Si. Results for 22 trace elements are presented. Strong Si avoidance behavior is demonstrated by As, Au, Ga, Ge, Sb, Sn, and Zn. Iridium, Os, Pt, Re, Ru, and W exhibit weak Si avoidance tendencies. Silicon appears to have no significant effect on the partitioning behaviors of Ag, Co, Cu, Cr, Ni, Pd, and V, all of which had similar partition coefficients over a wide range of Si liquid concentrations from Si-free to 13 wt%. The only elements in our experiments to show evidence of a potentially weak attraction to Si were Mo and Rh. Applications of the newly determined effects of Si to problems in planetary science indicate that (1) The elements Ni, Co, Mo, and W, which are commonly used in planetary differentiation models, are minimally affected by the presence of Si in the metal, especially in comparison to other effects such as from oxygen fugacity. 2) Reduced enstatite-rich meteorites may record a chemical signature due to Si in the metallic melts during partial melting, and if so, elements identified by this study as having strong Si avoidance may offer unique insight into unraveling the history of these meteorites.
Mobilization of Trace Metals in an Experimental Carbon Sequestration Scenario
NASA Astrophysics Data System (ADS)
Marcon, V.; Kaszuba, J. P.
2012-12-01
Mobilizing trace metals with injection of supercritical CO2 into deep saline aquifers is a concern for geologic carbon sequestration. The potential for leakage from these systems requires an understanding of how injection reservoirs interact with the overlying potable aquifers. Hydrothermal experiments were performed to evaluate metal mobilization and mechanisms of release in a carbonate storage reservoir and at the caprock-reservoir boundary. Experiments react synthetic Desert Creek limestone and/or Gothic Shale, formations in the Paradox Basin, Utah, with brine that is close to equilibrium with these rocks. A reaction temperature of 1600C accelerates the reaction kinetics without changing in-situ water-rock reactions. The experiments were allowed to reach steady state before injecting CO2. Changes in major and trace element water chemistry, dissolved carbon and sulfide, and pH were tracked throughout the experiments. CO2 injection decreases the pH by 1 to 2 units; concomitant mineral dissolution produces elevated Ba, Cu, Fe, Pb, and Zn concentrations in the brine. Concentrations subsequently decrease to approximately steady state values after 120-330 hours, likely due to mineral precipitation as seen in SEM images and predicted by geochemical modeling. In experiments that emulate the caprock-reservoir boundary, final Fe (0.7ppb), an element of secondary concern for the EPA, and Pb (0.05ppb) concentrations exceed EPA limits, whereas Ba (0.140ppb), Cu (48ppb), and Zn (433ppb) values remain below EPA limits. In experiments that simulate deeper reservoir conditions, away from the caprock boundary, final Fe (3.5ppb) and Pb (0.017ppb) values indicate less mobilization than seen at the caprock-reservoir boundary, but values still exceed EPA limits. Barium concentrations always remain below the EPA limit of 2ppb, but are more readily mobilized in experiments replicating deeper reservoir conditions. In both systems, transition elements Cd, Cr, Cu, Pb and Zn behave in a similar manner, increasing in concentration with injection but continually decreasing after about 830 hours until termination of the experiment. SEM images and geochemical models indicate initial dissolution of all rocks and minerals, re-precipitation of Ca-Mg-Fe carbonates and Fe-sulfides, and precipitation of anhydrite in both systems. Calcite dissolves more readily than dolomite in these experiments, but re-precipitates in veins on dolomite. If brines leak from a storage reservoir and mix with a potable aquifer, the experimental results suggest that Ba, Cu, and Zn will not be contaminants of concern. Pb, Fe and As (still under consideration) initially exceed the EPA threshold and may require careful attention in a sequestration scenario. However, experimentally observed trends of decreasing trace metal concentration suggest that these metals could become less of a concern during the life of a carbon repository. Finally, the caprock plays an active role in trace metal mobilization in the system. The caprock provides a source of metals, although subsequent precipitation may remove metals from solution.
Nasirian, Hassan; Vazirianzadeh, Babak; Taghi Sadeghi, Sayyed Mohammad; Nazmara, Shahrokh
2014-01-01
Abstract The quantity of some trace metals of mosquito larvae in Shadegan International Wetland from Iran was evaluated. Water, waterbed sediment, and mosquito larvae samplings were carried out from an urban site in the east of the wetland, using standard methods in December 2011. The identified Culiseta subochrea (Edwards) and Aedes caspius s.l. (Pallas) larvae, water, and waterbed sediment samples were analyzed for As, Cd, Co, Cr, Cu, Fe, Hg, Mn, Pb, and Zn trace metals using standard preparation and isolation procedure. Result showed that the waterbed sediment and Cu. subochrea larvae are polluted with all trace metals investigated except As and Hg. The trace metals bioaccumulated in the Cu. subochrea larvae range from 31.78 at the lowest level for Cr to 3822.7 at the highest level for Cd. In a conclusion, this is the first report confirmed that Cu. subochrea likely used as a bioindicator to trace metal pollution in marine ecosystems in the world, especially wetlands. PMID:25550357
Microbial biofilms control economic metal mobility in an acid-sulfate hydrothermal system
NASA Astrophysics Data System (ADS)
Phillips-Lander, C. M.; Roberts, J. A.; Hernandez, W.; Mora, M.; Fowle, D. A.
2012-12-01
Trace metal cycling in hydrothermal systems has been the subject of a variety of geochemical and economical geology studies. Typically in these settings these elements are sequestered in sulfide and oxide mineral fractions, however in near-surface low-temperature environments organic matter and microorganisms (typically in mats) have been implicated in their mobility through sorption. Here we specifically examine the role of microbial biofilms on metal partitioning in an acid-sulfate hydrothermal system. We studied the influence of microorganisms and microbial biofilms on trace metal adsorption in Pailas de Aguas I, an acid-sulfate hot spring on the southwest flank of Rincon de la Vieja, a composite stratovolcano in the Guanacaste Province, Costa Rica. Spring waters contain high suspended loads, and are characterized by high T (79.6-89.3oC), low pH (2.6-4), and high ionic strengths (I= 0.5-0.8). Waters contain high concentrations of the biogeochemically active elements Fe (4-6 mmol/l) and SO42- (38 mmol/l), but PO43- are below detection limits (bdl). Silver, Ni, and Mo concentrations are bdl; however other trace metals are present in solution in concentrations of 0.1-0.2 mg/l Cd, 0.2-0.4 mg/l Cr and V, 0.04-1 mg/l Cu,. Preliminary 16S rRNA analyses of microorganisms in sediments reveal several species of algae, including Galderia sp., Cyanidium sp, γ-proteobacteria, Acidithiobacillus caldus, Euryarcheota, and methanogens. To evaluate microbial biofilms' impact on trace metal mobility we analyzed a combination of suspended, bulk and biofilm associated sediment samples via X-ray diffraction (XRD) and trace element sequential extractions (SE). XRD analysis indicated all samples were primarily composed of Fe/Al clay minerals (nontronite, kaolinite), 2- and 6-line ferrihydrite, goethite, and hematite, quartz, and opal-α. SE showed the highest concentrations of Cu, Mo, and V were found in the suspended load. Molybdenum was found primarily in the residual and organic fractions of suspended sediments. Copper is distributed in all but the carbonate fraction of suspended sediments. Vanadium was bound primarily to the oxide and residual fractions with Si, which is probably found as opal-α. In contrast, biofilm sediments had the highest concentrations of Fe, Si, Cd, Al, Zn, Ag, and Ni. Trace metals were sequestered mainly in the organic fraction in decreasing concentrations of: Cu
Automation of high-frequency sampling of environmental waters for reactive species
NASA Astrophysics Data System (ADS)
Kim, H.; Bishop, J. K.; Wood, T.; Fung, I.; Fong, M.
2011-12-01
Trace metals, particularly iron and manganese, play a critical role in some ecosystems as a limiting factor to determine primary productivity, in geochemistry, especially redox chemistry as important electron donors and acceptors, and in aquatic environments as carriers of contaminant transport. Dynamics of trace metals are closely related to various hydrologic events such as rainfall. Storm flow triggers dramatic changes of both dissolved and particulate trace metals concentrations and affects other important environmental parameters linked to trace metal behavior such as dissolved organic carbon (DOC). To improve our understanding of behaviors of trace metals and underlying processes, water chemistry information must be collected for an adequately long period of time at higher frequency than conventional manual sampling (e.g. weekly, biweekly). In this study, we developed an automated sampling system to document the dynamics of trace metals, focusing on Fe and Mn, and DOC for a multiple-year high-frequency geochemistry time series in a small catchment, called Rivendell located at Angelo Coast Range Reserve, California. We are sampling ground and streamwater using the automated sampling system in daily-frequency and the condition of the site is substantially variable from season to season. The ranges of pH of ground and streamwater are pH 5 - 7 and pH 7.8 - 8.3, respectively. DOC is usually sub-ppm, but during rain events, it increases by an order of magnitude. The automated sampling system focuses on two aspects- 1) a modified design of sampler to improve sample integrity for trace metals and DOC and 2) remote controlling system to update sampling volume and timing according to hydrological conditions. To maintain sample integrity, the developed method employed gravity filtering using large volume syringes (140mL) and syringe filters connected to a set of polypropylene bottles and a borosilicate bottle via Teflon tubing. Without filtration, in a few days, the dissolved concentration of Fe and Mn in the ground and streamwater samples stored in low density polyethylene (LDPE) sample bags decreased by 89% and 97%, respectively. In some cases of groundwater, the concentration of Ca decreased by 25%, due to degassing of CO2. However, DOC of the samples in LDPE bags without filtration increased up to 50% in 2 weeks, suggesting contamination from the bag. Performance of the new design was evaluated using the Fe-Mn-spiked Rivendell samples and environmental water samples collected from 1) Rivendell, 2) the Strawberry Creek located at the University of California, Berkeley campus, and 3) the San Francisco Bay. The samples were filtered using the developed method and stored in room temperature in 2 - 3 weeks without further treatment. The method improved the sample integrity significantly; the average recovery rates of Fe, Mn, DOC, and Ca were 92%, 98%, 90%, and 97%, respectively.
Rezende, C E; Lacerda, L D; Ovalle, A R C; Souza, C M M; Gobo, A A R; Santos, D O
2002-07-01
The concentrations of Al, Fe, Mn, Zn, Cu, Pb, Ni, Cr, Ba, V, Sn and As in offshore bottom sediments from the Bacia de Campos oil field, SE Brazil, were measured at the beginning and at 7 months after completion of the drilling operation. Concentrations of Al, Fe, Ba, Cr, Ni and Zn were significantly higher closer to the drilling site compared to stations far from the site. Average concentrations of Al, Cu, and in particular of Ni, were significantly higher at the end of the drilling operation than at the beginning. Comparison between drilling area sediments with control sediments of the continental platform, however, showed no significant difference in trace metal concentrations. Under the operation conditions of this drilling event, the results show that while changes in some trace metal concentrations do occur during drilling operations, they are not significantly large to be distinguished from natural variability of the local background concentrations.
NASA Astrophysics Data System (ADS)
Thompson, A.; Chorover, J.; Chadwick, O.
2003-12-01
Iron (Fe)-oxides are important sorbents for nutrients, pollutants and natural organic matter (NOM). When flucutations in soil oxygen status exist, Fe can cycle through reduced and oxidized forms and thus greatly affect the aqueous conc. of nutrients and metals. We are examining the influence of oscillating oxic/anoxic conditions on Fe-oxide formation and biogeochemical processes (microbial community composition, and carbon, nutrient and trace metal availability). Our work makes use of a natural rainfall gradient ranging from 2.2 to 4.2 m mean annual precipitation (MAP) on the island of Maui, Hawaii, USA. All sites developed on a 400ky basaltic lava flow and comprise soils under similar vegetation. Solid phase Fe concentration and oxidation state vary systematically across this rainfall gradient with a sharp decrease in pedogenic Fe between 2.8 m and 3.5 m MAP that corresponds with an Eh of 330 mV (1-yr ave.). Fe isotopic composition and Fe-oxide associated rare earth elements (REE) also suggest a shift from ligand-promoted to redutive Fe dissolution with increasing rainfall. To examine the effects of multiple Fe oxidation/reduction cycles, we constructed a set of redox-stat reactors that maintain Eh values within a set range by small Eh-triggered additions of oxygen. Triplicate soil slurry reactors are subjected to redox (Eh) oscillations such that Fe is repeatedly cycled from oxidized to reduced forms. During our current experiment, we measure pH and Eh dynamics and monitor the distribution of Fe(II) and Fe(III), major ion and anion concentrations, a range of trace metals including the REE, and total organic carbon (TOC) in three Stokes-effective particle size fractions (<0.45 mm, <0.1 mm, and <0.02 mm) by cascade centrifugation and a <3000 MW fraction isolated via ultra-filtration. Each sample is then sequentially extracted in dilute (0.5 M) HCl and acid-ammonium oxalate. Concurrently, CO2 release is measured and DNA fingerprinting is used to track changes in the microbial community. Prior to implementing the rigorous sampling procedure above, we completed two preliminary reactor experiments focusing only on Fe distribution between aqueous, HCl, and oxalate extractions. These experiments illustrated (1) a distinct threshold for Fe oxidation at ~ 350 mV in the soils (pH 5) and (2) multiple redox cycles increased the HCl-extractable Fe(III) fraction relative to initial conditions. Unexpectedly, this increase occurred predominantly during reducing cycles-perhaps indicating a weakening of Fe-oxide structures during initiation of reducing conditions or oxidation of Fe(II) by NO3. By integrating Fe analysis with trace metal and microbial characterization in triplicate reactors, we will verify this increase in HCl-extractable Fe(III), and assess the impacts of Fe redox oscillation on biogeochemical processes.
Feng, Huan; Tappero, Ryan; Zhang, Weiguo; ...
2015-07-26
This study is focused on micro-scale measurement of metal (Ca, Cl, Fe, K, Mn, Cu, Pb, and Zn) distributions in Spartina alterniflora root system. The root samples were collected in the Yangtze River intertidal zone in July 2013. Synchrotron X-ray fluorescence (XRF), computed microtomography (CMT), and X-ray absorption near-edge structure (XANES) techniques, which provide micro-meter scale analytical resolution, were applied to this study. Although it was found that the metals of interest were distributed in both epidermis and vascular tissue with the varying concentrations, the results showed that Fe plaque was mainly distributed in the root epidermis. Other metals (e.g.,more » Cu, Mn, Pb, and Zn) were correlated with Fe in the epidermis possibly due to scavenge by Fe plaque. Relatively high metal concentrations were observed in the root hair tip. As a result, this micro-scale investigation provides insights of understanding the metal uptake and spatial distribution as well as the function of Fe plaque governing metal transport in the root system.« less
Metal elution from Ni- and Fe-based alloy reactors under hydrothermal conditions.
Faisal, Muhammad; Quitain, Armando T; Urano, Shin-Ya; Daimon, Hiroyuki; Fujie, Koichi
2004-05-20
Elution of metals from Ni- and Fe-based alloy (i.e. Inconel 625 and SUS 316) under hydrothermal conditions was investigated. Results showed that metals could be eluted even in a short contact time. At subcritical conditions, a significant amount of Cr was extracted from SUS 316, while only traces of Ni, Fe, Mo, and Mn were eluted. In contrast, Ni was removed in significant amounts compared to Cr when Inconel 625 was tested. Several factors including temperature and contact time were found to affect elution behavior. The presence of air in the fluid even promoted elution under subcritical conditions.
Assessment of trace metal pollution in sediments and intertidal fauna at the coast of Cameroon.
Ngeve, Magdalene N; Leermakers, Martine; Elskens, Marc; Kochzius, Marc
2015-06-01
Coastal systems act as a boundary between land and sea. Therefore, assessing pollutant concentrations at the coast will provide information on the impact that land-based anthropogenic activities have on marine ecosystems. Sediment and fauna samples from 13 stations along the whole coast of Cameroon were analyzed to assess the level of trace metal pollution in sediments and intertidal fauna. Sediments showed enrichment of As, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, V, and Zn. However, pollution of greater concern was observed for Cd, Cr, Cu, Ni, and Zn at the northern stations. Some sites recorded trace metal levels higher than recommended in sediment quality guidelines. Species diversity was low, and high bioaccumulation of trace metals was observed in biological samples. Some edible gastropod species accumulated trace metals above the safety limits of the World Health Organization, European Medicine Agency, and the US Environment Protection Agency. Although industrial pollution is significant along Cameroon's coast, natural pollution from the volcano Mount Cameroon is also of concern.
Gammons, C.H.; Nimick, D.A.; Parker, S.R.; Cleasby, T.E.; McCleskey, R. Blaine
2005-01-01
Three simultaneous 24-h samplings at three sites over a downstream pH gradient were conducted to examine diel fluctuations in heavy metal concentrations in Fisher Creek, a small mountain stream draining abandoned mine lands in Montana. Average pH values at the upstream (F1), middle (F2), and downstream (F3) monitoring stations were 3.31, 5.46, and 6.80, respectively. The downstream increase in pH resulted in precipitation of hydrous ferric oxide (HFO) and hydrous aluminum oxide (HAO) on the streambed. At F1 and F2, Fe showed strong diel cycles in dissolved concentration and Fe(II)/Fe(III) ratio; these cycles were attributed to daytime photoreduction of Fe(III) to Fe(II), reoxidation of Fe(II) to Fe(III), and temperature-dependent hydrolysis and precipitation of HFO. At the near-neutral downstream station, no evidence of Fe(III) photoreduction was observed, and suspended particles of HFO dominated the total Fe load. HFO precipitation rates between F2 and F3 were highest in the afternoon, due in part to reoxidation of a midday pulse of Fe2+ formed by photoreduction in the upper, acidic portions of the stream. Dissolved concentrations of Fe(II) and Cu decreased tenfold and 2.4-fold, respectively, during the day at F3. These changes were attributed to sorption onto fresh HFO surfaces. Results of surface complexation modeling showed good agreement between observed and predicted Cu concentrations at F3, but only when adsorption enthalpies were added to the thermodynamic database to take into account diel temperature variations. The field and modeling results illustrate that the degree to which trace metals adsorb onto actively forming HFO is strongly temperature dependent. This study is an example of how diel Fe cycles caused by redox and hydrolysis reactions can induce a diel cycle in a trace metal of toxicological importance in downstream waters. Copyright ?? 2005 Elsevier Ltd.
NASA Astrophysics Data System (ADS)
El Baz, Sherif M.; Khalil, Mohamed M.
2018-07-01
Trace metals contamination has been recently increased in the Egyptian Mediterranean coast owing to the nearby anthropological activities. This investigation aimed to detect the concentrations of six different trace metals (Fe, Mn, Cu, Cd, Pb and Zn) in surface sediments from the central part of the Egyptian Mediterranean coast, and to assess their state of contamination from different indices and risk factor calculations. Mean concentrations of Cu, Pb and Zn were lower and the mean concentration of Cd was higher compared to the background values. The assessment of pollution was mainly based on the contamination indices. Based on the contamination factor, Pb was the most enriched element followed by Cd, Mn, Zn and Cu. Most of the sites show low contamination with respect to Pb, Mn, Cd, Fe, Zn and Cu. The pollution load index also suggests that all the coastal sediments are unpolluted. According to the geoaccumulation index, the sediments were classified into unpolluted with Mn, Cd, Fe and Pb, and unpolluted to moderately polluted with Pb. Risk evaluation revealed that Cd had the greatest ecological risk, followed by Pb, Cu, Mn, while Zn had the lowest risk. With the aid of statistical methods, the origin of metals is classified into two clusters (A and B). Group A consists of Fe, Mn and Cu, whereas group B contains Zn, Pb and Cd. In the first cluster Fe and Mn are joined to each other at a positive and significant similarity (0.68). Fe is recognized as an indicator of lithogenous origin, therefore, its higher similarity with Mn may be indicative of the similar origin for Manganese. In the second cluster Pb and Zn are joined to each other at a positive and significant similarity (0.80). Pb is recognized as an indicator of anthropogenic origin, therefore, its higher similarity with Zn may be indicative of the similar origin for Zinc.
Budakoglu, Murat; Karaman, Muhittin; Kumral, Mustafa; Zeytuncu, Bihter; Doner, Zeynep; Yildirim, Demet Kiran; Taşdelen, Suat; Bülbül, Ali; Gumus, Lokman
2018-02-23
The major and trace element component of 48 recent sediment samples in three distinct intervals (0-10, 10-20, and 20-30 cm) from Lake Acıgöl is described to present the current contamination levels and grift structure of detrital and evaporate mineral patterns of these sediments in this extreme saline environment. The spatial and vertical concentrations of major oxides were not uniform in the each subsurface interval. However, similar spatial distribution patterns were observed for some major element couples, due mainly to the detrital and evaporate origin of these elements. A sequential extraction procedure including five distinct steps was also performed to determine the different bonds of trace elements in the < 60-μ particulate size of recent sediments. Eleven trace elements (Ni, Fe, Cd, Pb, Cu, Zn, As, Co, Cr, Al and Mn) in nine surface and subsurface sediment samples were analyzed with chemical partitioning procedures to determine the trace element percentage loads in these different sequential extraction phases. The obtained accuracy values via comparison of the bulk trace metal loads with the total loads of five extraction steps were satisfying for the Ni, Fe, Cd, Zn, and Co. While, bulk analysis results of the Cu, Ni, and V elements have good correlation with total organic matter, organic fraction of sequential extraction characterized by Cu, As, Cd, and Pb. Shallow Lake Acıgöl sediment is characteristic with two different redox layer a) oxic upper level sediments, where trace metals are mobilized, b) reduced subsurface level, where the trace metals are precipitated.
Ilyas, Asim; Shah, Munir H
2017-12-01
Imbalances in the concentrations of trace metals have become an increasingly recognized source of infirmity worldwide particularly in the development of ischemia heart disease (IHD). Present study is intended to analyze the concentrations of Ca, Cd, Co, Cr, Cu, Fe, K, Li, Mg, Mn, Na, Pb, Sr, and Zn in the blood and scalp hair of the patients and counterpart controls by flame atomic absorption spectrometry after wet-acid digestion. On the average, Cd, Co, Cr, Fe, K, Li, Mn, Na, and Pb revealed significantly elevated concentrations in the blood of the patients compared with the controls (p < 0.05), whereas mean levels of Ca, Cd, Fe, K, Li, Pb, and Sr in the scalp hair were significantly higher in the patients than the controls (p < 0.05). Most of the metals exhibited noticeable disparities in their concentrations based on gender, abode, dietary/smoking habits, and occupations of both donor groups. The correlation study and multivariate statistical analyses revealed some significantly divergent associations and apportionment of the metals in both donor groups. Overall, comparative variations of the metal contents in blood/scalp hair of the patients were significantly different than the controls; thus, evaluation of trace metals status may be indicative of pathological disorders, such as IHD.
Speciation and leaching of trace metal contaminants from e-waste contaminated soils.
Cui, Jin-Li; Luo, Chun-Ling; Tang, Chloe Wing-Yee; Chan, Ting-Shan; Li, Xiang-Dong
2017-05-05
Primitive electrical and electronic waste (e-waste) recycling activities have caused serious environmental problems. However, little is known about the speciation and leaching behaviors of metal contaminants at e-waste contaminated sites. This study investigated trace metal speciation/mobilization from e-waste polluted soil through column leaching experiments involving irrigation with rainwater for almost 2.5 years. Over the experimental period, Cu and Zn levels in the porewater were 0.14±0.08mg/L, and 0.16±0.08mg/L, respectively, increasing to 0.33±0.16mg/L, and 0.69±0.28mg/L with plant growth. The amounts of Cu, Zn, and Pb released in surface soil (0-2cm) contributed 43.8%, 22.5%, and 13.8%, respectively, to the original levels. The released Cu and Zn were primarily caused by the mobilization of the carbonate species of metals, including Cu(OH) 2 , CuCO 3 , and Zn 5 (CO 3 ) 2 (OH) 6 , and amorphous Fe/Mn oxides associated fractions characterized by sequential extraction coupling with X-ray absorption spectroscopy. During the experiments, trace metals were not detected in the effluent, and the re-sequestration of trace metals was mainly attributed to the adsorption on the abundant Fe/Mn oxides in the sub-layer soil. This study quantitatively elucidated the molecular speciation of Cu and Zn in e-waste contaminated soil during the column leaching process. Copyright © 2017 Elsevier B.V. All rights reserved.
Redox Conditions on Small Bodies
NASA Technical Reports Server (NTRS)
Jones, J. H.
2004-01-01
The Eucrite Parent Body (4 Vesta). The eucrites are basalts that contain approx. 18 wt% FeO and contain trace metal. The eucrites are very depleted in siderophile elements, so it appears that the source regions of these basalts once equilibrated with Fe-Ni metal. Therefore, it is of interest to ask what fo2 is required to precipitate metal from a liquid of eucrite composition. Or in other words, what f02 did eucrites form under? This fo2 has been determined experimentally by and was found to be IW-1. Therefore, eucrites formed at about IW-1. In addition, it is interesting to note that assuming X(sub feo) = alpha(sub FeO) allows calculation of eucrite fo2 (assuming equilibrium with Fe metal). This calculation yields the same result as the experiments to within approx. 0.25 log units, reinforcing this result.
Minor element distribution in iron disulfides in coal: a geochemical review
Kolker, Allan
2012-01-01
Electron beam microanalysis of coal samples in U.S. Geological Survey (USGS) labs confirms that As is the most abundant minor constituent in Fe disulfides in coal and that Se, Ni, and other minor constituents are present less commonly and at lower concentrations than those for As. In nearly all cases, Hg occurs in Fe disulfides in coal at concentrations below detection by electron beam instruments. Its presence is shown by laser ablation ICP-MS, by selective leaching studies of bulk coal, and by correlation with Fe disulfide proxies such as total Fe and pyritic sulfur. Multiple generations of Fe disulfides are present in coal. These commonly show grain-to-grain and within-grain minor- or trace element compositional variation that is a function of the early diagenetic, coalification, and post-coalification history of the coal. Framboidal pyrite is almost always the earliest Fe disulfide generation, as shown by overgrowths of later Fe disulfides which may include pyrite or marcasite. Cleat- (or vein) pyrite (or marcasite) is typically the latest Fe disulfide generation, as shown by cross-cutting relations. Cleat pyrite forms by fluid migration within a coal basin and consequently may be enriched in elements such as As by deposition from compaction-driven fluids, metal enriched basinal brines or hydrothermal fluids. In some cases, framboidal pyrite shows preferential Ni enrichment with respect to co-occurring pyrite forms. This is consistent with bacterial complexing of metals in anoxic sediments and derivation of framboidal pyrite from greigite (Fe3S4), an Fe monosulfide precursor to framboidal pyrite having the thio-spinel structure which accommodates transition metals. Elements such as As, Se, and Sb substitute for S in the pyrite structure whereas metals, including transition metals, Hg and Pb, are thought to substitute for Fe. Understanding the distribution of minor and trace elements in Fe disulfides in coal has important implications for their availability to the environment through coal mining and use, as well as for potential reduction by coal preparation, and for delineating diagenetic compositional changes throughout and after coal formation.
Seasonal variation and sources of dissolved trace metals in Maó Harbour, Minorca Island.
Martínez-Soto, Marly C; Tovar-Sánchez, Antonio; Sánchez-Quiles, David; Rodellas, Valentí; Garcia-Orellana, Jordi; Basterretxea, Gotzon
2016-09-15
The environmental conditions of semi-enclosed coastal water-bodies are directly related to the catchment, human activities, and oceanographic setting in which they are located. As a result of low tidal forcing, and generally weak currents, waters in Mediterranean harbours are poorly renewed, leading to quality deterioration. Here, we characterise the seasonal variation of trace metals (i.e. Co, Cd, Cu, Fe, Mo, Ni, Pb, and Zn) in surface waters, and trace metal content in sediments from Maó Harbour, a semi-enclosed coastal ecosystem in the NW Mediterranean Sea. Our results show that most of the dissolved trace metals in the waters of Maó Harbour exhibit a marked inner-outer concentration gradient, suggesting a permanent input into the inner part of the harbour. In general, metal concentrations in the waters of Maó Harbour are higher than those in offshore waters. Concentration of Cu (21±8nM), Fe (9.2±3.2nM) and Pb (1.3±0.4nM) are particularly high when compared with other coastal areas of the Mediterranean Sea. The concentration of some metals such as Cu and Zn increases during summertime, when the human population and boat traffic increase during the tourism season, and when resuspension from the metal enriched sediments is higher. The evaluation of the metal sources in the harbour reveals that, compared with other putative sources such as runoff, aerosol deposition and fresh groundwater discharges, contaminated sediments are the main source of the metals found in the water column, most likely through vessel-driven resuspension events. This study contributes to the understanding of the processes that control the occurrence and distribution of trace metals in Maó Harbour, thus aiding in the effective management of the harbour, and enhancing the overall quality of the seawater ecosystem. Copyright © 2016 Elsevier B.V. All rights reserved.
The Elemental Composition of Demospongiae from the Red Sea, Gulf of Aqaba
Mayzel, Boaz; Aizenberg, Joanna; Ilan, Micha
2014-01-01
Trace elements are vital for the growth and development of all organisms. Little is known about the elemental content and trace metal biology of Red Sea demosponges. This study establishes an initial database of sponge elemental content. It provides the necessary foundation for further research of the mechanisms used by sponges to regulate the uptake, accumulation, and storage of metals. The metal content of 16 common sponge species was determined using ICP measurements. A combination of statistical methods was used to determine the correlations between the metals and detect species with significantly high or low concentrations of these metals. Bioaccumulation factors were calculated to compare sponge metal content to local sediment. Theonella swinhoei contained an extremely high concentration of arsenic and barium, much higher (at least 200 times) than all other species and local sediment. Hyrtios erecta had significantly higher concentration of Al, Cr, Fe, Mn, Ti and V than all other species. This is due to sediment accumulation and inclusion in the skeleton fibers of this sponge species. Suberites clavatus was found to contain significantly higher concentration of Cd, Co, Ni and Zn than all other species and local sediment, indicating active accumulation of these metals. It also has the second highest Fe concentration, but without the comparably high concentrations of Al, Mn and Ti that are evident in H. erecta and in local sediment. These differences indicate active uptake and accumulation of Fe in S. clavatus, this was also noted in Niphates rowi. A significantly higher B concentration was found in Crella cyatophora compared to all other species. These results indicate specific roles of trace elements in certain sponge species that deserve further analysis. They also serve as a baseline to monitor the effects of anthropogenic disturbances on Eilat's coral reefs. PMID:24759635
NASA Astrophysics Data System (ADS)
Corrigan, Catherine M.; Chabot, Nancy L.; McCoy, Timothy J.; McDonough, William F.; Watson, Heather C.; Saslow, Sarah A.; Ash, Richard D.
2009-05-01
To better understand the partitioning behavior of elements during the formation and evolution of iron meteorites, two sets of experiments were conducted at 1 atm in the Fe-Ni-P system. The first set examined the effect of P on solid metal/liquid metal partitioning behavior of 22 elements, while the other set explored the effect of the crystal structures of body-centered cubic (α)- and face-centered cubic (γ)-solid Fe alloys on partitioning behavior. Overall, the effect of P on the partition coefficients for the majority of the elements was minimal. As, Au, Ga, Ge, Ir, Os, Pt, Re, and Sb showed slightly increasing partition coefficients with increasing P-content of the metallic liquid. Co, Cu, Pd, and Sn showed constant partition coefficients. Rh, Ru, W, and Mo showed phosphorophile (P-loving) tendencies. Parameterization models were applied to solid metal/liquid metal results for 12 elements. As, Au, Pt, and Re failed to match previous parameterization models, requiring the determination of separate parameters for the Fe-Ni-S and Fe-Ni-P systems. Experiments with coexisting α and γ Fe alloy solids produced partitioning ratios close to unity, indicating that an α versus γ Fe alloy crystal structure has only a minor influence on the partitioning behaviors of the trace element studied. A simple relationship between an element's natural crystal structure and its α/γ partitioning ratio was not observed. If an iron meteorite crystallizes from a single metallic liquid that contains both S and P, the effect of P on the distribution of elements between the crystallizing solids and the residual liquid will be minor in comparison to the effect of S. This indicates that to a first order, fractional crystallization models of the Fe-Ni-S-P system that do not take into account P are appropriate for interpreting the evolution of iron meteorites if the effects of S are appropriately included in the effort.
Regulating cellular trace metal economy in algae
DOE Office of Scientific and Technical Information (OSTI.GOV)
Blaby-Haas, Crysten E.; Merchant, Sabeeha S.
As indispensable protein cofactors, Fe, Mn, Cu and Zn are at the center of multifaceted acclimation mechanisms that have evolved to ensure extracellular supply meets intracellular demand. In starting with selective transport at the plasma membrane and ending in protein metalation, metal homeostasis in algae involves regulated trafficking of metal ions across membranes, intracellular compartmentalization by proteins and organelles, and metal-sparing/recycling mechanisms to optimize metal-use efficiency. Overlaid on these processes are additional circuits that respond to the metabolic state as well as to the prior metal status of the cell. Here, we focus on recent progress made toward understanding themore » pathways by which the single-celled, green alga Chlamydomonas reinhardtii controls its cellular trace metal economy. We also compare these mechanisms to characterized and putative processes in other algal lineages. Photosynthetic microbes continue to provide insight into cellular regulation and handling of Cu, Fe, Zn and Mn as a function of the nutritional supply and cellular demand for metal cofactors. We found that new experimental tools such as RNA-Seq and subcellular metal imaging are bringing us closer to a molecular understanding of acclimation to supply dynamics in algae and beyond.« less
Regulating cellular trace metal economy in algae
Blaby-Haas, Crysten E.; Merchant, Sabeeha S.
2017-06-30
As indispensable protein cofactors, Fe, Mn, Cu and Zn are at the center of multifaceted acclimation mechanisms that have evolved to ensure extracellular supply meets intracellular demand. In starting with selective transport at the plasma membrane and ending in protein metalation, metal homeostasis in algae involves regulated trafficking of metal ions across membranes, intracellular compartmentalization by proteins and organelles, and metal-sparing/recycling mechanisms to optimize metal-use efficiency. Overlaid on these processes are additional circuits that respond to the metabolic state as well as to the prior metal status of the cell. Here, we focus on recent progress made toward understanding themore » pathways by which the single-celled, green alga Chlamydomonas reinhardtii controls its cellular trace metal economy. We also compare these mechanisms to characterized and putative processes in other algal lineages. Photosynthetic microbes continue to provide insight into cellular regulation and handling of Cu, Fe, Zn and Mn as a function of the nutritional supply and cellular demand for metal cofactors. We found that new experimental tools such as RNA-Seq and subcellular metal imaging are bringing us closer to a molecular understanding of acclimation to supply dynamics in algae and beyond.« less
Determination of trace metals in drinking water in Irbid City-Northern Jordan.
Alomary, Ahmed
2013-02-01
Drinking water samples from Irbid, the second populated city in Jordan were analyzed for trace metals (As, Ba, Cd, Pb, Cr, Cu, Fe, Zn, Mn, Ni, and Se) content. The study was undertaken to determine if the metal concentrations were within the national and international guidelines. A total of 90 drinking water samples were collected from Al-Yarmouk University area. The samples were collected from three different water types: tap water (TW), home-purified water (HPW), and plant-purified water (PPW). All the samples were analyzed for trace metals using an inductively coupled plasma-optical emission spectrometry. All the samples analyzed were within the United States Environmental Protection Agency admissible pH limit (6.5-8.5). The results showed that concentrations of the trace metals vary significantly between the three drinking water types. The results showed that HPW samples have the lowest level of trace metals and the concentrations of some essential trace metals in these samples are less than the recommended amounts. Slight differences in the metal contents were found between HPW samples, little differences between PPW samples; however, significant differences were found between TW samples. Although some TW samples showed high levels of trace metals, however, the mean level of most elements determined in the samples were well within the Jordanian standards as well as the World Health Organization standards for drinking water.
Jones, Adele M; Xue, Youjia; Kinsela, Andrew S; Wilcken, Klaus M; Collins, Richard N
2016-03-15
Donnan dialysis has been applied to forty filtered drainage waters collected from five coastal lowland acid sulfate soil (CLASS) catchments across north-eastern NSW, Australia. Despite having average pH values<3.9, 78 and 58% of Al and total Fe, respectively, were present as neutral or negatively-charged species. Complementary isotope dilution experiments with (55)Fe and (26)Al demonstrated that only soluble (i.e. no colloidal) species were present. Trivalent rare earth elements (REEs) were also mainly present (>70%) as negatively-charged complexes. In contrast, the speciation of the divalent trace metals Co, Mn, Ni and Zn was dominated by positively-charged complexes and was strongly correlated with the alkaline earth metals Ca and Mg. Thermodynamic equilibrium speciation calculations indicated that natural organic matter (NOM) complexes dominated Fe(III) speciation in agreement with that obtained by Donnan dialysis. In the case of Fe(II), however, the free cation was predicted to dominate under thermodynamic equilibrium, whilst our results indicated that Fe(II) was mainly present as neutral or negatively-charged complexes (most likely with sulfate). For all other divalent metals thermodynamic equilibrium speciation calculations agreed well with the Donnan dialysis results. The proportion of Al and REEs predicted to be negatively-charged was also grossly underestimated, relative to the experimental results, highlighting possible inaccuracies in the stability constants developed for these trivalent Me(SO4)2(-) and/or Me-NOM complexes and difficulties in modeling complex environmental samples. These results will help improve metal mobility and toxicity models developed for CLASS-affected environments, and also demonstrate that Australian CLASS environments can discharge REEs at concentrations an order of magnitude greater than previously reported. Copyright © 2015 Elsevier B.V. All rights reserved.
NASA Astrophysics Data System (ADS)
Wiche, Oliver; Székely, Balazs; Moschner, Christin; Heilmeier, Hermann
2015-04-01
In recent studies root-soil interactions of white lupine (Lupinus albus L.) have drawn special attention to researchers due to its particularly high potential to increase bioavailability of phosphorous (P) and trace nutrients in soils. In mixed cultures, white lupine has the ability to mobilize P and trace nutrients in soil in excess of its own need and make this excess available for other intercropped companion species. While improved acquisition of P and improved yield parameters have mostly been documented in cereal-lupine intercrops, compared to sole crops, only a few recent studies have evidenced similar effects for trace elements e.g. Fe, Zn and Mn. In this preliminary study we tried to obtain more information about the mobilization of trace elements due to intercropping under field conditions. We hypothesize, that processes that lead to a better acquisition of trace nutrients might also affect other trace elements what could be useful for phytoremediation and phytomining research. Here we report the results of a semi-field experiment were we investigated the effects of an intercropping of white lupine with oat (Avena sativa L.) on the concentrations of trace metals in shoots of oat. We investigated the effects on 12 trace elements, including 4 elements with relevance for plant nutrition (P, Fe, Mn, Zn) and 8 trace elements, belonging to the group of metalloids, lanthanides and actinides with high relevance in phytoremediation (Cd, Pb Th, U) and phytomining research (Sc, La, Nd, Ge). The experiment was carried out on a semi-field lysimer at the off-site soil recycling and remediation center in Hirschfeld (Saxony, Germany). To test the intercropping-dependent mobilization of trace metals in soil and enhanced uptake of elements by oat, white lupine and oat were cultivated on 20 plots (4 m² each) in monocultures and mixed cultures and two different white lupin /oat-ratios (11% and 33%, respectively) applying various treatments. The geometrical arrangement of plots was randomized and every treatment was fivefold replicated. Soil solution was collected weekly with plastic suction cups. Concentrations of trace metals in shoots of oat and soil solution were measured with ICP-MS. As a result, we found that both, concentrations of trace elements in oat plants, as well as the mobility of P and trace metals in soil solution was increased by an intercropping with white lupine. Mixed culture of oat with 11% white lupin significantly increased the concentrations of the trace nutrients Fe, Mn and Zn, as well as the concentrations of the trace metals Pb, La, Nd, Sc, Th and U in tissues of oat. Surprisingly, mixed cultures with 33 % white lupin did not significantly affect trace metal concentrations in oat, what might be the consequence of an increasing competition of roots of white lupin and oat for nutrients and trace metals. In conclusion we found that mixed cultures of white lupin with cereals might be a powerful tool for enhanced phytoremediation and phytomining. However, processes involved in the physiochemical mechanism of element uptake as affected by the oat/white lupin co-cultivation remain unknown and further studies on this topic are planned. These studies have been carried out in the framework of the PhytoGerm project, financed by the Federal Ministry of Education and Research, Germany. The authors are grateful to students and laboratory assistants contributing in the field work and sample preparation.
Nasr, Samir M; Okbah, Mohamed A; El Haddad, Huda S; Soliman, Naglaa F
2015-07-01
A five-step sequential extraction technique, following Tessier's protocol, has been applied to determine the chemical association of Cd, Cu, Fe, Pb, and Zn with major sedimentary phases (exchangeable, carbonate, manganese and iron oxides, organic and residual fraction) in surface sediments from 14 stations off the Libyan Mediterranean coast. This study is a first approach of chemical fractionation of these metals in one of the most economically important area of the Libyan coastline in Mediterranean Sea. The total metal content was also determined. The total concentration of metals ranged from 5-10.5 mg/kg for Cd, 9.1-22.7 mg/kg for Cu, 141.8-1056.8 mg/kg for Fe, 18.9-56.9 mg/kg for Pb, and 11.6-30.5 mg/kg for Zn. The results of the partitioning study showed that the residual form was the dominant fraction of the selected metals among most of the studied locations. The degree of surface sediment contamination was computed for risk assessment code (RAC), individual contamination factor (ICF), and Global contamination factor (GCF). Risk assessment code classification showed that the relative amounts of easily dissolved phase of trace metals in the sediments are in the order of Pb>Zn>Cd>Cu>Fe. The results of ICF and GCF showed that Sirt and Abu Kammashand had higher GCF than other sites indicating higher environmental risk. In terms of ICF value, a decrease order in environmental risk by trace metals was Pb>Zn>Cu>Cd>Fe. Therefore, Pb had highest risk to water body.
Jonathan, M P; Aurioles-Gamboa, David; Villegas, Lorena Elizabeth Campos; Bohórquez-Herrera, Jimena; Hernández-Camacho, Claudia J; Sujitha, S B
2015-10-15
Concentrations of 11 trace metals (Fe, Mn, Cr, Cu, Ni, Co, Pb, Zn, Cd, As, Hg) in 40 fish species from Santa Maria Bay, Baja California Sur, Mexico, the strategically important area for marine mammals and organisms were analyzed. Based on their concentrations the ranking of metals Fe>Zn>Ni>Cr>Mn>Pb>Cu>Co>As>Cd>Hg suggests that organism size, metabolism and feeding habits are correlated with metal concentrations. Local geological formations affect the concentrations of different metals in the aquatic environment and are subsequently transferred to fishes. The correlation analysis suggests that metabolism and nurturing habits impact the concentration of metals. Concentrations of Fe and Mn appear to be influenced by scavenging and absorption processes, which vary by species. The considerable variability in the metal concentrations obtained in different species underscores the importance of regular monitoring. Copyright © 2015 Elsevier Ltd. All rights reserved.
NASA Astrophysics Data System (ADS)
Demina, Ludmila L.; Holm, Nils G.; Galkin, Sergey V.; Lein, Alla Yu.
2013-10-01
Along with summarizing the published literature and our own data some new results on properties of the trace metal biogeochemistry in the deep-sea hydrothermal ecosystems at the Mid-Atlantic Ridge (MAR) and East Pacific Rise (EPR) are shown. Differences in mean concentrations of big group of trace metals (Fe, Mn, Zn, Cu, Ni, Cr, Co, As, Pb, Cd, Ag, Hg) between the biotope water of the low- and high-temperature hydrothermal vent fields were firstly revealed. The same trace metals were studied in different groups of organisms within different temperature zones at one and the same vent field (9°50‧N EPR), as well as in fauna inhabiting geochemically different vent sites. Distribution patterns of Fe, Mn, Zn, Cu, Cd, Pb, Ag, Ni, Cr, Co, As, Se, Sb, and Hg in different taxa gave an evidence of the influence of environmental and biological parameters on their bioaccumulation in organisms. Among the animals a particular “champion” with respect to the trace metal content was found to be a polychaeta Alvinella pompejana that inhabits the hottest places of the vent sulfide chimneys of the 9°50‧N field, EPR. New data on the trace metal distribution between soft tissues and carbonate shell let us estimate a role of biomineralization in the accumulation of metals in the Bathimodiolus mussels. Contrasting geochemical behavior was revealed for Cu that is enriched in soft tissues of mussels and depleted in shells, on the one hand, and Mn that is accumulated almost totally in mussel shells, on the other hand. Deep-sea hydrothermal biological communities demonstrate a strong concentration function, and bioconcentration factors (BCF) of trace metals estimated for Bathimodiolus mussels collected at the four hydrothermal fields vary within the limits of n102-n105 and are similar to that of the littoral mussels. Due to this and to the high values of biomasses per square meter, the hydrothermal fauna may be considered as a newly discovered biological filter of the oceans.
Trace metals in liver from bluefish, tautog, and tilefish in relation to body length
DOE Office of Scientific and Technical Information (OSTI.GOV)
Mears, H.C.; Eisler, R.
1977-09-01
Livers from bluefish, tilefish and tautog collected during the summer of 1971 off the New Jersey coast were analyzed for Cd, Cr, Cu, Fe, Mn, Ni, and Zn by atomic absorption spectrophotometry. Liver ash from male and female tautog contained decreasing concentrations of Ni with increasing body length. Smaller males also contained greater levels of Cr and Cu in liver than larger tautogs. Larger tilefish contained proportionately more Cd, Cu, and Fe in liver than smaller tilefish. Decreasing levels of Mn and Zn with body length were apparent only for females. Livers from larger male bluefish were associated with highermore » concentrations of Fe than those from smaller males, while those from larger females contained lower concentrations of Cr than those from smaller females. The data suggest that future comparisons for trace metals which vary as a function of size be made only among fish of the same length.« less
Falandysz, Jerzy; Frankowska, Aneta; Jarzynska, Grazyna; Dryzałowska, Anna; Kojta, Anna K; Zhang, Dan
2011-01-01
This paper provides data on baseline concentrations, interrelationships and bioconcentration potential of 12 metallic elements by King Bolete collected from 11 spatially distant sites across Poland. There are significant differences in concentrations of metals (Al, Ba, Ca, Cd, Cu, Fe, K, Mg, Mn, Na, Sr, Zn) and their bioconcentration potential in King Bolete Boletus edulis at 11 spatially distant sites surveyed across Poland. These have resulted from significant geographical differences in trace metal concentrations in a layer (0-10 cm) of organic and mineral soil underneath to fruiting bodies and possible local bioavailabilities of macro- (Ca, K, Mg, Na) and trace metals (Al, Ba, Cd, Cu, Fe, Mn, Sr, Zn) to King Bolete. The use of highly appreciated wild-grown edible King Bolete mushroom has established a baseline measure of regional minerals status, heavy metals pollution and assessment of intake rates for wild mushroom dish fanciers against which future changes can be compared. Data on Cd, Cu and Zn from this study and from literature search can be useful to set the maximum limit of these metals in King Bolete collected from uncontaminated (background) areas. In this report also reviewed are data on Al, Ba, Ca, Cd, Cu, Fe, K, Mg, Mn, Na, Sr and Zn accumulation in King Bolete.
Witt, Emitt C; Wronkiewicz, David J; Pavlowsky, Robert T; Shi, Honglan
2013-09-01
Fugitive dust from 18 unsurfaced roadways in Missouri were sampled using a novel cyclonic fugitive dust collector that was designed to obtain suspended bulk samples for analysis. The samples were analyzed for trace metals, Fe and Al, particle sizes, and mineralogy to characterize the similarities and differences between roadways. Thirteen roads were located in the Viburnum Trend (VT) mining district, where there has been a history of contaminant metal loading of local soils; while the remaining five roads were located southwest of the VT district in a similar rural setting, but without any mining or industrial process that might contribute to trace metal enrichment. Comparison of these two groups shows that trace metal concentration is higher for dusts collected in the VT district. Lead is the dominant trace metal found in VT district dusts representing on average 79% of the total trace metal concentration, and was found moderately to strongly enriched relative to unsurfaced roads in the non-VT area. Fugitive road dust concentrations calculated for the VT area substantially exceed the 2008 Federal ambient air standard of 0.15μgm(-3) for Pb. The pattern of trace metal contamination in fugitive dust from VT district roads is similar to trace metal concentrations patterns observed for soils measured more than 40years ago indicating that Pb contamination in the region is persistent as a long-term soil contaminant. Published by Elsevier Ltd.
NASA Astrophysics Data System (ADS)
Wang, W.; Finlayson-Pitts, B. J.
2003-01-01
The ICP AES experiment reported here is suitable for use in a junior- or senior-level undergraduate instrumental analysis laboratory. The objective of this experiment is to analyze trace metals present in cigarette tobacco, the cigarette filter, and the ash obtained when the cigarette is burned. Two different brands of cigarettes, one with and one without a filter, were used. The filter was analyzed before and after smoke was drawn through it. The trace metals were extracted using concentrated nitric acid at room temperature and at 100 °C respectively, to test the extraction efficiency. Some tobacco samples were spiked with ZnCl2 and FeCl3 to assess the efficiency of the recovery. Zinc and iron are shown to be present in tobacco, filter, and ash, while chromium was above the detection limit only in the ash. These metals are concentrated in the ash compared to the tobacco by factors of ˜4 (Zn), 12 17 (Fe), and ≥ 2 (Cr). If sufficient laboratory time is available, this experiment could be paired with one using atomic absorption (AA) to demonstrate the advantages and disadvantages of ICP when compared to AA.
NASA Astrophysics Data System (ADS)
Feltzing, S.; Gustafsson, B.
1998-04-01
We have derived elemental abundances of O, Na, Mg, Al, Si, Ca, Ti, Cr, Mn, Fe, Co, Ni as well as for a number of s-elements for 47 G and K dwarf, with [Me/H]>0.1 dex. The selection of stars was based on their kinematics as well as on their uvby-beta photometry. One sample of stars on rather eccentric orbits traces the chemical evolution interior to the solar orbit and another, on circular orbits, the evolution around the solar orbit. A few Extreme Population I stars were included in the latter sample. The stars have -0.1 dex < [Fe/H] < 0.42 dex. The spectroscopic [Fe/H] correlate well with the [Me/H] derived from uvby-beta photometry. We find that the elemental abundances of Mg, Al, Si, Ca, Ti, Cr and Ni all follow [Fe/H]. Our data put further constraints on models of galactic chemical evolution, in particular of Cr, Mn and Co which have not previously been studied for dwarf stars with [Me/H] >0.1 dex. The increase in [Na/Fe] and [Al/Fe] as a function of [Fe/H] found previously by \\cite[Edvardsson et al. (1993a)]{Edv93} has been confirmed for [Na/Fe]. This upturning relation, and the scatter around it, are shown not to be due to a mixture of populations with different mean distances to the galactic centre. We do not confirm the same trend for aluminium, which is somewhat surprising since both these elements are thought to be produced in the same environments in the pre-supernova stars. Nor have we been able to trace any tendency for relative abundances of O, Si, and Ti relative to Fe to vary with the stellar velocities, i.e. the stars present mean distance to the galactic centre. These results imply that there is no significant difference in the chemical evolution of the different stellar populations for stars with [Me/H]>0.1 dex. We find that [O/Fe] continue to decline with increasing [Fe/H] and that oxygen and europium correlate well. However [Si/Fe] and [Ca/Fe] seem to stay constant. A real (``cosmic'') scatter in [Ti/Fe] at given [Fe/H] is suggested as well as a decreasing abundance of the s-elements relative to iron for the most metal-rich dwarf stars. We discuss our results in the context of recent models of galactic chemical evolution. In our sample we have included a few very metal rich stars, sometimes called SMR (super metal rich) stars. We find these stars to be among the most iron-rich in our sample but far from as metal-rich as indicated by their photometric metallicities. SMR stars on highly eccentric orbits, alleged to trace the evolution of the chemical evolution in the galactic Bulge, have previously been found overabundant in O, Mg and Si. We have included three such stars from the study by \\cite[Barbuy & Grenon (1990)]{Bar90}. We find them to be less metal rich and the other elemental abundances remain puzzling. Detailed spectroscopic abundance analyses of K dwarf stars are rare. Our study includes 5 K dwarf stars and has revealed what appears to be a striking example of overionization. The overionization is especially prominent for Ca, Cr and Fe. The origin of this apparent overionization is not clear and we discuss different explanations in some detail. Based on observations at the McDonald Observatory.
Ennouri, Rym; Zaaboub, Noureddine; Fertouna-Bellakhal, Mouna; Chouba, Lassad; Aleya, Lotfi
2016-03-01
Tunis Gulf (northern Tunisia, Mediterranean Sea) is of great economic importance due to its abundant fish resources. Rising urbanization and industrial development in the surrounding area have resulted in an increase in untreated effluents and domestic waste discharged into the gulf via its tributary streams. Metal (Cd, Pb, Hg, Cu, Zn, Fe, and Mn) and major element (Mg, Ca, Na, and K) concentrations were measured in the grain fine fraction <63 μm by atomic absorption spectrophotometry. Results showed varying spatial distribution patterns for metals, indicating complex origins and controlling factors such as anthropogenic activities. Sediment metal concentrations are ranked as follows: Fe > Mg > Zn > Mn > Pb > Cu > Cd > Hg. Metals tend to be concentrated in proximity to source points, suggesting that the mineral enrichment elements come from sewage of coastal towns and pollution from industrial dumps and located along local rivers, lagoons, and on the gulf shore itself. This study showed that trace metal and major element concentrations in surface sediments along the Tunis Gulf shores were lower than those found in other coastal areas of the Mediterranean Sea.
ThomasArrigo, Laurel K; Mikutta, Christian; Lohmayer, Regina; Planer-Friedrich, Britta; Kretzschmar, Ruben
2016-04-05
Iron-rich organic flocs are frequently observed in surface waters of wetlands and show a high affinity for trace metal(loid)s. Under low-flow stream conditions, flocs may settle, become buried, and eventually be subjected to reducing conditions facilitating trace metal(loid) release. In this study, we reacted freshwater flocs (704-1280 mg As/kg) from a minerotrophic peatland (Gola di Lago, Switzerland) with sulfide (5.2 mM, S(-II)spike/Fe = 0.75-1.62 mol/mol) at neutral pH and studied the speciation changes of Fe, S, and As at 25 ± 1 °C over 1 week through a combination of synchrotron X-ray techniques and wet-chemical analyses. Sulfidization of floc ferrihydrite and nanocrystalline lepidocrocite caused the rapid formation of mackinawite (52-81% of Fesolid at day 7) as well as solid-phase associated S(0) and polysulfides. Ferrihydrite was preferentially reduced over lepidocrocite, although neoformation of lepidocrocite from ferrihydrite could not be excluded. Sulfide-reacted flocs contained primarily arsenate (47-72%) which preferentially adsorbed to Fe(III)-(oxyhydr)oxides, despite abundant mackinawite precipitation. At higher S(-II)spike/Fe molar ratios (≥1.0), the formation of an orpiment-like phase accounted for up to 35% of solid-phase As. Despite Fe and As sulfide precipitation and the presence of residual Fe(III)-(oxyhydr)oxides, mobilization of As was recorded in all samples (Asaq = 0.45-7.0 μM at 7 days). Aqueous As speciation analyses documented the formation of thioarsenates contributing up to 33% of Asaq. Our findings show that freshwater flocs from the Gola di Lago peatland may become a source of As under sulfate-reducing conditions and emphasize the pivotal role Fe-rich organic freshwater flocs play in trace metal(loid) cycling in S-rich wetlands characterized by oscillating redox conditions.
Distribution of Cr, Pb, Cd, Zn, Fe and Mn in Lake Victoria sediments, East Africa
DOE Office of Scientific and Technical Information (OSTI.GOV)
Onyari, J.M.; Wandiga, S.O.
1989-06-01
The presence of many metals at trace or ultra-trace levels in the human environment has received increased global attention. Sediments as a sink for pollutants are widely recognized pollution sources and diagenesis and biochemical transformations within the sediment may mobilize pollutants posing a threat to a wider biological community. The natural (background) concentrations of heavy metals in lake sediments can be estimated either by analysis of surface sediments in non-polluted regions or by analysis of core samples antedating modern pollution. The distribution pattern of heavy metals in tropical freshwater systems has been little studied. The authors found increased concentrations ofmore » lead and other trace metals in Lake Victoria. Thus this study was initiated in order to further investigate the distribution patterns of lead and other metals in Lake Victoria.« less
McKay, R. M. L.; Geider, R. J.; LaRoche, J.
1997-01-01
Flavodoxin is a small electron-transfer protein capable of replacing ferredoxin during periods of Fe deficiency. When evaluating the suitability of flavodoxin as a diagnostic indicator for Fe limitation of phytoplankton growth, we examined its expression in two marine diatoms we cultured using trace-metal-buffered medium. Thalassio-sira weissflogii and Phaeodactylum tricornutum were cultured in ethylenediaminetetraacetic acid-buffered Sargasso Sea water containing from 10 to 1000 nM added Fe. Trace-metal-buffered cultures of each diatom maintained high growth rates across the entire range of Fe additions. Similarly, declines in chlorophyll/cell and in the ratio of photosystem II variable-to-maximum fluorescence were negligible (P. tricornutum) to moderate (T. weissflogii; 54% decline in chlorophyll/cell and 22% decrease in variable-to-maximum fluorescence). Moreover, only minor variations in photosynthetic parameters were observed across the range of additions. In contrast, flavodoxin was expressed to high levels in low-Fe cultures. Despite the inverse relationship between flavodoxin expression and Fe content of the medium, its expression was seemingly independent of any of the indicators of cell physiology that were assayed. It appears that flavodoxin is expressed as an early-stage response to Fe stress and that its accumulation need not be intimately connected to limitations imposed by Fe on the growth rate of these diatoms. PMID:12223732
Wirt, Laurie; Leib, K.J.; Bove, D.J.; Mast, M.A.; Evans, J.B.; Meeker, G.P.
1999-01-01
Prospect Gulch is a major source of iron, aluminum, zinc, and other metals to Cement Creek. Information is needed to prioritize remediation and develop strategies for cleanup of historical abandoned mine sites in Prospect Gulch. Chemical-constituent loads were determined in Prospect Gulch, a high-elevation alpine stream in southwestern Colorado that is affected by natural acid drainage from weathering of hydro-thermally altered igneous rock and acidic metal-laden discharge from historical abandoned mines. The objective of the study was to identify metal sources to Prospect Gulch. A tracer solution was injected into Prospect Gulch during water-quality sampling so that loading of geochemical constituents could be calculated throughout the study reach. A thunderstorm occurred during the tracer study, hence, metal loads were measured for storm-runoff as well as for base flow. Data from different parts of the study reach represents different flow conditions. The beginning of the reach represents background conditions during base flow immediately upstream from the Lark and Henrietta mines (samples PG5 to PG45). Other samples were collected during storm runoff conditions (PG100 to PG291); during the first flush of metal runoff following the onset of rainfall (PG303 to PG504), and samples PG542 to PG700 were collected during low-flow conditions. During base-flow conditions, the percentage increase in loads for major constituents and trace metals was more than an order of magnitude greater than the corresponding 36 % increase in stream discharge. Within the study reach, the highest percentage increases for dissolved loads were 740 % for iron (Fe), 465 % for aluminum (Al), 500 % for lead (Pb), 380 % for copper (Cu), 100 % for sulfate (SO4), and 50 % for zinc (Zn). Downstream loads near the mouth of Prospect Gulch often greatly exceeded the loads generated within the study reach but varied by metal species. For example, the study reach accounts for about 6 % of the dissolved-Fe load, 13 % of the dissolved-Al load, and 18 % of the dissolved-Zn load; but probably contributes virtually all of the dissolved Cu and Pb. The greatest downstream gains in dissolved trace-metal loads occurred near waste-rock dumps for the historical mines. The major sources of trace metals to the study reach were related to mining. The major source of trace metals in the reach near the mouth is unknown, however is probably related to weathering of highly altered igneous rocks, although an unknown component of trace metals could be derived from mining sources The late-summer storm dramatically increased the loads of most dissolved and total constituents. The effects of the storm were divided into two distinct periods; (1) a first flush of higher metal concentrations that occurred soon after rainfall began and (2) the peak discharge of the storm runoff. The first flush contained the highest loads of dissolved Fe, total and dissolved Zn, Cu, and Cd. The larger concentrations of Fe and sulfate in the first flush were likely derived from iron hydroxide minerals such as jarosite and schwertmanite, which are common on mine dumps in the Prospect Gulch drainage basin. Peak storm runoff contained the highest measured loads of total Fe, and of total and dissolved calcium, magnesium, silica and Al, which were probably derived from weathering of igneous rocks and clay minerals in the drainage basin.
Ebrahimzadeh, Mohammad Ali; Eslami, Shahram; Nabavi, Seyed Fazel; Nabavi, Seyed Mohammad
2011-12-01
The concentrations of Cr, Cu, Fe, Mn, Ni, Pb, Cd, and Zn were determined in the brain, heart, liver, gill, gonad, spleen, kidney, and red and white muscles of Liza saliens (leaping mullet). Trace element levels in fish samples were analyzed by flame atomic absorption spectrometry. Among the non-essential metals, the levels of Ni and Pb in the tissues were higher than limits for fish proposed by FAO/WHO, EU, and TFC. Generally, the levels of the non-essential metals were much higher than those of manganese in the red and white muscles. Fe distribution pattern in tissues was in order of spleen > liver > heart > gill > brain > kidney > gonad > red muscle > white muscle. Red muscle was not within the safe limits for human consumption because non-essential metal (Ni, Pb) contents were higher than standard limits.
Three-dimensional atlas of iron, copper, and zinc in the mouse cerebrum and brainstem.
Hare, Dominic J; Lee, Jason K; Beavis, Alison D; van Gramberg, Amanda; George, Jessica; Adlard, Paul A; Finkelstein, David I; Doble, Philip A
2012-05-01
Atlases depicting molecular and functional features of the brain are becoming an integral part of modern neuroscience. In this study we used laser ablation-inductively coupled plasma-mass spectrometry (LA-ICPMS) to quantitatively measure iron (Fe), copper (Cu), and zinc (Zn) levels in a serially sectioned C57BL/6 mouse brain (cerebrum and brainstem). Forty-six sections were analyzed in a single experiment of approximately 158 h in duration. We constructed a 46-plate reference atlas by aligning quantified images of metal distribution with corresponding coronal sections from the Allen Mouse Brain Reference Atlas. The 46 plates were also used to construct three-dimensional models of Fe, Cu, and Zn distribution. This atlas represents the first reconstruction of quantitative trace metal distribution through the brain by LA-ICPMS and will facilitate the study of trace metals in the brain and help to elucidate their role in neurobiology.
Distribution and speciation of trace elements in iron and manganese oxide cave deposits
DOE Office of Scientific and Technical Information (OSTI.GOV)
Frierdich, Andrew J.; Catalano, Jeffrey G.
2012-10-24
Fe and Mn oxide minerals control the distribution and speciation of heavy metals and trace elements in soils and aquatic systems through chemical mechanisms involving adsorption, incorporation, and electron transfer. The Pautler Cave System in Southwest Illinois, an analog to other temperate carbonate-hosted karst systems, contains Fe and Mn oxide minerals that form in multiple depositional environments and have high concentrations of associated trace elements. Synchrotron-based micro-scanning X-ray fluorescence ({mu}-SXRF) shows unique spatial distributions of Fe, Mn, and trace elements in mineral samples. Profile maps of Mn oxide cave stream pebble coatings show Fe- and As-rich laminations, indicating dynamic redoxmore » conditions in the cave stream. {mu}-SXRF maps demonstrate that Ni, Cu, and Zn correlate primarily with Mn whereas As correlates with both Mn and Fe; As is more enriched in the Fe phase. Zn is concentrated in the periphery of Mn oxide stream pebble coatings, and may be an indication of recent anthropogenic surface activity. X-ray absorption fine structure spectroscopy measurements reveal that As(V) occurs as surface complexes on Mn and Fe oxides whereas Zn(II) associated with Mn oxides is adsorbed to the basal planes of phyllomanganates in a tetrahedral coordination. Co(III) and Se(IV) are also observed to be associated with Mn oxides. The observation of Fe, Mn, and trace element banding in Mn oxide cave stream pebble coatings suggests that these materials are sensitive to and document aqueous redox conditions, similar to ferromanganese nodules in soils and in marine and freshwater sediments. Furthermore, speciation and distribution measurements indicate that these minerals scavenge trace elements and limit the transport of micronutrients and contaminants in karst aquifer systems while also potentially recording changes in anthropogenic surface activity and land-use.« less
The occurrence and distribution of trace metals in the Mississippi River and its tributaries
Taylor, Howard E.; Garbarino, J.R.; Brinton, T.I.
1990-01-01
Quantitative and semiquantitative analyses of dissolved trace metals are reported for designated sampling sites on the Mississippi River and its main tributaries utilizing depth-integrated and width-integrated sampling technology to collect statistically representative samples. Data are reported for three sampling periods, including: July-August 1987, November-December 1987, and May-June 1988. Concentrations of Al, As, Ba, Be, Cd, Co, Cr, Cu, Fe, Li, Mn, Mo, Pb, Sr, Tl, U, V, and Zn are reported quantitatively, with the remainder of the stable metals in the periodic table reported semiquantitatively. Correlations between As and V, Ba and U, Cu and Zn, Li and Ba, and Li and U are significant at the 99% confidence level for each of the sampling trips. Comparison of the results of this study for selected metals with other published data show generally good agreement for Cr, Cu, Fe, and Zn, moderate agreement for Mo, and poor agreement for Cd and V.
Chemical speciation of trace metals emitted from Indonesian peat fires for health risk assessment
NASA Astrophysics Data System (ADS)
Betha, Raghu; Pradani, Maharani; Lestari, Puji; Joshi, Umid Man; Reid, Jeffrey S.; Balasubramanian, Rajasekhar
2013-03-01
Regional smoke-induced haze in Southeast Asia, caused by uncontrolled forest and peat fires in Indonesia, is of major environmental and health concern. In this study, we estimated carcinogenic and non-carcinogenic health risk due to exposure to fine particles (PM2.5) as emitted from peat fires at Kalimantan, Indonesia. For the health risk analysis, chemical speciation (exchangeable, reducible, oxidizable, and residual fractions) of 12 trace metals (Al, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, Ti, V and Zn) in PM2.5 was studied. Results indicate that Al, Fe and Ti together accounted for a major fraction of total metal concentrations (~ 83%) in PM2.5 emissions in the immediate vicinity of peat fires. Chemical speciation reveals that a major proportion of most of the metals, with the exception of Cr, Mn, Fe, Ni and Cd, was present in the residual fraction. The exchangeable fraction of metals, which represents their bioavailability, could play a major role in inducing human health effects of PM2.5. This fraction contained carcinogenic metals such as Cd (39.2 ng m- 3) and Ni (249.3 ng m- 3) that exceeded their WHO guideline values by several factors. Health risk estimates suggest that exposure to PM2.5 emissions in the vicinity of peat fires poses serious health threats.
Minor and trace element concentrations in adjacent kamacite and taenite in the Krymka chondrite
NASA Astrophysics Data System (ADS)
Meftah, N.; Mostefaoui, S.; Jambon, A.; Guedda, E. H.; Pont, S.
2016-04-01
We report in situ NanoSIMS siderophile minor and trace element abundances in individual Fe-Ni metal grains in the unequilibrated chondrite Krymka (LL3.2). Associated kamacite and taenite of 10 metal grains in four chondrules and one matrix metal were analyzed for elemental concentrations of Fe, Ni, Co, Cu, Rh, Ir, and Pt. The results show large elemental variations among the metal grains. However, complementary and correlative variations exist between adjacent kamacite-taenite. This is consistent with the unequilibrated character of the chondrite and corroborates an attainment of chemical equilibrium between the metal phases. The calculated equilibrium temperature is 446 ± 9 °C. This is concordant with the range given by Kimura et al. (2008) for the Krymka postaccretion thermal metamorphism. Based on Ni diffusivity in taenite, a slow cooling rate is estimated of the Krymka parent body that does not exceed ~1K Myr-1, which is consistent with cooling rates inferred by other workers for unequilibrated ordinary chondrites. Elemental ionic radii might have played a role in controlling elemental partitioning between kamacite and taenite. The bulk compositions of the Krymka metal grains have nonsolar (mostly subsolar) element/Ni ratios suggesting the Fe-Ni grains could have formed from distinct precursors of nonsolar compositions or had their compositions modified subsequent to chondrule formation events.
Varol, Memet; Sünbül, Muhammet Raşit
2018-01-03
Freshwater mussels and crayfish are commonly used as biomonitors of trace metals. In the present study, the concentrations of ten metals were determined in mussels (Unio elongatulus eucirrus) and crayfish (Astacus leptodactylus) collected from the Keban Dam Reservoir in Turkey. The significant spatial differences in concentrations of studied metals except As in mussels were not found. However, Co, Cr, Cu, and Zn concentrations in mussels and As, Co, Cu, Fe, Pb, and Zn concentrations in crayfish showed significant seasonal differences. As, Cd, and Mn levels in mussels were about nine times higher than those in crayfish. The concentrations of Cd, Cr, Cu, Pb, Zn, and inorganic As in crayfish and mussels were lower than maximum permissible levels. When compared with other biomonitoring studies using mussels and crayfish, high concentrations of As, Cd, Co, Cr, and Ni in mussels and Cr and Ni in crayfish were observed due to lithogenic sources and anthropogenic activities in the basin. Bioconcentration factor values of Fe, Mn, Cd, and Zn in mussels and Zn, Cu, Fe, and Co in crayfish were > 1000, which indicates that both U. e. eucirrus and A. leptodactylus have potential to bioaccumulate these metals. Therefore, attention should be paid to mussels and crayfish from ecological and human health perspective, because they are potential vectors of metals to higher trophic levels.
Microscopic evaluation of trace metals in cloud droplets in an acid precipitation region.
Li, Weijun; Wang, Yan; Collett, Jeffrey L; Chen, Jianmin; Zhang, Xiaoye; Wang, Zifa; Wang, Wenxing
2013-05-07
Mass concentrations of soluble trace metals and size, number, and mixing properties of nanometal particles in clouds determine their toxicity to ecosystems. Cloud water was found to be acidic, with a pH of 3.52, at Mt. Lu (elevation 1,165 m) in an acid precipitation region in South China. A combination of Inductively Coupled Plasma Mass Spectrometry (ICPMS) and Transmission Electron Microscopy (TEM) for the first time demonstrates that the soluble metal concentrations and solid metal particle number are surprisingly high in acid clouds at Mt. Lu, where daily concentrations of SO2, NO2, and PM10 are 18 μg m(-3), 7 μg m(-3), and 22 μg m(-3). The soluble metals in cloudwater with the highest concentrations were zinc (Zn, 200 μg L(-1)), iron (Fe, 88 μg L(-1)), and lead (Pb, 77 μg L(-1)). TEM reveals that 76% of cloud residues include metal particles that range from 50 nm to 1 μm diameter with a median diameter of 250 nm. Four major metal-associated particle types are Pb-rich (35%), fly ash (27%), Fe-rich (23%), and Zn-rich (15%). Elemental mapping shows that minor soluble metals are distributed within sulfates of cloud residues. Emissions of fine metal particles from large, nonferrous industries and coal-fired power plants with tall stacks were transported upward to this high elevation. Our results suggest that the abundant trace metals in clouds aggravate the impacts of acid clouds or associated precipitation on the ecosystem and human health.
Atmospheric input of N, P, Fe and trace metals to north Indian Ocean
NASA Astrophysics Data System (ADS)
Sarin, Manmohan; Srinivas, Bikkina
2016-04-01
The air-sea deposition of chemical constituents to the north Indian Ocean is influenced by seasonal continental outflow during the late NE-monsoon (December-April). Our recent studies have focused on deposition of mineral dust, nutrients (N, P and Fe) and toxic trace metals to the Arabian Sea (ARS) and Bay of Bengal (BoB), two important limbs of the north Indian Ocean. The chemical composition of PM2.5 in the continental outflow to the marine atmospheric boundary layer reveals dominance of nss-SO42- (as high as 25 μg m-3) and abundance of dust varies from 3 to 20 μg m-3. A striking similarity in the temporal variability of total inorganic acidity (TIA = NO3- + nss-SO42-) and fractional solubility of aerosol-Fe (FeTot: 60 - 1145 ng m-3) provides evidence for chemical processing of mineral dust during atmospheric transport. The enhanced solubility of Fe has implications to further increase in the deposition of this micro-nutrient to ocean surface. The mass ratio of nutrients (NInorg/NTot, Norg/NTot and PInorg/nss-Ca2+) also suggests further increase in their air-sea deposition to the surface BoB. The dry-deposition flux of PInorgto BoB varies by one order of magnitude (0.5 - 5.0 μmol-P m-2 d-1; Av: 0.02 Tg P yr-1). Based on atmospheric deposition of P and Fe, C-fixation in BoB (˜1 Pg yr-1) is dominated by anthropogenic sources and that in ARS (0.3 Pg yr-1) is limited by P and Fe. This is attributed to poor fractional solubility (˜1%) of mineral dust over the Arabian Sea. However, N-fixation by diazotrophs in the two oceanic regions is somewhat similar (0.03 Pg yr-1). Our estimate of N-deposition (0.2 Tg yr-1) to the northern Indian Ocean is significantly lower than the model results (˜800 - 1200 mg-N m-2 yr-1 ≈ 5.7 - 8.6 Tg yr-1 by Duce et al. (2008); ˜4.1 Tg yr-1 by Okin et al. (2011); and ˜0.8 Tg yr-1 by Kanakidou et al. (2012). The increase in aerosol toxicity is also evident from high enrichment factors of anthropogenic trace metal (Pb, Cd, Cr, Cu and Mn). The enhanced solubility of anthropogenic fractions of trace metals, relative to their dust derived component, is an important issue for assessing factors that influence the marine ecosystem in the north Indian Ocean.
Marchand, C; Fernandez, J-M; Moreton, B
2016-08-15
Because of their physico-chemical inherent properties, mangrove sediments may act as a sink for pollutants coming from catchments. The main objective of this study was to assess the distribution of some trace metals in the tissues of various mangrove plants developing downstream highly weathered ferralsols, taking into account metals partitioning in the sediment. In New Caledonia, mangroves act as a buffer between open-cast mines and the world's largest lagoon. As a result of the erosion of lateritic soils, Ni and Fe concentrations in the sediment were substantially higher than the world average. Whatever the mangrove stand and despite low bioaccumulation and translocations factors, Fe and Ni were also the most abundant metals in the different plant tissues. This low bioaccumulation may be explained by: i) the low availability of metals, which were mainly present in the form of oxides or sulfur minerals, and ii) the root systems acting as barriers towards the transfer of metals to the plant. Conversely, Cu and Zn metals had a greater mobility in the plant, and were characterized by high bioconcentration and translocation factors compared to the other metals. Cu and Zn were also more mobile in the sediment as a result of their association with organic matter. Whatever the metal, a strong decrease of trace metal stock was observed from the landside to the seaside of the mangrove, probably as a result of the increased reactivity of the sediment due to OM enrichment. This reactivity lead to higher dissolution of bearing phases, and thus to the export of dissolved trace metals trough the tidal action. Cu and Zn were the less concerned by the phenomenon probably as a result of higher plant uptake and their restitution to the sediment with litter fall in stands where tidal flushing is limited. Copyright © 2016 Elsevier B.V. All rights reserved.
NASA Astrophysics Data System (ADS)
Milne, A.; Palmer, M.; Lohan, M. C.
2016-02-01
Particles play a fundamental role in the biogeochemical cycling of both major- and micro-nutrients in marine systems, including trace elements and isotopes. However, knowledge of particulate distributions, and their potential to regulate dissolved elemental concentrations, remains limited and poorly understood. The paradox is, that the oceanic inventory of trace metals is dominated by particulate inputs (e.g. aerosol deposition, shelf sediment resuspension). Moreover the labile fraction of particulate trace elements could be an important regulator of dissolved concentrations. Here we present particulate data from the UK GEOTRACES South Atlantic transect (GA10) from South Africa to Uruguay. Data from a range of elements (e.g. Fe, Al, Mn) revealed a greater input of particulate metals from the Argentine shelf (up to 290 nM of pFe) in comparison to the South African shelf (< 40 nM of pFe). Overall, higher concentrations of all metals were observed in the bottom waters of the Argentine basin and penetrated deeper up the water column (up to 1300 m), a result of intense benthic storms. The imprint of leakage from the Agulhas Current, identified through temperature and salinity, was observed in the upper water column profile of numerous particulate data (e.g. Pb, Ni, Cd). Measured elemental gradients, combined with measurements from a vertical mixing-profiler, will allow estimates of particulate fluxes to be calculated.
Schmidt, Thomas; Nelles, Michael; Scholwin, Frank; Pröter, Jürgen
2014-09-01
A trace element dosing strategy for the anaerobic digestion of wheat stillage was developed in this study. Mesophilic CSTR reactors were operated with the sulfuric substrate wheat stillage in some cases under trace element deficiency. After supplementing trace elements during the start-up, one of the elements of Fe, Ni, Co, Mo, and W were depleted in one digester while still augmenting the other elements to determine minimum requirements for each element. The depletion of Fe and Ni resulted in a rapid accumulation of volatile fatty acids while Co and W seem to have a long-term effect. Based on the results it was possible to reduce the dosing of trace elements, which is positive with reference to economic and environmental aspects. Copyright © 2014 Elsevier Ltd. All rights reserved.
Trace-element evidence for the origin of desert varnish by direct aqueous atmospheric deposition
NASA Astrophysics Data System (ADS)
Thiagarajan, Nivedita; Aeolus Lee, Cin-Ty
2004-07-01
Smooth rock surfaces in arid environments are often covered with a thin coating of Fe-Mn oxyhydroxides known as desert varnish. It is debated whether such varnish is formed (a) by slow diagenesis of dust particles deposited on rock surfaces, (b) by leaching from the underlying rock substrate, or (c) by direct deposition of dissolved constituents in the atmosphere. Varnishes collected from smooth rock surfaces in the Mojave Desert and Death Valley, California are shown here to have highly enriched and fractionated trace-element abundances relative to upper continental crust (UCC). They are highly enriched in Co, Ni, Pb and the rare-earth elements (REEs). In particular, they have anomalously high Ce/La and low Y/Ho ratios. These features can only be explained by preferential scavenging of Co, Ni, Pb and the REEs by Fe-Mn oxyhydroxides in an aqueous environment. High field strength elements (HFSEs: Zr, Hf, Ta, Nb, Th), however, show only small enrichments despite the fact that these elements should also be strongly scavenged by Fe-Mn oxyhydroxides. This suggests that their lack of enrichment is a feature inherited from a solution initially poor in HFSEs. The first two scenarios for varnish formation can be ruled out as follows. The high enrichment factors of Fe, Mn and many trace elements cannot be generated by mass loss associated with post-depositional diagenesis of dust particles because such a process predicts only a small increase in concentration. In addition, the highly fractionated abundance patterns of particle reactive element pairs (e.g., Ce/La and Y/Ho) rules out leaching of the rock substrate. This is because if leaching were to occur, varnishes would grow from the inside to the outside, and thus any particle-reactive trace element leached from the substrate would be quantitatively sequestered in the Fe-Mn oxyhydroxide layers, prohibiting any significant elemental fractionations. One remaining possibility is that the Fe, Mn and trace metals in varnish are derived from leaching of dust particles entrained in rain or fog droplets either in the atmosphere or during wet atmospheric deposition. The high trace metal enrichment factors require that most of the dust was physically removed before or during varnish formation. The remaining aqueous counterpart would be depleted in HFSEs and Th relative to the REEs, Co, Ni and Pb because the former are more insoluble and hence largely retained in the removed dust fraction. The high Ce/La ratios suggest that precipitation of trace metals may have been governed by equilibrium partitioning in an excess of wet atmospheric deposition. If varnishes are indeed derived from wet atmospheric deposition, they may provide a record of the aqueous component of atmospheric dust inputs to various environments.
Heavy metals in Lake Balaton: water column, suspended matter, sediment and biota.
Nguyen, H L; Leermakers, M; Osán, J; Török, S; Baeyens, W
2005-03-20
During the period 1999-2002, five sampling cruises have been carried out on Lake Balaton to assess trace metal distribution in the lake and to identify major sources. Eighteen elements, including Cr, Co, Ni, Cu, Zn, Cd, Pb (trace metals) and Al, Ba, Ca, Fe, K, Mg, Mn, Na, P, S, Sr (major metals), were determined in one or more of the lake's compartments. Lower trace metal concentrations in rainwater were observed in June and February 2000, while much higher levels were present in September 2001 (during a storm event) and in snow (February 2000). In the Northern and Western parts of the lake, especially at the inflow of river Zala and the locations of the yacht harbours, metal concentrations were higher in almost all compartments. Because the lake is very shallow, storm conditions also change significantly the metal distributions in the dissolved and particulate phases. The Kis-Balaton protection system located on Zala river functions very efficiently for retaining suspended particulate matter (SPM; 72% retention) and associated metals. Metal concentrations in surface sediments of the lake showed a high variability. After normalisation for the fine sediment fraction, only a few stations including Zala mouth appeared to be enriched in trace metals. In zooplankton, Zn seemed to be much more elevated compared to the other trace metals. Based on the molar ratios of the trace metals in the various compartments and input flows of the lake, several trends could be deduced. For example, molar ratios of the trace metals in the dissolved and solid (suspended particulate matter and sediments) phases in the lake are fairly similar to those in Zala River.
NASA Astrophysics Data System (ADS)
Woelfl, Stefan; Mages, Margarete; Torres, Patricio
2008-12-01
The aim of this study was to investigate (1) whether intestine endoparasites ( Diphyllobothrium latum) accumulate trace elements related to its body size and (2) whether parasites bioconcentrate more trace elements than their host. Freshwater fish (rainbow trout Oncorhynchus mykiss) were sampled in the deep, oligotrophic and uncontaminated Lake Riñihue in Southern Chile. The element concentration of different organs (intestine, muscle, liver) and of the intestine endoparasites were analyzed using total reflection X-ray fluorescence spectrometry. The results showed that the mass fraction for Mn, Fe, Ni, Cu, and Pb decreased significantly with the body size (dry weight) of the endoparasite. Only Zn did not reveal such a relationship. Small parasites accumulated up to 80 times more Fe, Ni, Mn, Pb, and Cu than large parasites. Compared to the fish organs, small parasites accumulated in maximum 35 to 307 times more Mn, 5 to 255 times more Fe, 98 to 220 times more Ni, 3 to 175 times more Cu, and 0.4 to 12 times more Zn than the fish. Lead was only found in the endoparasite, but not in the fish organs. We conclude that (1) D. latum is a good indicator for trace element accumulation in fishes and that (2) small endoparasites are more sensitive as bioindicators because they showed higher bioconcentrations of trace metals than larger parasites.
Adsorption of Heavy Metals in Industrial Wastewater by Magnetic Nano-particles
NASA Astrophysics Data System (ADS)
Tu, Y.; You, C.
2010-12-01
Industrial wastewater containing heavy metals is of great concern because of their toxic impact to living species and environments. Removal of metal ions from industrial effluent using nano-particles is an area of extensive research. This study collected wastewaters and effluents from 11 industrial companies in tanning, electronic plating, printed circuit board manufacturing, semi-conductor, and metal surface treatment industry and studied in detailed the major and trace element compositions to develop potential fingerprinting technique for pollutant source identification. The results showed that electronic plating and metal surface treatment industry produce high Fe, Mn, Cr, Zn, Ni and Mo wastewater. The tanning industry and the printed circuit board manufacturing industry released wastewater with high Fe and Cr, Cu and Ni, respectively. For semi-conductor industry, significant dissolved In was detected in wastewater. The absorption experiments to remove heavy metals in waters were conducted using Fe3O4 nano-particles. Under optimal conditions, more than 99 % dissolved metals were removed in a few minutes.
Controls on the Transition Metal Isotopic Composition of Seawater: Diatom Culture Experiments
NASA Astrophysics Data System (ADS)
Vance, D.; Archer, C.; Kennaway, G.; Cox, E.; Statham, P. J.
2004-12-01
Many transition metals are essential micronutrients for marine phytoplankton. As a result the expectation is that biological processes play an important, perhaps a dominant, role in their marine isotope geochemistry. These observations raise the prospect of using isotope records to trace transition metal micronutrient usage in the past oceans, an issue that is of importance to the efficiency of the biological pump and atmospheric carbon dioxide. As such, the characterisation of trace metal isotopic fractionations associated with marine primary productivity are an important scientific goal. Here we report fractionations associated with Fe, Cu and Zn sequestration by diatoms, one of the main primary producers in the oceans. Axenic unialgal cultures of Thalassiosira weissflogii and Thalassiosira pseudonana were established in artificial seawater + F/2 medium at 18° C on a 16:8 light:dark cycle. The cultures were filtered to separate diatom material from residual media and analysed for Zn, Cu and Fe concentrations and isotope composition using techniques described elsewhere1,2. Aliquots of the starting medium were also measured for each batch of cultures. The diatom organic material shows small, but consistent and resolvable, positive fractionations (0.1-0.3 per mil) for Fe, Cu and Zn relative to the starting medium. In the case of all three metals, but particularly for Zn (70-95% depending on experiment size), the diatoms had sequestered a large proportion of the available metal, suggesting that the fractionation factor for metal usage by the diatoms is much greater than 1.0001 to 1.0003. Time-series experiments are under way to determine the exact magnitude of the fractionation factor. The mass-balance is supported by the fact that the residual medium is around -0.4 per mil for Zn. The fact that diatoms incorporate trace metals that are isotopically heavier than the nutrient pool is a surprising result, the expectation having been that, as with carbon, the biological usage of trace metals would result in kinetic fractionations3. The positive fractionations necessitate an equilibrium process and, perhaps, active extra-cellular sequestration of trace metals. The second broader implication is that given the proposed role of diatoms in controlling the extreme depletion of Zn in open ocean surface waters, particularly in the Pacific where surface waters are have up to a factor of 250 less Zn than deep waters4, the depletion of the light isotope in surface waters and its enrichment in deep waters are predicted to be extreme. Zn, and other trace metal, isotopes may have an important role in recording this process in the past oceans. 1 C. Archer and D. Vance, 2004, J. Anal. Atom. Spectr. 19, 656-665. 2 J. Bermin, et al., 2004, this volume. 3 Pichat, S et al., 2003, Earth Planet. Sci. Lett. 210, 167-178. 4 Lohan, M.C. et al., 2002, Deep-Sea Res. II 49, 5793-5808.
Evaluation of Fe(II) oxidation at an acid mine drainage site using laboratory-scale reactors
NASA Astrophysics Data System (ADS)
Brown, Juliana; Burgos, William
2010-05-01
Acid mine drainage (AMD) is a severe environmental threat to the Appalachian region of the Eastern United States. The Susquehanna and Potomac River basins of Pennsylvania drain to the Chesapeake Bay, which is heavily polluted by acidity and metals from AMD. This study attempted to unravel the complex relationships between AMD geochemistry, microbial communities, hydrodynamic conditions, and the mineral precipitates for low-pH Fe mounds formed downstream of deep mine discharges, such as Lower Red Eyes in Somerset County, PA, USA. This site is contaminated with high concentrations of Fe (550 mg/L), Mn (115 mg/L), and other trace metals. At the site 95% of dissolved Fe(II) and 56% of total dissolved Fe is removed without treatment, across the mound, but there is no change in the concentration of trace metals. Fe(III) oxides were collected across the Red Eyes Fe mound and precipitates were analyzed by X-ray diffraction, electron microscopy and elemental analysis. Schwertmannite was the dominant mineral phase with traces of goethite. The precipitates also contained minor amounts of Al2O3, MgO,and P2O5. Laboratory flow-through reactors were constructed to quantify Fe(II) oxidation and Fe removal over time at terrace and pool depositional facies. Conditions such as residence time, number of reactors in sequence and water column height were varied to determine optimal conditions for Fe removal. Reactors with sediments collected from an upstream terrace oxidized more than 50% of dissolved Fe(II) at a ten hour residence time, while upstream pool sediments only oxidized 40% of dissolved Fe(II). Downstream terrace and pool sediments were only capable of oxidizing 25% and 20% of Fe(II), respectively. Fe(II) oxidation rates measured in the reactors were determined to be between 3.99 x 10-8and 1.94 x 10-7mol L-1s-1. The sediments were not as efficient for total dissolved Fe removal and only 25% was removed under optimal conditions. The removal efficiency for all sediments decreased as residence time decreased and as water column depth increased. Control reactors with Co-60 irradiated sediments showed an increase in Fe concentration as a result of dissolution of the sediments; thus, it was concluded that Fe(II) oxidation in the reactors was a result of biological processes and not abiotic oxidation. It was also concluded that Fe(II) oxidation and removal rates were dependent upon geochemical gradients (pH, Fe(II) concentration) rather than depositional facies. Fluorescent in situ hybridization was also performed on field and reactor samples to determine which microbial communities were responsible for the highest Fe(II) oxidation rates.
Yang, Wei; Li, Xiaoxiao; Pei, Jun; Sun, Tao; Shao, Dongdong; Bai, Junhong; Li, Yanxia
2017-12-01
We investigated the speciation of trace metals and their ecological risks to macrobenthic communities in a recovering coastal wetland of China's Yellow River Delta during the freshwater release project. We established 16 sampling sites in three restoration areas and one intertidal reference area, and collected sediments and macrobenthos four times from 2014 to 2015. The instability index for the trace metals showed a moderate risk for Mn and a high risk for Cd. For both Mn and Cd, the carbonate and FeMn-bound fractions appear to contribute mostly to the instability and bioavailability indexes, but for Cd, the exchangeable fraction also have a much higher contribution. The bioavailability index indicated higher bioavailability of trace metals in freshwater restoration areas than that in the intertidal area. The single-factor contamination index indicated that most trace metal concentrations in the macrobenthos were in excess of the national standard. The biota-sediment accumulation factor suggested that the macrobenthos accumulated most As, Cd, and Cu. Redundancy analysis showed clear relationships between the macrobenthos and sediment metal concentrations. Our results will help wetland managers to assess the bioaccumulation risks based on metal speciation, and to improve management of these recovering freshwater wetland ecosystems. Copyright © 2017 Elsevier Ltd. All rights reserved.
NASA Astrophysics Data System (ADS)
Fitzsimmons, J. N.; Parker, C.; Sherrell, R. M.
2016-02-01
The physicochemical speciation of trace metals in seawater influences their cycling as essential micronutrients for microorganisms or as tracers of anthropogenic influences on the marine environment. While chemical speciation affects lability, the size of metal complexes influences their ability to be accessed biologically and also influences their fate in the aggregation pathway to marine particles. In this study, we show that multiple trace metals in shelf and open ocean waters off northern California (IRN-BRU cruise, July 2014) have colloidal-sized components. Colloidal fractions were operationally defined using two ultrafiltration methods: a 0.02 µm Anopore membrane and a 10 kDa ( 0.003 µm) cross flow filtration (CFF) system. Together these two methods distinguished small (0.003 - 0.02 µm) and large (0.02 µm - 0.2 µm) colloids. As has been found previously for seawater in other ocean regimes, dissolved Fe had a broad size distribution with 50% soluble (<10 kDa) complexes and both small and large colloidal species. Dissolved Mn had no measurable colloidal component, consistent with its predicted chemical speciation as free Mn(II). Dissolved Cu, which like Fe is thought to be nearly fully organically bound in seawater, was only 25% colloidal, and these colloids were all small. Surprisingly Cd, Ni, and Pb also showed colloidal components (8-20%, 25-40%, and 10-50%) despite their hypothesized low organic speciation. Zn and Pb were nearly completely sorbed onto the Anopore membrane, making CFF the only viable ultrafiltration method for those elements. Zn suffered incomplete recovery ( 50-75%) through the CFF system but showed 30-85% colloidal contribution; thus, verifying a Zn colloidal phase with these methods is challenging. Conclusions will reveal links between the physical and chemical speciation for these metals and what role these metal colloids might have on trace metal exchange between the ocean margin and offshore waters.
Martin, G. D.; George, Rejomon; Shaiju, P.; Muraleedharan, K. R.; Nair, S. M.; Chandramohanakumar, N.
2012-01-01
Concentrations and distributions of trace metals (Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, and Zn) in surficial sediments of the Cochin backwaters were studied during both monsoon and pre-monsoon periods. Spatial variations were in accordance with textural charaterstics and organic matter content. A principal component analysis distinguished three zones with different metal accumulation capacity: (i) highest levels in north estuary, (ii) moderate levels in central zone, and (iii) lowest levels in southern part. Trace metal enrichments are mainly due to anthropogenic contribution of industrial, domestic, and agricultural effluents, whose effect is enhanced by settling of metals due to organic flocculation and inorganic precipitation associated with salinity changes. Enrichments factors using Fe as a normalizer showed that metal contamination was the product of anthropogenic activities. An assessment of degree of pollution-categorized sediments as moderately polluted with Cu and Pb, moderately-to-heavily polluted with Zn, and heavily-to-extremely polluted with Cd. Concentrations at many sites largely exceed NOAA ERL (e.g., Cu, Cr, and Pb) or ERM (e.g., Cd, Ni, and Zn). This means that adverse effects for benthic organisms are possible or even highly probable. PMID:22645488
Cruse, A.M.; Lyons, T.W.
2004-01-01
Regional geochemical differences within a laterally continuous, cyclic Pennsylvanian (Upper Carboniferous) shale in midcontinent North America are interpreted in light of models of glacioeustatic forcing and new views on water-column paleoredox stability and trace-metal behavior in black shale environments. Specifically, we characterize differences in transition metal (Fe, Mn, Mo, V, Ni, Zn, Pb and U) concentrations in black shales of the Hushpuckney Shale Member of the Swope Limestone in Iowa and equivalent black shale beds of the Coffeyville Formation in Oklahoma. Although C-S-Fe systematics and uniform 34S-depleted isotope ratios of pyrite indicate pervasive euxinic deposition (anoxic and sulfidic bottom waters) for these shales, regional variations can be inferred for the efficiency of Mo scavenging and for the rates of siliciclastic sedimentation as expressed in spatially varying Fe/Al ratios. Black shales in Iowa show Mo enrichment roughly five times greater than that observed in coeval euxinic shales in Oklahoma. By contrast, Fe/Al ratios in Oklahoma shales are as much as five times greater than the continental ratio of 0.5 observed in the over- and underlying oxic facies and in the coeval black shales in Iowa. Recent work in modern marine settings has shown that enrichments in Fe commonly result from scavenging in a euxinic water column during syngenetic pyrite formation. In contrast to Fe, the concentrations of other transition metals (Mo, V, Ni, Pb, Zn, U) are typically more enriched in the black shales in Iowa relative to Oklahoma. The transition metal trends in these Paleozoic shales are reasonably interpreted in terms of early fixation in organic-rich sediments due to euxinic water-column conditions. However, regional variations in (1) rates of siliciclastic input, (2) organic reservoirs, including relative inputs of terrestrial versus marine organic matter, and (3) additional inputs of metals to bottom waters from contemporaneous hydrothermal vents are additional key controls that lead to geographic variation in the extent of metal enrichments preserved in ancient organic-rich sediments. Published by Elsevier B.V.
Diyabalanage, Saranga; Abekoon, Sumith; Watanabe, Izumi; Watai, Chie; Ono, Yuko; Wijesekara, Saman; Guruge, Keerthi S; Chandrajith, Rohana
2016-06-01
The Mahaweli is the largest river basin in Sri Lanka that provides water to the dry zone region through multipurpose irrigation schemes . Selenium, arsenic, cadmium, and other bioimportant trace elements in surface waters of the upper Mahaweli River were measured using ICP-MS. Trace element levels were then compared with water from two other rivers (Maha Oya, Kalu Ganga) and from six dry zone irrigation reservoirs. Results showed that the trace metal concentrations in the Mahaweli upper catchment were detected in the order of Fe > Cu > Zn > Se > Cr > Mn > As > Ni > Co > Mo. Remarkably high levels of Ca, Cr, Co, Ni, Cu, As, and Se were observed in the Mahaweli Basin compared to other study rivers. Considerably high levels of Cr, Mn, Fe, Co, Ni, Cu, Zn, As, and Se were found in upstream tributaries of the Mahaweli River. Such metals possibly originated from phosphate and organic fertilizers that are heavily applied for tea and vegetable cultivations within the drainage basin. Cadmium that is often attributed to the etiology of unknown chronic kidney diseases in certain parts of the dry zone is much lower than previously reported levels. Decrease in these metals in the lower part of the Mahaweli River could be due to adsorption of trace metals onto sediment and consequent deposition in reservoirs.
Solubility of aerosol trace elements: Sources and deposition fluxes in the Canary Region
NASA Astrophysics Data System (ADS)
López-García, Patricia; Gelado-Caballero, María Dolores; Collado-Sánchez, Cayetano; Hernández-Brito, José Joaquín
2017-01-01
African dust inputs have important effects on the climate and marine biogeochemistry of the subtropical North Atlantic Ocean. The impact of dust inputs on oceanic carbon uptake and climate is dependent on total dust deposition fluxes as well as the bioavailability of nutrients and metals in the dust. In this work, the solubility of trace metals (Fe, Al, Mn, Co and Cu) and ions (Ca, sulphate, nitrate and phosphate) has been estimated from the analysis of a long-time series of 109 samples collected over a 3-year period in the Canary Islands. Solubility is primarily a function of aerosol origin, with higher solubility values corresponding to aerosols with more anthropogenic influence. Using soluble fractions of trace elements measured in this work, atmospheric deposition fluxes of soluble metals and nutrients have been calculated. Inputs of dissolved nutrients (P, N and Fe) have been estimated for the mixed layer. Considering that P is the limiting factor when ratios of these elements are compared with phytoplankton requirements, an increase of 0.58 nM of P in the mixed layer (∼150 m depth) and in a year can be estimated, which can support an increase of 0.02 μg Chla L-1 y-1. These atmospheric inputs of trace metals and nutrients appear to be significant relative to the concentrations reported in this region, especially during the summer months when the water column is more stratified and deep-water nutrient inputs are reduced.
Shulkin, Vladimir; Zhang, Jing
2014-11-15
This paper compares the distributions of dissolved and particulate forms of Mn, Fe, Ni, Cu, Zn, Cd, and Pb in the estuaries of the largest rivers in East Asia: the Amur River and the Changjiang (Yangtze River). High suspended solid concentrations, elevated pH, and relatively low dissolved trace metal concentrations are characteristics of the Changjiang. Elevated dissolved Fe and Mn concentrations, neutral pH, and relatively low suspended solid concentrations are characteristics of the Amur River. The transfer of dissolved Fe to suspended forms is typical in the Amur River estuary, though Cd and Mn tend to mobilize to solution, and Cu and Ni are diluted in the estuarine system. Metal concentrations in suspended matter in the Amur River estuary are controlled by the ratio of terrigenous riverine material, enriched in Al and Fe, and marine biogenic particles, enriched in Cu, Mn, Cd, and in some cases Ni. The increase in dissolved forms of Mn, Fe, Ni, Cu, Cd, and Pb compared with river end-member is unique to the Changjiang estuary. Particle-solution interactions are not reflected in bulk suspended-solid metal concentrations in the Changjiang estuary due to the dominance of particulate forms of these metals. Cd is an exception in the Changjiang estuary, where the increase in dissolved Cd is of comparable magnitude to the decrease in particulate Cd. Despite runoff in the Amur River being lower than that in the Changjiang, the fluxes of dissolved Mn, Zn and Fe in the Amur River exceed those in the Changjiang. Dissolved Ni, and Cd fluxes are near equal in both estuaries, but dissolved Cu is lower in the Amur River estuary. The hydrological and physico-chemical river characteristics are dominated at the assessment of river influence on the adjoining coastal sea areas despite differences in estuarine processes. Copyright © 2014 Elsevier B.V. All rights reserved.
Determination of trace and heavy metals in some commonly used medicinal herbs in Ayurveda.
Nema, Neelesh K; Maity, Niladri; Sarkar, Birendra K; Mukherjee, Pulok K
2014-11-01
Traditionally, the herbal drugs are well established for their therapeutic benefits. Depending upon their geographical sources sometimes the trace and heavy metals' content may differ, which may lead to severe toxicity. So, the toxicological and safety assessment of these herbal drugs are one of the major issues in recent days. Eight different plant species including Aloe vera, Centella asiatica, Calendula officinalis, Cucumis sativus, Camellia sinensis, Clitoria ternatea, Piper betel and Tagetes erecta were selected to determine their heavy and trace metals content and thereby to assure their safer therapeutic application. The trace and heavy metals were detected through atomic absorption spectrometry analysis. The selected medicinal plant materials were collected from the local cultivated regions of West Bengal, India, and were digested with nitric acid and hydrochloric acid as specified. Absorbance was measured through atomic absorption spectrometer (AA 303) and the concentration of different trace and heavy metals in the plant samples were calculated. The quantitative determinations were carried out using standard calibration curve obtained by the standard solutions of different metals. The contents of heavy metals were found to be within the prescribed limit. Other trace metals were found to be present in significant amount. Thus, on the basis of experimental outcome, it can be concluded that the plant materials collected from the specific region are safe and may not produce any harmful effect of metal toxicity during their therapeutic application. The investigated medicinal plants contain trace metals such as copper (Cu), chromium (Cr), manganese (Mn), iron (Fe) and nickel (Ni) as well as heavy metals such as arsenic (As), lead (Pb) and mercury (Hg), which were present within the permissible limit. © The Author(s) 2012.
Mimba, Mumbfu Ernestine; Ohba, Takeshi; Nguemhe Fils, Salomon César; Nforba, Melvin Tamnta; Numanami, Nozomi; Bafon, Tasin Godlove; Aka, Festus Tongwa; Suh, Cheo Emmanuel
2018-05-02
The distribution of trace metals in active stream sediments from the mineralized Lom Basin has been evaluated. Fifty-five bottom sediments were collected and the mineralogical composition of six pulverized samples determined by XRD. The fine fraction (< 150 µm) was subjected to total digestion (HClO 4 + HF + HCl) and analyzed for trace metals using a combination of ICP-MS and AAS analytical methods. Results show that the mineralogy of stream sediments is dominated by quartz (39-86%), phyllosilicates (0-45%) and feldspars (0-27%). Mean concentrations of the analyzed metals are low (e.g. As = 99.40 µg/kg, Zn = 573.24 µg/kg, V = 963.14 µg/kg and Cr = 763.93 µg/kg). Iron and Mn have significant average concentrations of 28.325 and 442 mg/kg, respectively. Background and threshold values of the trace metals were computed statistically to determine geochemical anomalies of geologic or anthropogenic origin, particularly mining activity. Factor analysis, applied on normalized data, identified three associations: Ni-Cr-V-Co-As-Se-pH, Cu-Zn-Hg-Pb-Cd-Sc and Fe-Mn. The first association is controlled by source geology and the neutral pH, the second by sulphide mineralization and the last by chemical weathering of ferromagnesian minerals. Spatial analysis reveals similar distribution trends for Co-Cr-V-Ni and Cu-Zn-Pb-Sc reflecting the lithology and sulphide mineralization in the basin. Relatively high levels of As were concordant with reported gold occurrences in the area while Fe and Mn distribution are consistent with their source from the Fe-bearing metamorphic rocks. These findings provide baseline geochemical values for common and parallel geological domains in the eastern region of Cameroon. Although this study shows that the stream sediments are not polluted, the evaluation of metal composition in environmental samples from abandoned and active mine sites for comparison and environmental health risk assessment is highly recommended.
Li, Jingxi; Sun, Chengjun; Zheng, Li; Jiang, Fenghua; Wang, Shuai; Zhuang, Zhixia; Wang, Xiaoru
2017-09-15
Trace metal contents in 38 species of tropical marine fishes harvested from the Spratly islands of China were determined by microwave digestion and inductively coupled plasma mass spectrometry analysis. Arsenic species were determined by high-performance liquid chromatography and inductively coupled plasma mass spectrometry analysis. The average levels of Al, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Mo, Cd, Pb, and U in the fish samples were 1.683, 0.350, 0.367, 2.954, 36.615, 0.087, 0.319, 1.566, 21.946, 20.845, 2.526, 3.583, 0.225, 0.140, and 0.061mg·kg -1 , respectively; Fe, Zn, and As were found at high concentrations. The trace metals exhibited significant positive correlation between each other, with r value of 0.610-0.852. Further analysis indicated that AsB (8.560-31.020mg·kg -1 ) was the dominant arsenic species in the fish samples and accounted for 31.48% to 47.24% of the total arsenic. As(III) and As(V) were detected at low concentrations, indicating minimal arsenic toxicity. Copyright © 2017. Published by Elsevier Ltd.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Wallace, A.; Cha, J.W.; Alexander, G.V.
Plants were grown in solution culture with different levels of Ca to further evaluate Ca relationships to trace metal uptake and to toxicity of trace metals. When tomato plants (Lycopersicon esculentum L., Tropic) were grown at a low level of Ca, the Zn, Cu, Fe, Mn, Al, and Ti concentrations of leaves, stems, and roots were considerably increased. The use of an excess of CaCO/sub 3/ which increased pH did not influence the trace metal concentrations of plants any more than did Ca/sup + +/. In a factorial experiment with bush beans (Phaseolus vulgaris L. C.V. Improved Tendergreen) with Camore » (10/sup -4/, 10/sup -2/, 10/sup -2/N) and Ni (0, 2 x 10/sup -6/ M, 2 x 10/sup -5/ M), Ni phytotoxicity and Ni uptake were decreased somewhat at the highest Ca level. High Ni tended to decrease the Ca concentration in leaves. High Ca and Ni both tended to decrease Fe, Cu, Zn, and Mn concentrations in leaves. The Ni had some interactions on the P concentrations of shoots.« less
Bashir, Fathi Alhashmi; Shuhaimi-Othman, Mohammad; Mazlan, A. G.
2012-01-01
This study is focused on evaluating the trace metal levels in water and tissues of two commercial fish species Arius thalassinus and Pennahia anea that were collected from Kapar and Mersing coastal waters. The concentrations of Fe, Zn, Al, As, Cd and Pb in these coastal waters and muscle, liver and gills tissues of the fishes were quantified. The relationship among the metal concentrations and the height and weight of the two species were also examined. Generally, the iron has the highest concentrations in both water and the fish species. However, Cd in both coastal waters showed high levels exceeding the international standards. The metal level concentration in the sample fishes are in the descending order livers > gills > muscles. A positive association between the trace metal concentrations and weight and length of the sample fishes was investigated. Fortunately the level of these metal concentrations in fish has not exceeded the permitted level of Malaysian and international standards. PMID:22046193
Trace metal contents of selected seeds and vegetables from oil producing areas of Nigeria.
Wegwu, Matthew O; Omeodu, Stephen I
2010-07-01
The concentrations of accumulated trace metals in selected seeds and vegetables collected in the oil producing Rivers State of Nigeria were investigated. The values were compared with those of seeds and vegetables cultivated in Owerri, a less industrialized area in Nigeria. The lead (Pb) and cadmium (Cd) contents of the seeds obtained from Rivers State ranged between 0.10 and 0.23 microg/g dry weight, while those of the seeds cultivated in Owerri fell below the detection limit of 0.01 microg/g dry weight. The highest manganese (Mn) level (902 microg/g dry weight) was found in Irvingia garbonesis seeds cultivated in Rivers State. Similarly, the highest nickel (Ni) value (199 microg/g dry weight) was also obtained in I. garbonesis, however, in the seeds sampled in Owerri. The highest copper (Cu), zinc (Zn), and iron (Fe) levels (16.8, 5.27, and 26.2 microg/g dry weight, resp.) were detected in seeds collected in Rivers State. With the exception of Talinum triangulae, Ocinum gratissimum, and Piper guineese, with Pb levels of 0.09, 0.10, and 0.11 microg/g dry weight, respectively, the Pb and Cd levels in the vegetables grown in Owerri fell below the detection limit of 0.01 microg/g dry weight. The trace metal with the highest levels in all the vegetables studied was Mn, followed by Fe. The highest concentrations of Ni and Cu occurred in vegetables collected from Rivers State, while the highest level of Zn was observed in Piper guineese collected in Owerri, with a value of 21.4 microg/g dry weight. Although the trace metal concentrations of the seeds and vegetables collected in Rivers State tended to be higher than those of the seeds and vegetables grown in Owerri, the average levels of trace metals obtained in this study fell far below the WHO specifications for metals in foods.
Determination of trace metals in spirits by total reflection X-ray fluorescence spectrometry
NASA Astrophysics Data System (ADS)
Siviero, G.; Cinosi, A.; Monticelli, D.; Seralessandri, L.
2018-06-01
Eight spirituous samples were analyzed for trace metal content with Horizon Total Reflection X-Ray Fluorescence (TXRF) Spectrometer. The expected single metal amount is at the ng/g level in a mixed aqueous/organic matrix, thus requiring a sample preparation method capable of achieving suitable limits of detection. On-site enrichment and Atmospheric Pressure-Vapor Phase Decomposition allowed to detect Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Sr and Pb with detection limits ranging from 0.1 ng/g to 4.6 ng/g. These results highlight how the synergy between instrument and sample preparation strategy may foster the use of TXRF as a fast and reliable technique for the determination of trace elements in spirituous samples, either for quality control or risk assessment purposes.
Bioactive trace metal time series during Austral summer in Ryder Bay, Western Antarctic Peninsula
NASA Astrophysics Data System (ADS)
Bown, Johann; Laan, Patrick; Ossebaar, Sharyn; Bakker, Karel; Rozema, Patrick; de Baar, Hein J. W.
2017-05-01
The Western Antarctic Peninsula, one of the most productive regions of the Southern Ocean, is currently affected by the increasing of atmospheric and oceanic temperatures. For several decades, the Rothera Time Series (RaTS) site located in Ryder Bay has been monitored by the British Antarctic Survey and has shown long lasting phytoplankton summer blooms (over a month) that are likely driven by the length of the sea ice season. The dynamics of phytoplankton blooms in Ryder Bay may just as well be influenced by natural fertilization of iron and other bioactive trace metals due to the proximity of land, islands and glaciers. For the first time, temporal distributions in the surface layer (0-75 m depth) of six bioactive trace metals (dissolved: Fe, Mn, Zn, Cd, Cu and dissolved labile Co) have been investigated with high temporal and spatial resolution at the RaTS site during a total of 2 and 3.5 months respectively, over two consecutive summers. Most of the studied trace elements showed wide ranges of concentrations and this dynamics appears to be driven by phytoplankton uptake, remineralization and occasional vertical mixing associated with storm episodes. The biological uptake of DMn, DZn, DCd, DCoL and DCu was proportional to uptake of phosphate and silicate, which was associated with weak to strong linear relationships depending on which phytoplankton bloom events was considered. This further suggests that the surface water distributions of these studied bio-active trace metals were mainly driven by biological uptake and remineralization during austral spring and summer in Ryder Bay. Even though DFe did not show any strong relationship with phosphate, DFe decreasing concentrations during each bloom event suggest that Fe is a key essential element for phytoplankton in the area of study. The consistency of trace metals/nutrient ratios during two consecutive summers indicates that over-winter scavenging removal was slow relative to mixing. The increase of DCd/P and DCoL/P drawdown ratios during the two consecutive blooms monitored during the second season could reflect the substitution of DZn by trace metals DCd and DCoL due to lowered DZn concentrations after the first bloom. Relationships of trace elements versus silicate appear to be dominated by diatoms abundances which tend to vary both at the season and bloom time scale. Simultaneous short-term events of depletions of both nutrients and bio-active trace metals might induce stress in the growth of the phytoplankton assemblage.
Bioaccumulation of trace metals in octocorals depends on age and tissue compartmentalization
Hwang, Jiang-Shiou; Huang, Ke Li; Huang, Mu-Yeh; Liu, Xue-Jun; Khim, Jong Seong; Wong, Chong Kim
2018-01-01
Trace metal dynamics have not been studied with respect to growth increments in octocorals. It is particularly unknown whether ontogenetic compartmentalization of trace metal accumulation is species-specific. We studied here for the first time the intracolonial distribution and concentrations of 18 trace metals in the octocorals Subergorgia suberosa, Echinogorgia complexa and E. reticulata that were retrieved from the northern coast of Taiwan. Levels of trace metals were considerably elevated in corals collected at these particular coral habitats as a result of diverse anthropogenic inputs. There was a significant difference in the concentration of metals among octocorals except for Sn. Both species of Echinogorgia contained significantly higher concentrations of Cu, Zn and Al than Subergorgia suberosa. We used for the first time exponential growth curves that describe an age-specific relationship of octocoral trace metal concentrations of Cu, Zn, Cd, Cr and Pb where the distance from the grip point was reflecting younger age as linear regressions. The larger colony (C7) had a lower accumulation rate constant than the smaller one (C6) for Cu, Zn, Cd, Cr and Pb, while other trace metals showed an opposite trend. The Cu concentration declined exponentially from the grip point, whereas the concentrations of Zn, Cd, Cr and Pb increased exponentially. In S. suberosa and E. reticulata, Zn occurred primarily in coenosarc tissues and Zn concentrations increased with distance from the grip point in both skeletal and coenosarc tissues. Metals which appeared at high concentrations (e.g. Ca, Zn and Fe) generally tended to accumulate in the outer coenosarc tissues, while metals with low concentrations (e.g. V) tended to accumulate in the soft tissues of the inner skeleton. PMID:29684058
Góral, Marta; Szefer, Piotr; Ciesielski, Tomasz; Warzocha, Jan
2009-10-01
The concentrations of Ag, Cd, Co, Cr, Cu, Fe, Ni, Pb, Mn and Zn in Saduria entomon and adjacent bottom sediments from the southern Baltic were determined by FAAS. In order to estimate the strength of correlations between accumulated elements in these crustaceans and surficial sediment, bioaccumulation factors (BAFs) were calculated. The results of factor analysis (FA) and the Kruskal-Wallis analysis of variance (ANOVA) clearly indicate geographical differences between the concentrations of these elements. Cd, Co, Fe, Ni, Pb and Zn levels were higher in S. entomon from the Gulf of Gdańsk, whereas Cr and Mn levels were higher in the crustaceans inhabiting open Baltic waters. The concentrations of Ag and Cu were comparable in both regions. There was a tendency for metal concentrations to distinguish organisms inhabiting the muddy bottom from those living in sandy sediments. The granulometric composition of the sediment appears to influence trace metal bioavailability. The results show that S. entomon could be a valuable sentinel organism for biomonitoring heavy metal contamination in the southern Baltic.
Late Reduction Textures in Almahata Sitta Ureilite
NASA Technical Reports Server (NTRS)
Herrin, J. S.; Le, L.; Zolensky, M. E.; Ito, M.; Jenniskens, P.; Shaddad, M. H.
2009-01-01
The Almahata Sitta ureilite, derived from asteroid 2008 TC3, consists of many individual fragments recovered from the Nubian dessert strewn field [1]. Like most ureilites, it contains abundant carbon and exhibits examples of disequilibrium textures that record a late reduction event accompanied by rapid cooling (tens of degC/h) from high temperatures (1150-1300 C). Variations in Fe/Mg of silicate minerals are accompanied by variations in Fe/Mn, indicating loss of Fe into metal [2]. In coarser-grained fragments of Almahata Sitta, olivine exhibits irregular high mg# rims in contact with networks of interstitial metal 5- 20 microns in typical thickness. This is a common ureilite texture thought to be driven by the reaction of graphite to a CO gas phase and the concurrent reduction of FeO in olivine to Fe metal, with excess silica going primarily into pyroxene (2MgFeSiO4 + C approaches MgSiO4 + MgSiO3 + 2Fe + CO) [3, see also 4,5,6]. Other fragments of Almahata Sitta exhibit anomalous textures such as fine grain size, high porosity, and abundant graphite. Within these fragments pyroxene locally exhibits high-mg# rims in contact with metal and a discreet silica phase, suggesting that the reduction mechanism MgFeSi2O6 + C approaches MgSiO3 + Fe + SiO2 + CO. Metals in Almahata Sitta are particularly unaltered in comparison to ureilite finds. Variations in minor and trace element composition of this metal might partly result from localized dilution as iron is supplied by reduction of silicates.
PIXE as a complement to ICP-OES trace metal analysis in Sudanese medicinal plants.
Mubark Ebrahim, Ammar; Etayeb, M A; Khalid, H; Noun, Manale; Roumie, M; Michalke, B
2014-08-01
This paper compares trace element concentrations (Ca, K, Sr, Fe, Mn, Zn, Ni, Cu, Co and Cr) in 27 Sudanese medical plants determined in parallel by PIXE and ICP-OES to get information on which technique is preferable at different matrices and element concentrations. PIXE correlates well to ICP-OES for Sr, Mn, Ca, K, Zn and Fe determinations. ICP-OES seems to be the superior technique over PIXE when measuring low concentrated elements (chromium, cobalt, nickel and copper) in the medicinal plants. Copyright © 2014 Elsevier Ltd. All rights reserved.
TRACE METAL CONTENT (Cu, Zn, Mn AND Fe) IN URTICA DIOICA L. AND PLANTAGO MAJOR L.
Krolak, Elzbieta; Raczuk, Jolanta; Borkowska, Lidia
2016-11-01
The aim of the study was to compare the contents of Cu, Zn, Mn and Fe in the washed and unwashed leaves and roots of two plant species: Urica dioica L. and Plantago major L., used in herbal medicine. These two herb species occur in the same environmental habitats, yet their morphological structure is different. The soil and plant samples for analyses were collected from an uncontaminated area in Eastern Poland. In each habitat location, the samples were taken from sandy soils with slightly acidic and neutral pH values. The obtained results showed that U. dioica and P. major accumulated similar amounts of trace metals, such as: Cu, Zn and Fe, in leaves, despite the differences in the morphological structure of their overground parts. The content of Mn in leaves U. dioica was about twice as much as in P. major. Also, no differences in the metal content were observed between washed and unwashed leaves of both species. However, in the same habitat conditions, a significantly higher content of Cu, Zn and Mn was found in the roots of P. major than U. dioica. The content of Fe in the roots was similar in both species. P. major and U. dioica may be a valuable source of microelements, if they are obtained from unpolluted habitats.
Trace element distributions in the water column near the Deepwater Horizon well blowout.
Joung, DongJoo; Shiller, Alan M
2013-03-05
To understand the impact of the Deepwater Horizon well blowout on dissolved trace element concentrations, samples were collected from areas around the oil rig explosion site during four cruises in early and late May 2010, October 2010, and October 2011. In surface waters, Ba, Fe, Cu, Ni, Mn, and Co were relatively well correlated with salinity during all cruises, suggesting mixing with river water was the main influence on metal distributions in these waters. However, in deep oil/gas plumes (1000-1400 m depth), modestly elevated concentrations of Co and Ba were observed in late May, compared with postblowout conditions. Analysis of the oil itself along with leaching experiments confirm the oil as the source of the Co, whereas increased Ba was likely due to drilling mud used in the top kill attempt. Deep plume dissolved Mn largely reflected natural benthic input, though some samples showed slight elevation probably associated with the top kill. Dissolved Fe concentrations were low and also appeared largely topographically controlled and reflective of benthic input. Estimates suggest that microbial Fe demand may have affected the Fe distribution but probably not to the extent of Fe becoming a growth-limiting factor. Experiments showed that the dispersant can have some limited impact on dissolved-particulate metal partitioning.
He, Mei; Ke, Cai-Huan; Wang, Wen-Xiong
2010-03-24
In current human health risk assessment, the maximum acceptable concentrations of contaminants in food are mostly based on the total concentrations. However, the total concentration of contaminants may not always reflect the available amount. Bioaccessibility determination is thus required to improve the risk assessment of contaminants. This study used an in vitro digestion model to assess the bioaccessibility of several trace elements (As, Cd, Cu, Fe, Se, and Zn) in the muscles of two farmed marine fish species (seabass Lateolabrax japonicus and red seabream Pagrosomus major ) of different body sizes. The total concentrations and subcellular distributions of these trace elements in fish muscles were also determined. Bioaccessibility of these trace elements was generally high (>45%), and the lowest bioaccessibility was observed for Fe. Cooking processes, including boiling, steaming, frying, and grilling, generally decreased the bioaccessibility of these trace elements, especially for Cu and Zn. The influences of frying and grilling were greater than those of boiling and steaming. The relationship of bioaccessibility and total concentration varied with the elements. A positive correlation was found for As and Cu and a negative correlation for Fe, whereas no correlation was found for Cd, Se, and Zn. A significant positive relationship was demonstrated between the bioaccessibility and the elemental partitioning in the heat stable protein fraction and in the trophically available fraction, and a negative correlation was observed between the bioaccessibility and the elemental partitioning in metal-rich granule fraction. Subcellular distribution may thus affect the bioaccessibility of metals and should be considered in the risk assessment for seafood safety.
NASA Astrophysics Data System (ADS)
Horstmann, Marian; Humayun, Munir; Harries, Dennis; Langenhorst, Falko; Chabot, Nancy L.; Bischoff, Addi; Zolensky, Michael E.
2013-05-01
Meteorite fusion crusts form during the passage of a meteoroid through the Earth's atmosphere and are highly oxidized intergrowths as documented by the presence of e.g., oxides. The porous and irregular fusion crust surrounding the Almahata Sitta sulfide-metal assemblage MS-166 was found highly enriched in wüstite (Fe1-xO). Frictional heating of the outer portions of the assemblage caused partial melting of predominantly the Fe-sulfide and minor amounts of the outer Ni-rich portions of the originally zoned metal in MS-166. Along with melting significant amounts of oxygen were incorporated into the molten fusion crust and mainly FeS was oxidized and desulfurized to form wüstite. Considerable amounts of FeS were lost due to ablation, whereas the cores of the large metal grains appear largely unmelted leaving behind metal grains and surrounding wüstite-rich material (matte). Metal grains along with the surrounding matte typically form an often highly porous framework of globules interconnected with the matte. Although textures and chemical composition suggest that melting of Fe,Ni metal occurred only partially (Ni-rich rims), there is a trace elemental imprint of siderophile element partitioning influenced by oxygen in the metallic melt as indicated by the behavior of W and Ga, the two elements significantly affected by oxygen in a metallic melt. It is remarkable that MS-166 survived the atmospheric passage as troilite inclusions in iron meteorites are preferentially destroyed.
NASA Astrophysics Data System (ADS)
Johansen, Anne M.; Hoffmann, Michael R.
2003-07-01
Ambient aerosol samples were collected over the Arabian Sea during the month of March of 1997, aboard the German R/V Sonne, as part of the German Joint Global Ocean Flux Study (JGOFS) project. This is the third study in a series of analogous measurements taken over the Arabian Sea during different seasons of the monsoon. Dichotomous high-volume collector samples were analyzed for ferrous iron immediately after collection, while trace metals, anions, and cations were determined upon return to the laboratory. The main crustal component was geochemically well represented by the average crustal composition and amounted to 5.94 ± 3.08 μg m-3. An additional crustal constituent of clay-like character, rich in water-soluble Ca and Mg, was seen in the fine fraction in air masses of Arabian origin. Total ferrous iron concentrations varied from 3.9 to 17.2 ng m-3 and averaged 9.8 ± 3.4 ng m-3, with 87.2% of Fe(II) present in the fine aerosol fraction. Fe(II) concentrations accounted for on average 1.3 ± 0.5% of the total Fe. While ferrous iron in the coarse fraction appeared to be correlated with the main crustal component, the fine Fe(II) fraction exhibited a more complex behavior. The anthropogenic contribution to the aerosol, as traced by Pb, Zn, and some anions and cations, was found to be considerably larger, especially during the first 10 days of this cruise, than in previously collected samples from the inter-monsoon and southwest monsoon of 1995.
NASA Astrophysics Data System (ADS)
Zhang, Li; Chang, Xijun; Li, Zhenhua; He, Qun
2010-02-01
A new selective solid-phase extractant using activated carbon as matrix which was purified, oxidized and modified by triethylenetetramine (AC-TETA) was prepared and characterized by FT-IR spectroscopy. At pH 4, quantitative extraction of trace Cr(III), Fe(III) and Pb(II) was obtained and determined by inductively coupled plasma optical emission spectrometry (ICP-OES). Complete elution of the adsorbed metal ions from the sorbent surface was carried out using 0.5 mol L -1 HCl. The maximum static adsorption capacity of sorbent for Cr(III), Fe(III) and Pb(II) was 34.6, 36.5 and 51.9 mg g -1, respectively. The time of quantitative adsorption was less than 2 min. The detection limits of the method was found to be 0.71, 0.35 and 0.45 ng mL -1 for Cr(III), Fe(III) and Pb(II), and the relative standard deviation (RSD) was 3.7%, 2.2% and 2.5%, respectively. Moreover, the method was free from interference with common coexiting ions. The method was also successfully applied to the preconcentration of trace Cr(III), Fe(III) and Pb(II) in synthetic samples and a real sample with satisfactory results.
Preparation and electrical properties of Cr 2O 3 gate insulator embedded with Fe dot
NASA Astrophysics Data System (ADS)
Yokota, Takeshi; Kuribayashi, Takaaki; Murata, Shotaro; Gomi, Manabu
2008-09-01
We investigated the electrical properties of a metal (Au)/insulator (magneto-electric materials: Cr 2O 3)/magnetic materials (Fe)/tunnel layer (Cr 2O 3)/semiconductor (Si) capacitor. This capacitor shows the typical capacitance-voltage ( C- V) properties of an Si-MIS capacitor with hysteresis depending on the Fe dispersibility which is determined by the deposition condition. The C- V curve of the only sample having a 0.5 nm Fe layer was seen to have a hysteresis window with a clockwise trace, indicating that electrons have been injected into the ultra-thin Fe layer. The samples having Fe layers of other thicknesses show a counterclockwise trace, which indicates that the film has mobile ionic charges due to the dispersed Fe. These results indicated that the charge-injection site, which works as a memory, in the Cr 2O 3 can be prepared by Fe insertion, which is deposited using well-controlled conditions. The results also revealed the possibility of an MIS capacitor containing both ferromagnetic materials and an ME insulating layer in a single system.
The geochemical cycling of trace elements in a biogenic meromictic lake
NASA Astrophysics Data System (ADS)
Balistrieri, Laurie S.; Murray, James W.; Paul, Barbara
1994-10-01
The geochemical processes affecting the behavior and speciation of As, Co, Cr, Cu, Fe, Mn, Mo, Ni, Pb, V, and Zn in Hall Lake, Washington, USA, are assessed by examining dissolved and acid soluble particulate profiles of the elements and utilizing results from thermodynamic calculations. The water column of this meromictic lake is highly stratified and contains distinctive oxic, suboxic, and anoxic layers. Changes in the redox state of the water column with depth affect the distribution of all the elements studied. Most noticeable are increases in dissolved Co, Cr, Fe, Mn, Ni, Pb, and Zn concentrations across the oxic-suboxic boundary, increases in dissolved As, Co, Cr, Fe, Mn, and V concentrations with depth in the anoxic layer, significant decreases in dissolved Cu, Ni, Pb, and Zn concentrations in the anoxic region below the sulfide maximum, and large increases in acid soluble particulate concentrations of As, Cr, Cu, Fe, Mo, Ni, Pb, V, and Zn in the anoxic zone below the sulfide maximum. Thermodynamic calculations for the anoxic region indicate that all redox sensitive elements exist in their reduced forms, the primary dissolved forms of Cu, Ni, Pb, and Zn are metal sulfide solution complexes, and solid sulfide phases of Cu, Fe, Mo, and Pb are supersaturated. Calculations using a vertical diffusion and reaction model indicate that the oxidation rate constant for Mn(II) in Hall Lake is estimated to be 0.006 d -1 and is at the lower end of the range of microbial oxidation rates observed in other natural systems. The main geochemical processes influencing the distribution and speciation of trace elements in Hall Lake appear to be transformations of dissolved elements between their oxidation states (As, Cr, Cu, Fe, Mn, V), cocycling of trace elements with Mn and Fe (As, Co, Cr, Cu, Mo, Ni, Pb, V, Zn), formation of soluble metal sulfide complexes (Co, Cu, Ni, Pb, Zn), sorption (As, Co, Cr, Ni, V), and precipitation (Cu, Fe, Mn, Mo, Pb, Zn).
The geochemical cycling of trace elements in a biogenic meromictic lake
Balistrieri, L.S.; Murray, J.W.; Paul, B.
1994-01-01
The geochemical processes affecting the behavior and speciation of As, Co, Cr, Cu, Fe, Mn, Mo, Ni, Pb, V, and Zn in Hall Lake, Washington, USA, are assessed by examining dissolved and acid soluble particulate profiles of the elements and utilizing results from thermodynamic calculations. The water column of this meromictic lake is highly stratified and contains distinctive oxic, suboxic, and anoxic layers. Changes in the redox state of the water column with depth affect the distribution of all the elements studied. Most noticeable are increases in dissolved Co, Cr, Fe, Mn, Ni, Pb, and Zn concentrations across the oxic-suboxic boundary, increases in dissolved As, Co, Cr, Fe, Mn, and V concentrations with depth in the anoxic layer, significant decreases in dissolved Cu, Ni, Pb, and Zn concentrations in the anoxic region below the sulfide maximum, and large increases in acid soluble particulate concentrations of As, Cr, Cu, Fe, Mo, Ni, Pb, V, and Zn in the anoxic zone below the sulfide maximum. Thermodynamic calculations for the anoxic region indicate that all redox sensitive elements exist in their reduced forms, the primary dissolved forms of Cu, Ni, Pb, and Zn are metal sulfide solution complexes, and solid sulfide phases of Cu, Fe, Mo, and Pb are supersaturated. Calculations using a vertical diffusion and reaction model indicate that the oxidation rate constant for Mn(II) in Hall Lake is estimated to be 0.006 d-1 and is at the lower end of the range of microbial oxidation rates observed in other natural systems. The main geochemical processes influencing the distribution and speciation of trace elements in Hall Lake appear to be transformations of dissolved elements between their oxidation states (As, Cr, Cu, Fe, Mn, V), cocycling of trace elements with Mn and Fe (As, Co, Cr, Cu, Mo, Ni, Pb, V, Zn), formation of soluble metal sulfide complexes (Co, Cu, Ni, Pb, Zn), sorption (As, Co, Cr, Ni, V), and precipitation (Cu, Fe, Mn, Mo, Pb, Zn). ?? 1994.
LA-ICP-MS Study of Trace Elements in the Chanuskij Metal
NASA Technical Reports Server (NTRS)
Petaev, Michail I.
2005-01-01
This progress report covers work done during the second year of the 3-year proposal. During this year we resolved many issues relevant to the analytical technique developed by us for measuring trace elements in meteoritic metals. This technique was used to measure concentrations of Fe, Ni, Co, Cr, Cu, Ga, Ge, As, Mo, Ru, Rh, Pd, Sb, W, Re, Os, Ir, Pt, and Au in eight large (120 - 160 microns) metal grains from both "igneous" and "metamorphic" lithologies of the Chanuskij silicate inclusions. The first application of OUT technique to metal grains from thin sections showed some limitations. Small thickness of metal grains in the thin section limited the signal to 3-4 time-slices instead of 10- 1 1 ones in polished sections of iron meteorites studied before.
Odiwe, Anthony I; Adesanwo, Adeyemi T J; Olowoyo, Joshua O; Raimi, Idris O
2014-04-01
The level of air pollution around the automobile mechanic workshops has been generally overlooked. This study, examined the level of trace metals in automobile mechanic workshops and the suitability of using transplanted lichen thalli of Lepraria incana for measuring air pollution in such areas. Samples of the lichen thalli were transplanted into seven different sites and were attached to the bark of trees at each site. The samples were harvested from the sites after 3-month exposure. Concentrations of Pb, Cu, Cd, Fe, Zn, and S content were determined using an atomic absorption spectrophotometer. Results showed that there was a significant difference in the trace metals concentrations across the sites (p < 0.05). The analyzed lichen samples showed a range of 91.26-119.35 ppm for Fe, 30.23-61.32 ppm for Zn, 1.25-2.45 ppm for Cu, 0.017-0.043 ppm for Cd, 0.018-0.051 ppm, and 0.37-0.42 ppm for S. From the study, sites 6 and 7 presented higher concentrations of Cd, Pb, and Zn than other sites. The enrichment factor calculated showed that Zn, Cd, and Pb were greatly enriched from the workshops. The trend in the concentration of these heavy metals suggests that activities in these workshops might become a major source of certain heavy metals in the environment and if the pollution activities persist, it might become worrisome over time.
NASA Astrophysics Data System (ADS)
Cole, Devon B.; Zhang, Shuang; Planavsky, Noah J.
2017-10-01
The enrichment and depletion of redox sensitive trace metals in marine sediments have been used extensively as paleoredox proxies. The trace metals in shale are comprised of both detrital (transported or particulate) and authigenic (precipitated, redox-driven) constituents, potentially complicating the use of this suite of proxies. Untangling the influence of these components is vital for the interpretation of enrichments, depletions, and isotopic signals of iron (Fe), chromium (Cr), uranium (U), and vanadium (V) observed in the rock record. Traditionally, a single crustal average is used as a cutoff for detrital input, and concentrations above or below this value are interpreted as redox derived authigenic enrichment or depletion, while authigenic isotopic signals are frequently corrected for an assumed detrital contribution. Building from an extensive study of soils across the continental United States - which upon transport will become marine sediments - and their elemental concentrations, we find large deviations from accepted crustal averages in redox-sensitive metals (Fe, Cr, U, V) compared to typical detrital tracers (Al, Ti, Sc, Th) and provide new estimates for detrital contributions to the ocean. The variability in these elemental ratios is present over large areas, comparable to the catchment-size of major rivers around the globe. This heterogeneity in detrital flux highlights the need for a reevaluation of how the detrital contribution is assessed in trace metal studies, and the use of confidence intervals rather than single average values, especially in local studies or in the case of small authigenic enrichments.
Can Biomass Burning Explain Isotopically Light Fe in Marine Aerosols?
NASA Astrophysics Data System (ADS)
Sherry, A. M.; Anbar, A. D.; Herckes, P.; Romaniello, S. J.
2016-02-01
Iron (Fe) is an important micronutrient that limits primary productivity in large parts of the ocean. In these regions, atmospheric aerosol deposition is an important source of Fe to the surface ocean and thus has a critical impact on ocean biogeochemistry. Fe-bearing aerosols originate from many sources with potentially distinct Fe isotopic compositions. Consequently, Fe isotopes may provide a new tool to trace the sources of aerosol Fe to the oceans. Mead et al. (2013) first discovered that Fe in the fine fraction of Bermuda aerosols is often isotopically lighter than Fe from known anthropogenic and crustal sources. 1 These authors suggested that this light isotopic signature was likely the result of biomass burning, since Fe in plants is the only known source of isotopically light Fe. More recently, Conway et al. found that Fe in the soluble fraction of aerosols collected during 2010-2011 North Atlantic GEOTRACES cruises also showed light isotope values, which they likewise attributed to biomass burning.2 These studies are further supported by new modeling work which suggests that biomass burning aerosols should contribute significant amounts of soluble Fe to tropical and southern oceans.3To test if biomass burning releases aerosols with a light Fe isotope composition, we are conducting lab-scale biomass burning experiments using natural samples of vegetation and leaf litter. Burn aerosols were collected on cellulose filters, then digested and analyzed for trace metal concentrations using inductively-coupled mass spectrometry (ICP-MS). Fe isotopes were determined by using multiple collector ICP-MS following separation and purification of Fe using anion exchange chromatography. We will discuss metal concentration and isotope data from these experiments with implications for the interpretation of Fe isotope signals in aerosol samples. 1Mead, C et al. GRL, 2013, 40, 5722-5727. 2 Conway, T et al. Goldschmidt Abs 2015 593. 3Ito, A. ES&T Lett, 2015, 2, 70-75.
Griffin, W.L.; Slack, J.F.; Ramsden, A.R.; Win, T.T.; Ryan, C.G.
1996-01-01
Trace element contents of tourmalines from massive sulfide deposits and tourmalinites have been determined in situ by proton microprobe; >390 analyses were acquired from 32 polished thin sections. Concentrations of trace elements in the tourmalines vary widely, from <40 to 3,770 ppm Mn, <4 to 1,800 ppm Ni, <2 to 1,430 ppm Cu, <9 to 4,160 ppm Zn, 3 to 305 ppm Ga, <6 to 1,345 ppm Sr, <10 to 745 ppm Sn, <49 to 510 ppm Ba, and <3 to 4,115 ppm Pb. Individual grains and growth zones are relatively homogeneous, suggesting that these trace elements are contained within the crystal structure of the tourmaline, and are not present in inclusions. The highest base metal contents are in ore-related tourmaline samples from Kidd Creek (Ontario), Broken Hill (Australia), and Sazare (Japan). Tourmaline data from these and many other massive sulfide deposits cluster by sample and display broadly linear trends on Zn vs. Fe plots, suggesting chemical control by temperature and hydrothermal and/or metamorphic fluid-mineral equilibria. Significant Ni occurs only in samples from the Kidd Creek Cu-Zn-Pb-Ag deposit, which is associated with a large footwall ultramafic body. An overall antithetic relationship between Zn and Ni probably reflects fluid source controls. Mn is correlated with Fe in tourmalines from barren associations, and possibly in some tourmalines associated with sulfide vein deposits. Sn increases systematically with Fe content irrespective of association; the highest values are found in schorls from granites. Other trace elements are generally uncorrelated with major element concentrations (e.g., Sr-Ca). Base metal proportions in the tourmalines show systematic patterns on ternary Cu-Pb-Zn diagrams that correlate well with the major commodity metals in the associated massive sulfide deposits. For example, data for tourmalines from Cu-Zn deposits (e.g., Ming mine, Newfoundland) fall mainly on the Cu-Zn join, whereas those from Pb-Zn deposits (e.g., Broken Hill, Australia) plot on the Pb-Zn join; no data fall on the Cu-Pb join, consistent with the lack of this metal association in massive sulfide deposits. The systematic relationship between base metal proportions in the tourmalines and the metallogeny of the host massive sulfide deposits indicates that the analyzed tourmalines retain a strong chemical signature of their original hydrothermal formation, in spite of variable metamorphic recrystallization. Such trace element patterns in massive sulfide tourmalines may be useful in mineral exploration, specifically for the evaluation of tourmaline concentrations in rocks, soils, and stream sediments.
Gilchrist, S.; Gates, A.; Szabo, Z.; Lamothe, P.J.
2009-01-01
A sulfur and trace element enriched U-Th-laced tailings pile at the abandoned Phillips Mine in Garrison, New York, releases acid mine drainage (AMD, generally pH < 3, minimum pH 1.78) into the first-order Copper Mine Brook (CMB) that drains into the Hudson River. The pyrrhotite-rich Phillips Mine is located in the Highlands region, a critical water source for the New York metro area. A conceptual model for derivation/dissolution, sequestration, transport and dilution of contaminants is proposed. The acidic water interacts with the tailings, leaching and dissolving the trace metals. AMD evaporation during dry periods concentrates solid phase trace metals and sulfate, forming melanterite (FeSO4.7H2O) on sulfide-rich tailings surfaces. Wet periods dissolve these concentrates/precipitates, releasing stored acidity and trace metals into the CMB. Sediments along CMB are enriched in iron hydroxides which act as sinks for metals, indicating progressive sequestration that correlates with dilution and sharp rise in pH when mine water mixes with tributaries. Seasonal variations in metal concentrations were partly attributable to dissolution of the efflorescent salts with their sorbed metals and additional metals from surging acidic seepage induced by precipitation.
Influence of life history and sex on metal accumulation in two beetle species (insecta: Coleoptera)
DOE Office of Scientific and Technical Information (OSTI.GOV)
Lindqvist, L.; Block, M.
1997-04-01
Insects are important components of most terrestrial environments owing to their great abundance, biomass and diversity. They also make up an important food resource for other animals. Consequently, in many food webs insects constitute important links in metal-transport chains between trophic levels. Therefore trace-metal concentrations in insects have an important influence on the trace-metal distribution in the biosphere. In various insects, Cd, Cu and Zn are usually accumulated to the extent that they reach levels above those of the food, whereas Fe is not. In response to metal pollution, accumulation of nonessential metals was found to increase markedly, whereas essentialmore » metals accumulated less owing to regulating mechanisms in the insects. In polluted environments, metal concentrations were found to be higher in predatory invertebrates than in phytophagous ones in studies where insects were analysed in broad categories such as families. However, no such trend was observed when species were treated separately. The pattern of metal accumulation can differ between species. This is true even for species utilizing the same food resource. For instance, concentrations of Cd, Cu and Fe differed between four species of sawflies feeding on pine needles from the same locality. It is therefore likely that insects with different food sources accumulate metals differently depending on the concentration and chemical form of the metals in the food. There have been few studies aimed at determining whether patterns of metal accumulation differ between males and females of the same species. In one such study on the sawfly Neodiprion sertifer concentrations of Cd, Cu and Fe tended to be higher in males than in females. However, this pattern was not found in two other sawfly species. Target organs for Cd were found to differ between males and females in the grasshopper Aiolopus thalassinus. The testis accumulated Cd to a higher degree than the ovaries.« less
Trace metals in the living and nonliving components of scleractinian corals.
Reichelt-Brushett, A J; McOrist, G
2003-12-01
Trace metals in coral tissue and skeleton have been investigated in various ways since the early seventies. More recently it has been suggested that the symbiotic zooxanthellae may play an important role in the accumulation and regulation of trace metals. Furthermore gamete development and mucus production may influence the metal accumulation and loss in corals. Many studies have attempted to use the annual growth bands in coral skeletons to investigate historical pollution events. However the relationship between the metal concentrations in the surrounding environment and the incorporation of this into coral skeleton is not well understood. This paper explains a method for investigating metal loads in coral tissue, zooxanthellae and skeleton. Furthermore, it presents new information suggesting that zooxanthellae accumulate most metals (Al, Fe, As, Mn, Ni, Cu, Zn, Cd, Pb) in greater concentrations than the coral tissue. Coral skeletons had consistently lower metal concentration than the zooxanthellae, tissue and gametes. The loss of zooxanthellae during stress events may have a significant contribution to the total metal loads in corals. The use of corals as biomonitors should carefully factor in zooxanthellae densities and gamete development before conclusions are drawn.
Dispersion model on PM₂.₅ fugitive dust and trace metals levels in Kuwait Governorates.
Bu-Olayan, A H; Thomas, B V
2012-03-01
Frequent dust storms and recent environmental changes were found to affect the human health especially in residents of arid countries. Investigations on the PM(2.5) fugitive dust in six Kuwait Governorate areas using dispersion Gaussian plume modeling revealed significant relationship between low rate of pollutant emission, low wind velocity, and stable weather conditions' matrix causing high rate of dust deposition in summer than in winter. The rate of dust deposition and trace metals levels in PM(2.5) were in the sequence of G-VI > G-I > G-II > G-V > G-III > G-IV. Trace metals were observed in the sequence of Al > Fe > Zn > Ni > Pb > Cd irrespective of the Governorate areas and the two seasons. The high rate of dust deposition and trace metals in PM(2.5) was reflected by the vast open area, wind velocity, and rapid industrialization besides natural and anthropogenic sources. A combination of air dispersion modeling and nephalometric and gravimetric studies of this kind not only determines the seasonal qualitative and quantitative analyses on the PM(2.5) dust deposition besides trace metals apportionment in six Kuwait Governorate areas, but also characterizes air pollution factors that could be used by environmentalist to deduce preventive measures.
Cu(2+) and Fe(2+) mediated photodegradation studies of soil-incorporated chlorpyrifos.
Rafique, Nazia; Tariq, Saadia R; Ahad, Karam; Taj, Touqeer
2016-03-01
The influences of Cu(2+) and Fe(2+) on the photodegradation of soil-incorporated chlorpyrifos were investigated in the present study. The soil samples spiked with chlorpyrifos and selected metal ions were irradiated with UV light for different intervals of time and analyzed by HPLC. The unsterile and sterile control soil samples amended with pesticides and selected metals were incubated in the dark at 25 °C for the same time intervals. The results of the study evidenced that photodegradation of chlorpyrifos followed the first-order kinetics. The dissipation t0.5 of chlorpyrifos was found to decrease from 41 to 20 days under UV irradiation. The rate of chlorpyrifos photodegradation was increased in the presence of both metals, i.e., Cu(2+) and Fe(2+). Thus, initially observed t0.5 of 19.8 days was decreased to 4.39 days in the case of Cu(+2) and 19.25 days for Fe(+2). Copper was found to increase the rate of photodegradation by 4.5 orders of magnitude while the microbial degradation of chlorpyrifos was increased only twofold. The microbial degradation of chlorpyrifos was only negligibly affected by Fe(2+) amendment. The studied trace metals also affected the abiotic degradation of the pesticide in the order Cu(2+) > Fe(2+).
NASA Astrophysics Data System (ADS)
Liu, Ruixia; Lead, Jamie R.; Zhang, Hao
2013-05-01
Cross flow ultrafiltration (CFUF) and diffusive gradients in thin films (DGT) with open pore gel (OP) and restricted pore gel (RP) were used to measure trace metal speciation in selected UK freshwaters. The proportions of metals present in particulate forms (>1 μm) varied widely between 40-85% Pb, 60-80% Al, 7-56% Mn, 10-49% Cu, 0-55% Zn, 20-38% Cr, 20-30% Fe, 6-25% Co, 5-22% Cd and <7% Ni. In the colloidal fraction (2 kDa-1 μm) values varied between 53-91% Pb, 33-55% Al, 21-55% Cu, 20-44% Fe, 34-36% Cr, 20-40% Cd, 7-28% Co and Ni, 2-32% Zn and <8% Mn. Wide variations were also observed in the ultrafiltered fraction (<2 kDa). These results indicated that colloids indeed influenced the occurrence and transport of Al, Fe, Cr, Co, Ni, Cu, Zn, Cr and Pb metals in rivers, while inorganic or organic colloids did not exert an important control on Mn transport in the selected freshwaters. Of total species, total labile metal measured by DGT-OP accounted for 1.4-50% for Al, Fe, Co, Ni, Cu, Cd and Pb in all selected waters. Of these metals total labile Pb concentration was the lowest with value less than 1.4% although this value slightly increased after deducting particulate fractions. In some waters, a majority of total Mn, Zn and Cr is DGT labile, in which the DGT labile Mn fraction accounted for 98-118% of the total dissolved phase. In most cases, the inorganic labile concentration measured by DGT-RP was lower than the total labile metal concentration. By the combination of CFUF and DGT techniques, the concentrations of total labile and inorganic labile metal species in CFUF-derived truly dissolved phase were measured in four water samples. 100% of ultrafiltered Mn species was found to be total DGT labile. The proportions of total labile metal species were lower than those of ultrafiltered fraction for Al, Fe, Co, Ni, Cu, Cd and Pb in all selected waters, and Cr and Zn in some cases, indicating a large amount of natural complexing ligands with smaller size for the metals to form kinetically inert species or thermodynamically stable complexes. Observed discrepancies in metal speciation between metals and within sampling sites were related to the differences in the characteristics of the metals and the nature of water sources.
Assessment of total soil and plant trace elements in rice-based production systems in NE Italy
NASA Astrophysics Data System (ADS)
Bini, Claudio; Nadimi-Goki, Mandana; Kato, Yoichi; Vianello, Gilmo; Vittori, Livia; Wahsha, Mohammad; Spiandorello, Massimo
2014-05-01
Macro- and micronutrients concentrations, and PTEs contents in soils and plants (rice) from the rice district in the Venetian territory (NE Italy) have been determined by ICP-MS spectrometry, with the following aims: - to determine the background levels of macro- and microelements in the study area; - to assess possible contamination of soils and plants; - to calculate the Translocation Factor (TF) of metals from soil to plant, and the possible hazard for human health. Four rice plots with different rotation systems were investigated from seedling time to harvesting; sampling of soils (0-30cm) and plants was carried out 4 times during growing season (three replicates). Rice plants were separated into roots, stems, leaves and grains, and then oven-dried. Chemical and physical analyses were carried out at the Soil Science Lab of the University of Bologna and Venice, respectively. The results obtained point to a land with moderate soil contamination by trace elements (namely Li, Sn, Tl, Sr, Ti, Fe). Heavy metal (Sb, As, Be, Cd, Co, Cr, Ni, Pb, Cu, V, Zn ) concentrations in soils are below the threshold indicated by the Italian legislation (DM 152/2006). Cd, Sn, and Ti contents in soils are positively correlated with soil pH, while As, Fe, Li, Ti, Tl and Zn are negatively correlated with organic matter content. With the exception of Strontium, soil metal contents are always correlated between variable couples. HMs in plants vary according to the sampling season, texture and moisture, and soil pH. Most non-essential trace elements are accumulated in rice roots and, only in cases of essential micronutrients, in leaves. Therefore, rice can be assumed as an accumulator plant of As, Pb, Cr, Ba, and Ti, whereas it is as an indicator plant for Cu, Fe, Ni, Mn and Zn. The results of multiple linear regression analysis showed that soil pH has a larger effect on Ba, Cr, Cu, Fe, Mn, Ni, Ti and Zn concentrations in grain than other soil parameters. The average translocation of metals from soil to root was found to be >1, irrespective of the essential/not essential function; conversely, only essential elements ((Cu, Fe, Mn, Zn) are translocated rather easily from roots to leaves (TF ≤1) via phloem (TF< <1), and very little translocated to grains (TF< <1). Therefore, it is suggested that rice could be useful in contaminated-sites restoration projects by the phytostabilization technique. Moreover, there is very limited hazard for human population consuming rice crops. Key Words: Macro- and micronutrients concentrations, heavy metals, trace elements, rice plant, Italy, accumulator plant, indicator plant * Corresponding author. Tel.: +39 3891356251 E-mail address: mandy.nadimi@gmail.com
Red sea corals as biomonitors of trace metal pollution.
Hanna, R G; Muir, G L
1990-05-01
Red Sea corals have been found to be biomonitors of trace metal pollution. A comparative study was undertaken on three species from a polluted area near a desalination plant at Jeddah (Saudi Arabia) and from an unpolluted area. The results show that corals take-up trace elements from their aquatic environment and thereby act to record changes in the composition of that environment. Variations in the composition of skeletons and soft tissues of corals have been correlated with changes in sea water composition. Three coral species, Porites lutea, Goniastrea retiformis and Pocillopora verrucosa have been analysed for Hg, Cu, Zn, Pb, Mn, Fe, Ni, Cd, V, Al, Cr, Mg, B, Ca, and Sr in both skeletal and soft tissues. Results show that corals in the polluted areas have significantly higher concentrations of trace elements compared to that of corals from unpolluted areas.
Yang, Jie; Teng, Yanguo; Song, Liuting; Zuo, Rui
2016-01-01
Road and foliar dust samples from four land-use districts of Panzhihua City, a famous V-Ti magnetite production area of China, were collected to investigate the sources and distribution characteristics of 9 heavy metals (V, Pb, Cd, Cu, Zn, Ni, Cr, Fe, and Mn). The results suggest that foliar samples had smaller particle size and higher heavy metal contents than road dusts. The contamination assessments of heavy metals were as follows: Pb and V (significant enrichment) > Zn, Ni, Cr, Fe, and Mn (moderate enrichment) > Cd and Ni (minimal enrichment). Statistical analyses showed Pb, as the primary pollution element, originated from waste incineration and lead-fuel combustion. The sources of Zn, Ni, Cr, Fe, V, and Mn were fugitive dust and traffic activities. Potential origins of Cu were corrosion of alloys used in vehicle components, vehicle covers, or other metallic surfaces and materials. The sources of Cd were different from any other heavy metals. Traffic and industrial activities were the main anthropogenic origins of heavy metals in dusts of Panzhihua, and more attention should be paid to heavy metal pollution in agricultural area. PMID:27992518
Yang, Jie; Teng, Yanguo; Song, Liuting; Zuo, Rui
2016-01-01
Road and foliar dust samples from four land-use districts of Panzhihua City, a famous V-Ti magnetite production area of China, were collected to investigate the sources and distribution characteristics of 9 heavy metals (V, Pb, Cd, Cu, Zn, Ni, Cr, Fe, and Mn). The results suggest that foliar samples had smaller particle size and higher heavy metal contents than road dusts. The contamination assessments of heavy metals were as follows: Pb and V (significant enrichment) > Zn, Ni, Cr, Fe, and Mn (moderate enrichment) > Cd and Ni (minimal enrichment). Statistical analyses showed Pb, as the primary pollution element, originated from waste incineration and lead-fuel combustion. The sources of Zn, Ni, Cr, Fe, V, and Mn were fugitive dust and traffic activities. Potential origins of Cu were corrosion of alloys used in vehicle components, vehicle covers, or other metallic surfaces and materials. The sources of Cd were different from any other heavy metals. Traffic and industrial activities were the main anthropogenic origins of heavy metals in dusts of Panzhihua, and more attention should be paid to heavy metal pollution in agricultural area.
Rumisha, Cyrus; Mdegela, Robinson H; Kochzius, Marc; Leermakers, Martine; Elskens, Marc
2016-10-01
Mangroves ecosystems support livelihood and economic activities of coastal communities in the tropics and subtropics. Previous reports have documented the inefficiency of waste treatment facilities in Tanzania to contain trace metals. Therefore, the rapidly expanding coastal population and industrial sector is likely to threaten mangrove ecosystems with metal pollution. This study analysed trace metals in 60 sediment samples and 160 giant tiger prawns from the Tanzanian coast in order to document the distribution of trace metals and to establish if measured levels present a threat to mangrove fauna and are of public health importance. High levels of Cr, Co, Cu, Fe, Mn, Ni, and V was observed in mangroves of river Pangani, Wami, and Rufiji. Multivariate analysis showed that they originate mainly from weathering and erosion in the river catchments. Extreme enrichment of Cd was observed in a mangrove affected by municipal sewage. The distribution of Hg, Pb, and Zn was related with urbanisation and industrial activities along the coast. The metal pollution index was high at Pangani, Saadani, and Rufiji, suggesting that these estuarine mangroves are also affected by human activities in the catchment. Moderate to considerable ecological risks were observed in all sampled mangroves, except for Kilwa Masoko. It was revealed that As, Cd, and Hg present moderate risks to fauna. High levels of Cu, Fe and Zn were observed in prawns but the level of the non-essential Cd, Hg, and Pb did not exceed the maximum allowed levels for human consumption. However, based on the trends of fish consumption in the country, weekly intake of Hg is likely to exceed provisional tolerable weekly intake level, especially in fishing communities. This calls for measures to control Hg emissions and to strengthen sewage and waste treatment in coastal cities and urban centres in the basin of major rivers. Copyright © 2016 Elsevier Inc. All rights reserved.
NASA Astrophysics Data System (ADS)
Vidal-Durà, Andrea; Burke, Ian T.; Stewart, Douglas I.; Mortimer, Robert J. G.
2018-07-01
Estuarine environments are considered to be nutrient buffer systems as they regulate the delivery of nutrients from rivers to the ocean. In the Humber Estuary (UK) seawater and freshwater mixing during tidal cycles leads to the mobilisation of oxic surface sediments (0-1 cm). However, less frequent seasonal events can also mobilise anoxic subsurface (5-10 cm) sediments, which may have further implications for the estuarine geochemistry. A series of batch experiments were carried out on surface and subsurface sediments taken from along the salinity gradient of the Humber Estuary. The aim was to investigate the geochemical processes driving major element (N, Fe, S, and Mn) redox cycling and trace metal behaviour during simulated resuspension events. The magnitude of major nutrient and metal release was significantly greater during the resuspension of outer estuarine sediments rather than from inner estuarine sediments. When comparing resuspension of surface versus subsurface sediment, only the outer estuary experiments showed significant differences in major nutrient behaviour with sediment depth. In general, any ammonium, manganese and trace metals (Cu and Zn) released during the resuspension experiments were rapidly removed from solution as new sorption sites (i.e. Fe/Mn oxyhydroxides) formed. Therefore Humber estuary sediments showed a scavenging capacity for these dissolved species and hence may act as an ultimate sink for these elements. Due to the larger aerial extent of the outer estuary intertidal mudflats in comparison with the inner estuary area, the mobilisation of the outer estuary sediments (more reducing and richer in sulphides and iron) may have a greater impact on the transport and cycling of nutrients and trace metals. Climate change-associated sea level rise combined with an increasing frequency of major storm events in temperate zones, which are more likely to mobilise deeper sediment regions, will impact the nutrient and metal inputs to the coastal waters, and therefore enhance the likelihood of eutrophication in this environment.
Pekey, Hakan; Karakaş, Duran; Bakoğlu, Mithat
2004-11-01
Surface water samples were collected from ten previously selected sites of the polluted Dil Deresi stream, during two field surveys, December 2001 and April 2002. All samples were analyzed using ICP-AES, and the concentrations of trace metals (Al, As, Ba, Cd, Co, Cr, Cu, Fe, Pb, Sn and Zn) were determined. The results were compared with national and international water quality guidelines, as well as literature values reported for similar rivers. Factor analysis (FA) and a factor analysis-multiple regression (FA-MR) model were used for source apportionment and estimation of contributions from identified sources to the concentration of each parameter. By a varimax rotated factor analysis, four source types were identified as the paint industry; sewage, crustal and road traffic runoff for trace metals, explaining about 83% of the total variance. FA-MR results showed that predicted concentrations were calculated with uncertainties lower than 15%.
Adsorption of humic acids and trace metals in natural waters
NASA Technical Reports Server (NTRS)
Leung, W. H.
1982-01-01
Studies concerning the interactions between suspended hydrous iron oxide and dissolved humic acids and trace metals are reported. As a major component of dissolved organic matters and its readiness for adsorption at the solid/water interface, humic acids may play a very important role in the organometallic geochemistry of suspended sediments and in determining the fate and distribution of trace metals, pesticides and anions in natural water systems. Most of the solid phases in natural waters contain oxides and hydroxides. The most simple promising theory to describe the interactions of hydrous iron oxide interface is the surface complex formation model. In this model, the adsorptions of humic acids on hydrous iron oxide may be interpreted as complex formation of the organic bases (humic acid oxyanions) with surface Fe ions. Measurements on adsorptions were made in both fresh water and seawater. Attempts have been made to fit our data to Langmuir adsorption isotherm. Adsorption equilibrium constants were determined.
THE WEATHERING OF A SULFIDE OREBODY: SPECIATION AND FATE OF SOME POTENTIAL CONTAMINANTS
DOE Office of Scientific and Technical Information (OSTI.GOV)
Courtin-Nomade, Alexandra; Grosbois, Cecile; Marcus, Matthew A.
2010-07-16
Various potentially toxic trace elements such as As, Cu, Pb and Zn have been remobilized by the weathering of a sulfide orebody that was only partially mined at Leona Heights, California. As a result, this body has both natural and anthropogenically modified weathering profiles only 500 m apart. The orebody is located in a heavily urbanized area in suburban Oakland, and directly affects water quality in at least one stream by producing acidic conditions and relatively high concentrations of dissolved elements (e.g., {approx}500 mg/L Cu, {approx}3700 mg/L Zn). Micrometric-scale mineralogical investigations were performed on the authigenic metal-bearing phases (less thanmore » 10 {mu}m in size) using electron-probe micro-analysis (EPMA), micro-Raman, micro X-ray absorption spectroscopy (mXAS), scanning X-ray diffraction (mSXRD) and scanning X-ray fluorescence (mSXRF) mapping techniques. Those measurements were coupled with classical mineralogical laboratory techniques, X-ray diffraction (XRD) and scanning electron microscopy (SEM). Authigenic metal-bearing phases identified are mainly sulfates (jarosite, epsomite, schwertmannite), Fe (oxy-)hydroxides (goethite, hematite and poorly crystalline Fe products) and poorly crystalline Mn (hydr-)oxides. Sulfates and Fe (oxy-)hydroxides are the two main secondary products at both sites, whereas Mn (hydr-) oxides were only observed in the samples from the non-mining site. In these samples, the various trace elements show different affinities for Fe or Mn compounds. Lead is preferentially associated with Mn (hydr-)oxides and As with Fe (oxy-)hydroxides or sulfates. Copper association with Mn and Fe phases is questionable, and the results obtained rather indicate that Cu is present as individual Cu-rich grains (Cu hydroxides). Some ochreous precipitates were found at both sites and correspond to a mixture of schwertmannite, goethite and jarosite containing some potentially toxic trace elements such as Cu, Pb and Zn. According to the trace element distribution and relative abundance of the unweathered sulfides, this orebody still represents a significant reservoir of potential contaminants for the watershed, especially in the non-mining site, as a much greater proportion of sulfides is left to react and because of the lower porosity in this site.« less
The weathering of a sulfide orebody: Speciation and fate of some potential contaminants
Courtin-Nomade, A.; Grosbois, C.; Marcus, M.A.; Fakra, S.C.; Beny, J.-M.; Foster, A.L.
2009-01-01
Various potentially toxic trace elements such as As, Cu, Pb and Zn have been remobilized by the weathering of a sulfide orebody that was only partially mined at Leona Heights, California. As a result, this body has both natural and anthropogeni- cally modified weathering profiles only 500 m apart. The orebody is located in a heavily urbanized area in suburban Oakland, and directly affects water quality in at least one stream by producing acidic conditions and relatively high concentrations of dissolved elements (e.g., ??500 ??g/L Cu, ??3700 ??g/L Zn). Micrometric-scale mineralogical investigations were performed on the authigenic metal-bearing phases (less than 10 ??m in size) using electron-probe micro-analysis (EPMA), micro-Raman, micro X-ray absorption spectroscopy (??XAS), scanning X-ray diffraction ((??SXRD) and scanning X-ray fluorescence (??-SXRF) mapping techniques. Those measurements were coupled with classical mineralogical laboratory techniques, X-ray diffraction (XRD) and scanning electron microscopy (SEM). Authigenic metal-bearing phases identified are mainly sulfates (jarosite, epsomite, schwertmannite), Fe (oxy-)hydroxides (goethite, hematite and poorly crystalline Fe products) and poorly crystalline Mn (hydr-)oxides. Sulfates and Fe (oxy-)hydroxides are the two main secondary products at both sites, whereas Mn (hydr-) oxides were only observed in the samples from the non-mining site. In these samples, the various trace elements show different affinities for Fe or Mn compounds. Lead is preferentially associated with Mn (hydr-)oxides and As with Fe (oxy-)hydroxides or sulfates. Copper association with Mn and Fe phases is questionable, and the results obtained rather indicate that Cu is present as individual Cu-rich grains (Cu hydroxides). Some ochreous precipitates were found at both sites and correspond to a mixture of schwertmannite, goethite and jarosite containing some potentially toxic trace elements such as Cu, Pb and Zn. According to the trace element distribution and relative abundance of the unweathered sulfides, this orebody still represents a significant reservoir of potential contaminants for the watershed, especially at the non-mining site, as a much greater proportion of sulfides is left to react and because of the lower porosity at this site.
Odigie, Kingsley O; Flegal, A Russell
2014-01-01
The amounts of labile trace metals: [Co] (3 to 11 µg g-1), [Cu] (15 to 69 µg g-1), [Ni] (6 to 15 µg g-1), [Pb] (7 to 42 µg g-1), and [Zn] (65 to 500 µg g-1) in ash collected from the 2012 Williams Fire in Los Angeles, California attest to the role of fires in remobilizing industrial metals deposited in forests. These remobilized trace metals may be dispersed by winds, increasing human exposures, and they may be deposited in water bodies, increasing exposures in aquatic ecosystems. Correlations between the concentrations of these trace metals, normalized to Fe, in ash from the fire suggest that Co, Cu, and Ni in most of those samples were predominantly from natural sources, whereas Pb and Zn were enriched in some ash samples. The predominantly anthropogenic source of excess Pb in the ash was further demonstrated by its isotopic ratios (208Pb/207Pb: 206Pb/207Pb) that fell between those of natural Pb and leaded gasoline sold in California during the previous century. These analyses substantiate current human and environmental health concerns with the pyrogenic remobilization of toxic metals, which are compounded by projections of increases in the intensity and frequency of wildfires associated with climate change.
Braide, V B
1984-01-01
Studies on total hydroxyproline concentrations in urine of rats infused with toxic doses of CaEDTA at 6 mmol/kg per 24 hr for 48 hr or injected i.p. with the chelate at 4.8 mmol/kg/day for 10 days, indicate a two- to six-fold increase in urine excretion of the imino acid. This is due to increased degradation of collagen induced by CaEDTA. CaEDTA infusion was also shown to enhance urine excretion of some trace metals (Zn, Mn, Cu and Fe). Rats infused with CaEDTA for 36 hr showed a gradual fall in concentration of hydroxyproline in the urine, following cessation of chelate infusion. The decline in hydroxyproline concentrations was faster in rats receiving trace metal (Zn, Co, Mn or Ni) treatment during the post-CaEDTA infusion period; suggesting that the metals may affect collage, making the protein less susceptible to degradation in the body.
Nasrolahi, A; Smith, B D; Ehsanpour, M; Afkhami, M; Rainbow, P S
2014-10-01
The fouling barnacle Amphibalanus amphitrite is a cosmopolitan biomonitor of trace metal bioavailabilities, with an international comparative data set of body metal concentrations. Bioavailabilities of As, Cd, Cr, Cu, Fe, Mn, Pb, V and Zn to A. amphitrite were investigated at 19 sites along the Iranian coast of the understudied Persian Gulf. Commercial and fishing ports showed extremely high Cu bioavailabilities, associated with high Zn bioavailabilities, possibly from antifouling paints and procedures. V availability was raised at one port, perhaps associated with fuel leakage. Cd bioavailabilities were raised at sites near the Strait of Hormuz, perhaps affected by adjacent upwelling off Oman. The As data allow a reinterpretation of the typical range of accumulated As concentrations in A. amphitrite. The Persian Gulf data add a new region to the A. amphitrite database, confirming its importance in assessing the ecotoxicologically significant trace metal contamination of coastal waters across the world. Copyright © 2014 Elsevier Ltd. All rights reserved.
Bioavailable metals in tourist beaches of Richards Bay, Kwazulu-Natal, South Africa.
Vetrimurugan, E; Jonathan, M P; Roy, Priyadarsi D; Shruti, V C; Ndwandwe, O M
2016-04-15
Acid Leachable Trace Metal (ALTMs) concentrations in tourist beaches of Richards Bay, Kwazulu-Natal, South Africa were assessed. 53 surface sediment samples were collected from five different beaches (Kwambonambi Long Beach; Nhlabane Beach; Five Mile Beach; Alkanstrand Beach and Port Durnford Beach). The results of ALTMs (Fe, Mn, Cr, Cu, Ni, Co, Pb, Cd, Zn, As, Hg) suggest that they are enriched naturally and with some local industrial sources for (avg. in μgg(-1)) Fe (3530-7219), Mn (46-107.11), Cd (0.43-1.00) and Zn (48-103.98). Statistical results indicate that metal concentrations were from natural origin attributed to leaching, weathering process and industrial sources. Comparative studies of metal concentrations with sediment quality guidelines and ecotoxicological values indicate that there is no adverse biological effect. Enrichment factor and geoaccumulation indices results indicate moderate enhancement of Fe (Igeo class 1 in FMB), Cd (EF>50; Igeo classes 2-4) and Zn (Igeo classes 1 & 2). Copyright © 2016 Elsevier Ltd. All rights reserved.
Souza, A M; Salviano, A M; Melo, J F B; Felix, W P; Belém, C S; Ramos, P N
2016-01-01
In this study we determined the concentration of metals (Cd, Cr, Cu, Fe, Mn, Ni, Pb and Zn) in the water lower São Francisco River basin, to evaluate the influence of urbanization and industrialization on environmental changes in the water resource. All samples were analyzed using the IUPAC adapted method and processed in an atomic absorption spectrophotometer. The sampling stations located near the industrial areas were influenced by industrialization because they presented higher concentrations of Cd, Cr, Ni and Cu. The other sampled locations showed changes with regard the trace elements probably originating in the soil, like Fe, Zn and Pb. There was a gradual increase in the concentrations of metals, in general, in the period of highest rainfall of the hydrographic network. Overall, except for Zn and Mn, the trace elements exceeded the maximum allowed value established by national legislation (CONAMA). Lower São Francisco River basin has suffered interference from urbanization and industrialization, so awareness programs should be developed so as to control and lessen future problems.
Karlsson, Stefan; Sjöberg, Viktor; Ogar, Anna
2015-04-01
The use of nitrogen as plasma gas for microwave plasma atomic emission spectroscopy (MP AES) is an interesting development in analytical science since the running cost can be significantly reduced in comparison to the inductively coupled argon plasma. Here, we evaluate the performance of the Agilent 4100 MP AES instrument for the analysis of principal metals (Ca, K, Mg, and Na), lithogenic metals (Al, Fe, and Mn) and selected trace metals (As, Ba, Cd, Co, Cr, Cu, Mo, Ni, Pb, V, and Zn) in nitric acid plant digests. The digests were prepared by microwave-assisted dissolution of dry plant material from sunflower (Helianthus annuus) in concentrated nitric acid. Comparisons are made with analysis of the same solutions with ICP-MS (Agilent 7500cx) using the octopole reaction system (ORS) in the collision mode for As, Fe, and V. The limits of detection were usually in the low µg L(-1) range and all principal and lithogenic metals were successfully determined with the MP AES and provided almost identical results with the ICP-MS. The same applies for the selected trace metals except for As, Co and Mo where the concentrations were below the detection limit with the MP AES. For successful analysis we recommend that (i) only atom lines are used, (ii) ionization is minimized (e.g. addition of CsNO3) and (iii) the use of internal standards should be considered to resolve spectral interferences. Copyright © 2014 Elsevier B.V. All rights reserved.
Molybdenum drawdown during Cretaceous Oceanic Anoxic Event 2
NASA Astrophysics Data System (ADS)
Goldberg, Tatiana; Poulton, Simon W.; Wagner, Thomas; Kolonic, Sadat F.; Rehkämper, Mark
2016-04-01
During the Cretaceous greenhouse, episodes of widespread ocean deoxygenation were associated with globally occurring events of black shale deposition. Possibly the most pronounced of these oceanic anoxic events (OAE's) was the Cenomanian-Turonian OAE2 (∼94 Ma). However, although certain redox sensitive trace metals tend to be preferentially sequestered in sediments deposited under anoxic conditions, with Mo drawdown being specifically prone to euxinic settings, these elements are generally somewhat depleted in sediments deposited during OAE2. To understand the driving factors responsible for this depleted trace metal drawdown, we have studied a low latitude section from the proto-North Atlantic Ocean (Tarfaya S57), where existing biomarker and iron-sulphur data point to a dominantly euxinic water column, with periodic transitions to ferruginous (Fe-rich) water column conditions. We utilise a variety of redox proxies (Fe-speciation, redox sensitive trace metals and Mo isotopes), which, in combination, allows us to evaluate the detailed nature of ocean redox conditions and hence controls on trace metal drawdown. The results suggest that seawater δ98Mo values may have ranged between ∼0.6 and 1.1‰ during OAE2, likely connected to changes in the local Mo reservoir as a consequence of low and probably heterogeneous concentrations of Mo in the ocean. The very low Mo/TOC ratios at Tarfaya and elsewhere in the proto-North Atlantic may support a model in which deep-water circulation was partially restricted within and between the North Atlantic and other ocean basins. We propose that the combination of a low and possibly heterogeneous δ98Mo of seawater Mo, together with low Mo/TOC ratios, points to a large decrease in the global oceanic Mo reservoir during OAE2, reflecting a major global scale increase in Mo drawdown under persistent euxinic conditions.
A First Analysis of Metallome Biosignatures of Hyperthermophilic Archaea
Cameron, Vyllinniskii; House, Christopher H.; Brantley, Susan L.
2012-01-01
To date, no experimental data has been reported for the metallome of hyperthermophilic microorganisms although their metal requirements for growth are known to be unique. Here, experiments were conducted to determine (i) cellular trace metal concentrations of the hyperthermophilic Archaea Methanococcus jannaschii and Pyrococcus furiosus, and (ii) a first estimate of the metallome for these hyperthermophilic species via ICP-MS. The metal contents of these cells were compared to parallel experiments using the mesophilic bacterium Escherichia coli grown under aerobic and anaerobic conditions. Fe and Zn were typically the most abundant metals in cells. Metal concentrations for E. coli grown aerobically decreased in the order Fe > Zn > Cu > Mo > Ni > W > Co. In contrast, M. jannaschii and P. furiosus show almost the reverse pattern with elevated Ni, Co, and W concentrations. Of the three organisms, a biosignature is potentially demonstrated for the methanogen M. jannaschii that may, in part, be related to the metallome requirements of methanogenesis. The bioavailability of trace metals more than likely has varied through time. If hyperthermophiles are very ancient, then the trace metal patterns observed here may begin to provide some insights regarding Earth's earliest cells and in turn, early Earth chemistry. PMID:23243390
Gurumurthy, G P; Balakrishna, K; Tripti, M; Audry, Stéphane; Riotte, Jean; Braun, J J; Udaya Shankar, H N
2014-04-01
The study presents a 3-year time series data on dissolved trace elements and rare earth elements (REEs) in a monsoon-dominated river basin, the Nethravati River in tropical Southwestern India. The river basin lies on the metamorphic transition boundary which separates the Peninsular Gneiss and Southern Granulitic province belonging to Archean and Tertiary-Quaternary period (Western Dharwar Craton). The basin lithology is mainly composed of granite gneiss, charnockite and metasediment. This study highlights the importance of time series data for better estimation of metal fluxes and to understand the geochemical behaviour of metals in a river basin. The dissolved trace elements show seasonality in the river water metal concentrations forming two distinct groups of metals. First group is composed of heavy metals and minor elements that show higher concentrations during dry season and lesser concentrations during the monsoon season. Second group is composed of metals belonging to lanthanides and actinides with higher concentration in the monsoon and lower concentrations during the dry season. Although the metal concentration of both the groups appears to be controlled by the discharge, there are important biogeochemical processes affecting their concentration. This includes redox reactions (for Fe, Mn, As, Mo, Ba and Ce) and pH-mediated adsorption/desorption reactions (for Ni, Co, Cr, Cu and REEs). The abundance of Fe and Mn oxyhydroxides as a result of redox processes could be driving the geochemical redistribution of metals in the river water. There is a Ce anomaly (Ce/Ce*) at different time periods, both negative and positive, in case of dissolved phase, whereas there is positive anomaly in the particulate and bed sediments. The Ce anomaly correlates with the variations in the dissolved oxygen indicating the redistribution of Ce between particulate and dissolved phase under acidic to neutral pH and lower concentrations of dissolved organic carbon. Unlike other tropical and major world rivers, the effect of organic complexation on metal variability is negligible in the Nethravati River water.
NASA Astrophysics Data System (ADS)
Koukina, S. E.; Lobus, N. V.; Peresypkin, V. I.; Dara, O. M.; Smurov, A. V.
2017-11-01
Major (Si, Al, Fe, Ti, Mg, Ca, Na, K, S, P), minor (Mn) and trace (Li, V, Cr, Co, Ni, Cu, Zn, As, Sr, Zr, Mo, Cd, Ag, Sn, Sb, Cs, Ba, Hg, Pb, Bi and U) elements, their chemical forms and the mineral composition, organic matter (TOC) and carbonates (TIC) in surface sediments from the Cai River estuary and Nha Trang Bay were first determined along the salinity gradient. The abundance and ratio of major and trace elements in surface sediments are discussed in relation to the mineralogy, grain size, depositional conditions, reference background and SQG values. Most trace-element contents are at natural levels and are derived from the composition of rocks and soils in the watershed. A severe enrichment of Ag is most likely derived from metal-rich detrital heavy minerals such as Ag-sulfosalts. Along the salinity gradient, several zones of metal enrichment occur in surface sediments because of the geochemical fractionation of the riverine material. The parts of actually and potentially bioavailable forms (isolated by four single chemical reagent extractions) are most elevated for Mn and Pb (up to 36% and 32% of total content, respectively). The possible anthropogenic input of Pb in the region requires further study. Overall, the most bioavailable parts of trace elements are associated with easily soluble amorphous Fe and Mn oxyhydroxides. The sediments are primarily enriched with bioavailable metal forms in the riverine part of the estuary. Natural (such as turbidities) and human-generated (such as urban and industrial activities) pressures are shown to influence the abundance and speciation of potential contaminants and therefore change their bioavailability in this estuarine system.
Bibby, Rebecca L; Webster-Brown, Jenny G
2005-05-01
Suspended particulate matter (SPM) is an important transport agent for metal contaminants in streams, particularly during high flow periods such as storm events. For highly contaminated urban catchments in the greater Auckland (New Zealand) area, trace metal partitioning between the dissolved phase and SPM was determined, and SPM characterised in terms of its Si, Al, Fe, Mn, Zn, Cu, Pb, TOC, TON and PO(4) concentrations, as well as particle size, abundance, type and surface area. This data was compared to similar data from representative non-urban catchments in the Auckland region, the Kaipara River and Waikato River catchments, to identify any significant differences in the SPM and its potential trace metal adsorption capacity. Trace metal partitioning was assessed by way of a distribution coefficient: K(D)=[Me(SPM)]/[Me(DISS)]. Auckland urban SPM comprises quartz, feldspars and clay minerals, with Fe-oxides and minor Mn-oxides. No particles of anthropogenic origin, other than glass shards, were observed. No change in urban SPM particle size or SSA was observed with seasonal change in temperature, but the nature of the SPM was observed to change with flow regime. The abundance of finer particles, SSA and Al content of the SPM increased under moderate flow conditions; however, Si/Al ratios remained constant, confirming the importance of aluminosilicate detrital minerals in surface run-off. The SPM Fe content was observed to decrease with increased flow and was attributed to dilution of SPM Fe-oxide of groundwater origin. The Kaipara River SPM was found to be mineralogically, chemically and biologically similar to the urban SPM. However, major differences between urban catchment SPM and SPM from the much larger (non-urban) Waikato River were observed, and attributed to a higher abundance of diatoms. The Fe content of the Waikato River SPM was consistently lower (<5%), and the Si/Al ratio and Mn content was higher. Such differences observed between urban and non-urban SPM did not appear to affect the partitioning of Zn and Cu; however, Pb in the Kaipara and Waikato Rivers was found to be more associated with the dissolved phase. This is likely to reflect higher particulate Pb inputs to urban systems.
Dial, Angela R; Misra, Sambuddha; Landing, William M
2015-04-30
Accurate determination of trace metals has many applications in environmental and life sciences, such as constraining the cycling of essential micronutrients in biological production and employing trace metals as tracers for anthropogenic pollution. Analysis of elements such as Fe, As, Se, and Cd is challenged by the formation of polyatomic mass spectrometric interferences, which are overcome in this study. We utilized an Octopole Collision/Reaction Cell (CRC)-equipped Quadrupole-Inductively Coupled Plasma Mass Spectrometer for the rapid analysis of small volume samples (~250 μL) in a variety of matrices containing HNO3 and/or HCl. Efficient elimination of polyatomic interferences was demonstrated by the use of the CRC in Reaction Mode (RM; H2 gas) and in Collision-Reaction Mode (CRM; H2 and He gas), in addition to hot plasma (RF power 1500 W) and cool plasma (600 W) conditions. It was found that cool plasma conditions with RM achieved the greatest signal sensitivity while maintaining low detection limits (i.e. (56) Fe in 0.44 M HNO3 has a sensitivity of 160,000 counts per second (cps)-per-1 µg L(-1) and a limit of detection (LoD) of 0.86 ng L(-1) ). The average external precision was ≤ ~10% for minor (≤10 µg L(-1) ) elements measured in a 1:100 dilution of NIST 1643e and for iron in rainwater samples under all instrumental operating conditions. An improved method has been demonstrated for the rapid multi-element analysis of trace metals that are challenged by polyatomic mass spectrometric interferences, with a focus on (56) Fe, (75) As, (78) Se and (111) Cd. This method can contribute to aqueous environmental geochemistry and chemical oceanography, as well as other fields such as forensic chemistry, agriculture, food chemistry, and pharmaceutical sciences. Copyright © 2015 John Wiley & Sons, Ltd.
NASA Astrophysics Data System (ADS)
Dia, A.; Davranche, M.; Fakih, M.; Nowack, B.; Morin, G.; Gruau, G.
2009-04-01
Iron (III) oxides are ubiquitous components of soils, sediments, aquifers and geological materials. Trace metals associate with Fe (III) oxides as adsorbed or co-precipitated species and, consequently the biogeochemical cycles of Fe and trace metals are closely linked. Using a new monitoring tool recently developed, this study was dedicated to understand how do interplay biological and mineralogical (crystallographic and specific surface area) controls in the Fe oxyhydroxide reductive dissolution within soils and which can be the consequences on associated trace metal release. For this purpose, polymer slides covered by synthetic As-spiked ferrihydrite (As-Fh) or As-spiked lepidocrocite (As-Lp) were inserted into an organic-rich wetland soil in non conventional columns system under anaerobic conditions. This technique was developed to allow the insertion of slides into a structured soil without significant disturbance and to avoid the mechanical abrasion of oxides from slides that would occur in an equilibrium batch system under stirring. Slides were recovered after different periods of time to evaluate (i) the impact of (bio)reduction on both Fe-oxide dissolution and secondary mineral precipitation and, (ii) the subsequent effects on As mobility. XRF analyses of the slides were conducted before and after contact with the soil to determine the amount of Fe and associated As remaining on the slides. Fe(II), acetate, nitrate, sulphate and total metals of the soil solution was followed through time by ion chromatography and ICP-MS measurements. The important bacterial colonization and occurrence of biofilm evidenced by SEM analyses of the slides suggested the presence of biologically mediated processes. As previously shown elsewhere the kinetics of the suspected occurring bacterial reduction differ significantly from abiotic reduction data from literature. The important point is that conversely to what has been observed in published experimental data, the dissolution rates remained here fairly constant through time since the organic matter present in the interacting solution complexed the released Fe(II), which was therefore not able to accumulate onto the bacterial cell surfaces. The organic matter mediated complexation of Fe(II) prevented thus the progressive inhibition of the enzymatic reduction to occur as elsewhere evidenced with other experimental conditions. As expected, the reductive dissolution of the less crystallized ferrihydrite started quicker than that of lepidocrocite. The newly formed minerals were mostly composed of Fe-sulphides. Iron(II) complexation by organic molecules in solution likely prevented formation of secondary Fe(II, III)-rich minerals. The relative proportion of As(III) increased with time on the As-Fh slides, and was combined with a decrease of the Fe/As ratio, suggesting a partial adsorption of As(III) onto minerals. By contrast, for lepidocrocite, the Fe/As ratio increased, suggesting that As(III) was less readsorbed due the lower available site number and the deletion of As adsorption sites on the reduced lepidocrocite surface. Only a weak proportion of As(III) was sequestered by readsorption onto unreduced Fe-oxides and possibly on secondary Fe-sulphide minerals, especially when the iron oxide had a low surface area. Therefore, wetlands and their waterlogged soils could be a non negligible source of As within soils, migrating first through soil solutions and then to the whole hydrosystem.
Parker, S.R.; Gammons, C.H.; Jones, Clain A.; Nimick, D.A.
2007-01-01
Mining-impacted streams have been shown to undergo diel (24-h) fluctuations in concentrations of major and trace elements. Fisher Creek in south-central Montana, USA receives acid rock drainage (ARD) from natural and mining-related sources. A previous diel field study found substantial changes in dissolved metal concentrations at three sites with differing pH regimes during a 24-h period in August 2002. The current work discusses follow-up field sampling of Fisher Creek as well as field and laboratory experiments that examine in greater detail the underlying processes involved in the observed diel concentration changes. The field experiments employed in-stream chambers that were either transparent or opaque to light, filled with stream water and sediment (cobbles coated with hydrous Fe and Al oxides), and placed in the stream to maintain the same temperature. Three sets of laboratory experiments were performed: (1) equilibration of a Cu(II) and Zn(II) containing solution with Fisher Creek stream sediment at pH 6.9 and different temperatures; (2) titration of Fisher Creek water from pH 3.1 to 7 under four different isothermal conditions; and (3) analysis of the effects of temperature on the interaction of an Fe(II) containing solution with Fisher Creek stream sediment under non-oxidizing conditions. Results of these studies are consistent with a model in which Cu, Fe(II), and to a lesser extent Zn, are adsorbed or co-precipitated with hydrous Fe and Al oxides as the pH of Fisher Creek increases from 5.3 to 7.0. The extent of metal attenuation is strongly temperature-dependent, being more pronounced in warm vs. cold water. Furthermore, the sorption/co-precipitation process is shown to be irreversible; once the Cu, Zn, and Fe(II) are removed from solution in warm water, a decrease in temperature does not release the metals back to the water column. ?? 2006 Springer Science+Business Media B.V.
Exposure of women to trace elements through the skin by direct contact with underwear clothing.
Nguyen, Thao; Saleh, Mahmoud A
2017-01-02
Heavy metals pose a potential danger to human health when present in textile materials. In the present study, inductive coupled plasma mass spectrometry (ICPMS) was used to determine the concentrations and the identity of extractable inorganic elements from different brands of women undergarments. A total of 120 samples consisting of 63 cottons, 44 nylons and 13 polyesters manufactured in 14 different countries having different colors were analyzed for their extractable metals contents. Elements analyzed were Ag, Al, As, Ba, Be, Bi, Ca, Cd, Co, Cr, Cu, Fe, Hg, K, Li, Mg, Mn, Na, Ni, Pb, Sb, Se, Sr, Ti, V and Zn. Cotton undergarments were rich in Al, Fe and Zn, nylon undergarments had high levels of Cr, Cu and Al, while polyester fabrics contained higher levels of Ni and Fe compared to cotton or nylon. With respect to manufacturing countries, China, Egypt and India showed the highest concentrations of metals in all fabrics. With respect to the color, black garments were characteristic by high concentration of Fe, blue colors with Cu, brown garments with Fe and Cu, green garments with Cu and Fe, pink garments with Al, purple garments with Al and Cu and red garments with Cr, Zn and Al. The consumer should be made aware of the potential dangers of these metals in their clothing.
Particulate air pollution from bushfires: human exposure and possible health effects.
Karthikeyan, Sathrugnan; Balasubramanian, Rajasekhar; Iouri, Kostetski
2006-11-01
Toxicological studies have implicated trace metals adsorbed onto airborne particles as possible contributors to respiratory and/or cardiovascular inflammation. In particular, the water-soluble metal content is considered to be a harmful component of airborne particulate matter. In this work, the trace metal characteristics of airborne particulate matter, PM2.5, collected in Singapore from February to March 2005 were investigated with specific reference to their bioavailability. PM2.5 mass concentrations varied between 20.9 mug/m3 and 46.3 microg/m3 with an average mass of 32.8 microg/m3. During the sampling period, there were several bushfires in Singapore that contributed to sporadic increases in the particulate air pollution, accompanied by an acrid smell and asthma-related allergies. The aerosol samples were subjected to analysis of trace elements for determining their total concentrations as well as their water soluble fractions. Our results showed an increase in concentration of several water-soluble trace metals during bushfires compared to their urban background levels in Singapore. In order to measure the human exposure to particulate air pollution, the daily respiratory uptake (DRU) of several trace metals was calculated and compared between haze and nonhaze periods. The DRU values were significantly higher for several metals, including Zn, Cu, and Fe, during bushfires. Electron paramagnetic resonance (EPR) measurements showed that the particulate samples collected during bush fires generate more toxic hydroxyl radicals (OH.) than those in the background air, due to the presence of more soluble iron ions.
NASA Astrophysics Data System (ADS)
Hissler, C.; Stille, P.; Juilleret, J.; Iffly, J.; Perrone, T.; Morvan, G.
2013-12-01
Weathering mantels are widespread worldwide and include lateritic, sandy and kaolinite-rich saprolites and residuals of partially dissolved carbonate rocks. These old regolith systems have a complex history of formation and may present a polycyclic evolution due to successive geological and pedogenetic processes that affected the profile. Until now, only few studies highlighted the unusual content of associated trace elements in this type of weathering mantle. For instance, these enrichments can represent about five times the content of the underlying Bajocian to Oxfordian limestone/marl complexes, which have been relatively poorly studied compared to weathering mantle developed on magmatic bedrocks. Up to now, neither soil, nor saprolite formation has to our knowledge been geochemically elucidated. Therefore, the aim of this study was to examine more closely the soil forming dynamics and the relationship of the chemical soil composition to potential sources (saprolite, Bajocian silty marls and limestones, atmospheric particles deposition...). Of special interest has also been the origin of trace metals and the processes causing their enrichments. Especially Rare Earth Element (REE) distribution patterns and Sr, Nd and Pb isotope ratios are particularly well suited to identify trace element migration, to recognize origin and mixing processes and, in addition, to decipher possible anthropogenic and/or "natural" atmosphere-derived contributions to the soil. Moreover, leaching experiments shall help to identify mobile phases in the soil system. This may inform on the stability of trace elements and especially on their behaviour in these Fe-enriched carbonate systems. Trace metal migration and enrichments were studied on a cambisol developing on an underlying Jurassic limestone. The base is strongly enriched among others in rare earth elements (ΣREE: 2640ppm) or redox-sensitive elements such as Fe (44 wt.%), V (920ppm), Cr (700ppm), Zn (550ppm), As (260ppm), Co (45ppm) and Cd (2.4ppm). The underlying limestone and marl show, compared to average world carbonates, enrichments in the same elements and trace element distribution patterns similar to the soil suggesting their close genetic relationship. Pb, Sr and Nd isotope data allow to identify three principal components in the soil: a silicate-rich phase at close to the surface, a strongly trace metal enriched component at the bottom of the soil profile and an anthropogenic, atmosphere- derived component detected in the soil leachates. The isotopic mixing curves defined by the soil samples point to the close genetic connection between upper and lowermost soil horizons. The Nd isotopic composition of the leachates of all soil horizons are in contrast to the untreated soil and residual soil samples very homogeneous suggesting that the leachable phases of the upper and lower soil horizons are genetically connected. The downward migration of the trace metals is stopped at this soil level due to the presence of important secondary calcite precipitations, smectite and Fe-oxide accumulations. Mass balance calculations indicate that the enrichment process goes along with a volume increase relative to the bottom soil horizons.
Composition and genesis of ferromanganese deposits from the northern South China Sea
NASA Astrophysics Data System (ADS)
Zhong, Yi; Chen, Zhong; González, Francisco Javier; Hein, James R.; Zheng, Xufeng; Li, Gang; Luo, Yun; Mo, Aibin; Tian, Yuhang; Wang, Shuhong
2017-05-01
Marine ferromanganese (Fe-Mn) nodules and crusts are archives of past environmental conditions and potential mineral resources. Over the last 30 years, many have been discovered in the northern South China Sea (SCS). To determine the origin of the Fe-Mn deposits, a comprehensive laboratory analysis of physical properties, mineralogy and geochemistry was conducted on newly collected Fe-Mn nodule/crust samples. The results revealed that there are three types of Fe-Mn deposits: (1) Fe-rich nodules containing essentially goethite occur on the northeastern slope of the SCS, with high Fe, low Mn (Mn/Fe = 0.03) and low trace metals and rare earth elements concentrations; (2) Smooth Fe-Mn nodules and crusts composed of asbolane, todorokite and CFA occur along the northwestern marginal of the SCS that have similar Fe and Mn contents (Mn/Fe = 1.21), moderate trace metal enrichments, and a positive Ce anomaly; (3) Fe-Mn nodules and crusts composed of asbolane, todorokite and birnessite that occur in the central basin of the SCS have higher Mn and lower Fe contents (Mn/Fe = 1.45). This depositional pattern was associated with major changes in oceanographic conditions and tectonic regimes. The northeastern slope deposits occur in a contourite depositional system, are strongly enriched in Fe relative to Mn (average 38.7% and 0.96%, respectively), formed from the combination of hydrogenetic and diagenetic processes. We propose a new genetic model for Fe-Mn nodules, which formed through the oxidation of pyrite and pyrite-barite concretions that formed by rapid early diagenetic growth (average 3320 mm/Myr) on continental margins above the carbonate compensation depth, and dominated by hydrocarbon seep structures and strong erosive action of bottom currents along the northeastern slope. In contrast, the introduction of vigorous deep-water flow from the North Pacific promoted the slow growth (4-7 mm/Myr) of hydrogenetic Fe-Mn nodules and crusts along the northwestern margin. Finally, hydrogenetic growth of Fe-Mn nodules and crusts in the central basin may have been enhanced by volcanic processes. Our data provide new insights into the genesis and province characteristics of the Fe-Mn nodules and crusts of the northern SCS.
Juárez, Andrea; Arribére, María A; Arcagni, Marina; Williams, Natalia; Rizzo, Andrea; Ribeiro Guevara, Sergio
2016-09-01
Vegetation associated with lacustrine systems in Northern Patagonia was studied for heavy metal and trace element contents, regarding their elemental contribution to these aquatic ecosystems. The research focused on native species and exotic vascular plant Salix spp. potential for absorbing heavy metals and trace elements. The native species studied were riparian Amomyrtus luma, Austrocedrus chilensis, Chusquea culeou, Desfontainia fulgens, Escallonia rubra, Gaultheria mucronata, Lomatia hirsuta, Luma apiculata, Maytenus boaria, Myrceugenia exsucca, Nothofagus antarctica, Nothofagus dombeyi, Schinus patagonicus, and Weinmannia trichosperma, and macrophytes Hydrocotyle chamaemorus, Isöetes chubutiana, Galium sp., Myriophyllum quitense, Nitella sp. (algae), Potamogeton linguatus, Ranunculus sp., and Schoenoplectus californicus. Fresh leaves were analyzed as well as leaves decomposing within the aquatic bodies, collected from lakes Futalaufquen and Rivadavia (Los Alerces National Park), and lakes Moreno and Nahuel Huapi (Nahuel Huapi National Park). The elements studied were heavy metals Ag, As, Cd, Hg, and U, major elements Ca, K, and Fe, and trace elements Ba, Br, Co, Cr, Cs, Hf, Na, Rb, Se, Sr, and Zn. Geochemical tracers La and Sm were also determined to evaluate contamination of the biological tissues by geological particulate (sediment, soil, dust) and to implement concentration corrections.
NASA Astrophysics Data System (ADS)
Zhang, X.; McRose, D. L.; Darnajoux, R.; Bellenger, J. P.; Kraepiel, A. M. L.
2015-12-01
Biological N2 fixation, catalyzed by the metalloenzyme nitrogenase, is a critical process that makes life possible on Earth. Environmental N2 fixation has been automatically attributed to canonical Mo-based nitrogenases despite over two decades of knowledge that two other metalloenzyme forms of nitrogenase exist: those containing catalytic V or Fe-only. A key area of missing information is the contribution of the "alternative" V and Fe-only nitrogenases, as the interpretation of field data to construct budgets and assess N availability depends on the type of nitrogenase metalloenzyme used to fix N2. Additionally, substantial changes in metal speciation over geological time may have favored the use of different metalloenzymes, with implications for evolution of the biosphere. Despite the potential importance of alternative nitrogenases in modern and ancient N cycling, few methods can determine their contributions to environmental N2 fixation. Here, we present new isotopic methods to distinguish between the activities of Mo, V, and Fe-only nitrogenases. We show evidence for alternative N2 fixation in diverse environments (cyanolichens, microbial mats, sediments, leaf litter), thereby linking a key process in the nitrogen cycle to specific metalloenzyme forms of nitrogenase. The results invite a reexamination of the conditions under which the different nitrogenase metalloenzymes are active and may lead to new insights into the coupling of the cycles of nitrogen and trace metals.
Flow of essential elements in subcellular fractions during oxidative stress.
Lago, Larissa; Nunes, Emilene A; Vigato, Aryane A; Souza, Vanessa C O; Barbosa, Fernando; Sato, João R; Batista, Bruno L; Cerchiaro, Giselle
2017-02-01
Essential trace elements are commonly found in altered concentrations in the brains of patients with neurodegenerative diseases. Many studies in trace metal determination and quantification are conducted in tissue, cell culture or whole brain. In the present investigation, we determined by ICP-MS Fe, Cu, Zn, Ca, Se, Co, Cr, Mg, and Mn in organelles (mitochondria, nuclei) and whole motor neuron cell cultured in vitro. We performed experiments using two ways to access oxidative stress: cell treatments with H 2 O 2 or Aβ-42 peptide in its oligomeric form. Both treatments caused accumulation of markers of oxidative stress, such as oxidized proteins and lipids, and alteration in DNA. Regarding trace elements, cells treated with H 2 O 2 showed higher levels of Zn and lower levels of Ca in nuclei when compared to control cells with no oxidative treatments. On the other hand, cells treated with Aβ-42 peptide in its oligomeric form showed higher levels of Mg, Ca, Fe and Zn in nuclei when compared to control cells. These differences showed that metal flux in cell organelles during an intrinsic external oxidative condition (H 2 O 2 treatment) are different from an intrinsic external neurodegenerative treatment.
Shah, Mohammad Tahir; Khan, Sardar; Saddique, Umar; Gul, Nida; Khan, Muhammad Usman; Malik, Riffat Naseem; Farooq, Muhammad; Naz, Alia
2013-01-01
This study investigates the wild plant species for their phytoremediation potential of macro and trace metals (MTM). For this purpose, soil and wild plant species samples were collected along mafic and ultramafic terrain in the Jijal, Dubair, and Alpuri areas of Kohistan region, northern Pakistan. These samples were analyzed for the concentrations of MTM (Na, K, Ca, Mg, Fe, Mn, Pb, Zn, Cd, Cu, Cr, Ni, and Co) using atomic absorption spectrometer (AAS-PEA-700). Soil showed significant (P < .001) contamination level, while plants had greater variability in metal uptake from the contaminated sites. Plant species such as Selaginella jacquemontii, Rumex hastatus, and Plectranthus rugosus showed multifold enrichment factor (EF) of Fe, Mn, Cr, Ni, and Co as compared to background area. Results revealed that these wild plant species have the ability to uptake and accumulate higher metals concentration. Therefore, these plant species may be used for phytoremediation of metals contaminated soil. However, higher MTM concentrations in the wild plant species could cause environmental hazards in the study area, as selected metals (Fe, Mn, Cr, Ni, Co, and Pb) have toxicological concerns. PMID:24078907
A hydrogen-oxidizing, Fe(III)-reducing microorganism from the Great Bay estuary, New Hampshire
Caccavo, F.; Blakemore, R.P.; Lovley, D.R.
1992-01-01
A dissimilatory Fe(III)- and Mn(IV)-reducing bacterium was isolated from bottom sediments of the Great Bay estuary, New Hampshire. The isolate was a facultatively anaerobic gram-negative rod which did not appear to fit into any previously described genus. It was temporarily designated strain BrY. BrY grew anaerobically in a defined medium with hydrogen or lactate as the electron donor and Fe(III) as the electron acceptor. BrY required citrate, fumarate, or malate as a carbon source for growth on H2 and Fe(III). With Fe(III) as the sole electron acceptor, BrY metabolized hydrogen to a minimum threshold at least 60-fold lower than the threshold reported for pure cultures of sulfate reducers. This finding supports the hypothesis that when Fe(III) is available, Fe(III) reducers can outcompete sulfate reducers for electron donors. Lactate was incompletely oxidized to acetate and carbon dioxide with Fe(III) as the electron acceptor. Lactate oxidation was also coupled to the reduction of Mn(IV), U(VI), fumarate, thiosulfate, or trimethylamine n-oxide under anaerobic conditions. BrY provides a model for how enzymatic metal reduction by respiratory metal-reducing microorganisms has the potential to contribute to the mobilization of iron and trace metals and to the immobilization of uranium in sediments of Great Bay Estuary.
The Unique Biogeochemical Signature of the Marine Diazotroph Trichodesmium
Nuester, Jochen; Vogt, Stefan; Newville, Matthew; Kustka, Adam B.; Twining, Benjamin S.
2012-01-01
The elemental composition of phytoplankton can depart from canonical Redfield values under conditions of nutrient limitation or production (e.g., N fixation). Similarly, the trace metal metallome of phytoplankton may be expected to vary as a function of both ambient nutrient concentrations and the biochemical processes of the cell. Diazotrophs such as the colonial cyanobacteria Trichodesmium are likely to have unique metal signatures due to their cell physiology. We present metal (Fe, V, Zn, Ni, Mo, Mn, Cu, Cd) quotas for Trichodesmium collected from the Sargasso Sea which highlight the unique metallome of this organism. The element concentrations of bulk colonies and trichomes sections were analyzed by ICP-MS and synchrotron x-ray fluorescence, respectively. The cells were characterized by low P contents but enrichment in V, Fe, Mo, Ni, and Zn in comparison to other phytoplankton. Vanadium was the most abundant metal in Trichodesmium, and the V quota was up to fourfold higher than the corresponding Fe quota. The stoichiometry of 600C:101N:1P (mol mol−1) reflects P-limiting conditions. Iron and V were enriched in contiguous cells of 10 and 50% of Trichodesmium trichomes, respectively. The distribution of Ni differed from other elements, with the highest concentration in the transverse walls between attached cells. We hypothesize that the enrichments of V, Fe, Mo, and Ni are linked to the biochemical requirements for N fixation either directly through enrichment in the N-fixing enzyme nitrogenase or indirectly by the expression of enzymes responsible for the removal of reactive oxygen species. Unintentional uptake of V via P pathways may also be occurring. Overall, the cellular content of trace metals and macronutrients differs significantly from the (extended) Redfield ratio. The Trichodesmium metallome is an example of how physiology and environmental conditions can cause significant deviations from the idealized stoichiometry. PMID:22557997
Zhong, Cong; Yang, Zhongfang; Jiang, Wei; Hu, Baoqing; Hou, Qingye; Yu, Tao; Li, Jie
2016-12-15
Industrialization and urbanization have led to a deterioration in air quality and provoked some serious environmental concerns. Fifty-four samples of atmospheric deposition were collected from an emerging industrial area and analyzed to determine the concentrations of 11 trace elements (As, Cd, Cu, Fe, Hg, Mn, Mo, Pb, Se, S and Zn). Multivariate geostatistical analyses were conducted to determine the spatial distribution, possible sources and enrichment degrees of trace elements in atmospheric deposition. Results indicate that As, Fe and Mo mainly originated from soil, their natural parent materials, while the remaining trace elements were strongly influenced by anthropogenic or natural activities, such as coal combustion in coal-fired power plants (Pb, Se and S), manganese ore (Mn, Cd and Hg) and metal smelting (Cu and Zn). The results of ecological geochemical assessment indicate that Cd, Pb and Zn are the elements of priority concern, followed by Mn and Cu, and other heavy metals, which represent little threat to local environment. It was determine that the resuspension of soil particles impacted the behavior of heavy metals by 55.3%; the impact of the coal-fired power plants was 18.9%; and the contribution of the local manganese industry was 9.6%. The comparison of consequences from various statistical methods (principal component analysis (PCA), cluster analysis (CA), enrichment factor (EF) and absolute principle component score (APCS)-multiple linear regression (MLR)) confirmed the credibility of this research. Copyright © 2016 Elsevier B.V. All rights reserved.
Porcal, Petr; Koprivnjak, Jean-François; Molot, Lewis A; Dillon, Peter J
2009-09-01
Dissolved organic matter, measured as dissolved organic carbon (DOC), is an important component of aquatic ecosystems and of the global carbon cycle. It is known that changes in DOC quality and quantity are likely to have ecological repercussions. This review has four goals: (1) to discuss potential mechanisms responsible for recent changes in aquatic DOC concentrations; (2) to provide a comprehensive overview of the interactions between DOC, nutrients, and trace metals in mainly boreal environments; (3) to explore the impact of climate change on DOC and the subsequent effects on nutrients and trace metals; and (4) to explore the potential impact of DOC cycling on climate change. We review recent research on the mechanisms responsible for recent changes in aquatic DOC concentrations, DOC interactions with trace metals, N, and P, and on the possible impacts of climate change on DOC in mainly boreal lakes. We then speculate on how climate change may affect DOC export and in-lake processing and how these changes might alter nutrient and metal export and processing. Furthermore, the potential impacts of changing DOC cycling patterns on climate change are examined. It has been noted that DOC concentrations in lake and stream waters have increased during the last 30 years across much of Europe and North America. The potential reasons for this increase include increasing atmospheric CO(2) concentration, climate warming, continued N deposition, decreased sulfate deposition, and hydrological changes due to increased precipitation, droughts, and land use changes. Any change in DOC concentrations and properties in lakes and streams will also impact the acid-base chemistry of these waters and, presumably, the biological, chemical, and photochemical reactions taking place. For example, the interaction of trace metals with DOC may be significantly altered by climate change as organically complexed metals such as Cu, Fe, and Al are released during photo-oxidation of DOC. The production and loss of DOC as CO(2) from boreal lakes may also be affected by changing climate. Climate change is unlikely to be uniform spatially with some regions becoming wetter while others become drier. As a result, rates of change in DOC export and concentrations will vary regionally and the changes may be non-linear. Climate change models predict that higher temperatures are likely to occur over most of the boreal forests in North America, Europe, and Asia over the next century. Climate change is also expected to affect the severity and frequency of storm and drought events. Two general climate scenarios emerge with which to examine possible DOC trends: warmer and wetter or warmer and drier. Increasing temperature and hydrological changes (specifically, runoff) are likely to lead to changes in the quality and quantity of DOC export from terrestrial sources to rivers and lakes as well as changes in DOC processing rates in lakes. This will alter the quality and concentrations of DOC and its constituents as well as its interactions with trace metals and the availability of nutrients. In addition, export rates of nutrients and metals will also change in response to changing runoff. Processing of DOC within lakes may impact climate depending on the extent to which DOC is mineralized to dissolved inorganic carbon (DIC) and evaded to the atmosphere or settles as particulate organic carbon (POC) to bottom sediments and thereby remaining in the lake. The partitioning of DOC between sediments and the atmosphere is a function of pH. Decreased DOC concentrations may also limit the burial of sulfate, as FeS, in lake sediments, thereby contributing acidity to the water by increasing the formation of H(2)S. Under a warmer and drier scenario, if lake water levels fall, previously stored organic sediments may be exposed to greater aeration which would lead to greater CO(2) evasion to the atmosphere. The interaction of trace metals with DOC may be significantly altered by climate change. Iron enhances the formation of POC during irradiation of lake water with UV light and therefore may be an important pathway for transfer of allochthonous DOC to the sediments. Therefore, changing Fe/DOC ratios could affect POC formation rates. If climate change results in altered DOC chemistry (e.g., fewer and/or weaker binding sites) more trace metals could be present in their toxic and bioavailable forms. The availability of nutrients may be significantly altered by climate change. Decreased DOC concentrations in lakes may result in increased Fe colloid formation and co-incident loss of adsorbable P from the water column. Climate change expressed as changes in runoff and temperature will likely result in changes in aquatic DOC quality and concentration with concomitant effects on trace metals and nutrients. Changes in the quality and concentration of DOC have implications for acid-base chemistry and for the speciation and bioavailability of certain trace metals and nutrients. Moreover, changes in DOC, metals, and nutrients are likely to drive changes in rates of C evasion and storage in lake sediments. The key controls on allochthonous DOC quality, quantity, and catchment export in response to climate change are still not fully understood. More detailed knowledge of these processes is required so that changes in DOC and its interactions with nutrients and trace metals can be better predicted based on changes caused by changing climate. More studies are needed concerning the effects of trace metals on DOC, the effects of changing DOC quality and quantity on trace metals and nutrients, and how runoff and temperature-related changes in DOC export affect metal and nutrient export to rivers and lakes.
Glass, Jennifer B.; Orphan, Victoria J.
2011-01-01
Fluxes of greenhouse gases to the atmosphere are heavily influenced by microbiological activity. Microbial enzymes involved in the production and consumption of greenhouse gases often contain metal cofactors. While extensive research has examined the influence of Fe bioavailability on microbial CO2 cycling, fewer studies have explored metal requirements for microbial production and consumption of the second- and third-most abundant greenhouse gases, methane (CH4), and nitrous oxide (N2O). Here we review the current state of biochemical, physiological, and environmental research on transition metal requirements for microbial CH4 and N2O cycling. Methanogenic archaea require large amounts of Fe, Ni, and Co (and some Mo/W and Zn). Low bioavailability of Fe, Ni, and Co limits methanogenesis in pure and mixed cultures and environmental studies. Anaerobic methane oxidation by anaerobic methanotrophic archaea (ANME) likely occurs via reverse methanogenesis since ANME possess most of the enzymes in the methanogenic pathway. Aerobic CH4 oxidation uses Cu or Fe for the first step depending on Cu availability, and additional Fe, Cu, and Mo for later steps. N2O production via classical anaerobic denitrification is primarily Fe-based, whereas aerobic pathways (nitrifier denitrification and archaeal ammonia oxidation) require Cu in addition to, or possibly in place of, Fe. Genes encoding the Cu-containing N2O reductase, the only known enzyme capable of microbial N2O conversion to N2, have only been found in classical denitrifiers. Accumulation of N2O due to low Cu has been observed in pure cultures and a lake ecosystem, but not in marine systems. Future research is needed on metalloenzymes involved in the production of N2O by enrichment cultures of ammonia oxidizing archaea, biological mechanisms for scavenging scarce metals, and possible links between metal bioavailability and greenhouse gas fluxes in anaerobic environments where metals may be limiting due to sulfide-metal scavenging. PMID:22363333
Mendil, Durali; Demirci, Zafer; Tuzen, Mustafa; Soylak, Mustafa
2010-03-01
Fish species (Sarda sarda, Mulus barbatus ponticus, Trachurus trachurus and Merlangius merlangus) were collected from the Black sea, Turkey between 2008 and 2009 (spring, summer, autumn and winter). The samples were analyzed using flame and graphite furnace atomic absorption spectrometry after microwave digestion. The maximum metal concentrations were found to be as 25.5-41.4 microg/g (Fe), 17.8-25.7 microg/g (Zn), 0.28-0.64 microg/g (Pb), 0.64-0.99 microg/g (Cr), 1.3-3.6 microg/g (Mn), 1.4-1.9 microg/g (Cu), 0.18-0.35 microg/g (Cd) and 0.25-0.42 microg/g (Co) for fish species. The concentration of trace metals in samples is depended on fish species. Some species is accumulated trace metals at high ratio. Trace element levels in analyzed fish species were acceptable to human consumption at nutritional and toxic levels. The levels of lead and cadmium in fish samples were higher than the recommended legal limits. Copyright (c) 2009 Elsevier Ltd. All rights reserved.
Le Croizier, Gaël; Schaal, Gauthier; Gallon, Régis; Fall, Massal; Le Grand, Fabienne; Munaron, Jean-Marie; Rouget, Marie-Laure; Machu, Eric; Le Loc'h, François; Laë, Raymond; De Morais, Luis Tito
2016-12-15
The link between trophic ecology and metal accumulation in marine fish species was investigated through a multi-tracers approach combining fatty acid (FA) and stable isotope (SI) analyses on fish from two contrasted sites on the coast of Senegal, one subjected to anthropogenic metal effluents and another one less impacted. The concentrations of thirteen trace metal elements (As, Cd, Co, Cr, Cu, Fe, Li, Mn, Ni, Pb, Sn, U, and Zn) were measured in fish liver. Individuals from each site were classified into three distinct groups according to their liver FA and muscle SI compositions. Trace element concentrations were tested between groups revealing that bioaccumulation of several metals was clearly dependent on the trophic guild of fish. Furthermore, correlations between individual trophic markers and trace metals gave new insights into the determination of their origin. Fatty acids revealed relationships between the dietary regimes and metal accumulation that were not detected with stable isotopes, possibly due to the trace metal elements analysed in this study. In the region exposed to metallic inputs, the consumption of benthic preys was the main pathway for metal transfer to the fish community while in the unaffected one, pelagic preys represented the main source of metals. Within pelagic sources, metallic transfer to fish depended on phytoplankton taxa on which the food web was based, suggesting that microphytoplankton (i.e., diatoms and dinoflagellates) were a more important source of exposition than nano- and picoplankton. This study confirmed the influence of diet in the metal accumulation of marine fish communities, and proved that FAs are very useful and complementary tools to SIs to link metal accumulation in fish with their trophic ecology. Copyright © 2016 Elsevier B.V. All rights reserved.
Laser stereolithography by multilayer sintering of metal powders
NASA Astrophysics Data System (ADS)
Jendrzejewski, Rafal; Serbinski, W.; Sliwinski, Gerard
1997-10-01
Process parameters of the lser stereolithography by means of metal powder sintering are experimentally investigated for the bronze B10, Fe-Cr and Al-Ni alloys, pure Sn, and Cu. The multilaye structures ae prepared trace-on-trace by remelting of the previously deposited mela powder under the cw CO2 laser irradiation in an Ar flow environment. Severl trces of a hiehght of 0.1 - 0.9 mm connected via fusion zones are produced for each samle which results inan efficient formautlion f avolumetric structures of dimensins usfficient for microanalysis ndconsiderationof th emultlayer goemtry. For th beam intensities of about 105 W/cm2 and smaple feeding rates of 0.8 - 1.8 m/min th fusin zone thickness donot 4xceed several percent of th layer height. Rsutls indicate, that th epowderized Fe-Cr anAl-Ni alloys and also bronze B10 are well suited for a fast prorotyping due to th low porosity, homogeneous structure and good mechaniclpropetis acheivable.
Macro- and microelement distribution in organs of Glyceria maxima and biomonitoring applications.
Klink, Agnieszka; Stankiewicz, Andrzej; Wisłocka, Magdalena; Polechońska, Ludmiła
2014-07-01
The content of nutrients (N, P, K, Ca and Mg) and of trace metals (Fe, Cu, Mn, Zn, Pb, Cd, Co and Ni) in water, bottom sediments and various organs of Glyceria maxima from 19 study sites selected in the Jeziorka River was determined. In general, the concentrations of nutrients recorded in the plant material decreased in the following order: leaf>root>rhizome>stem, while the concentrations of the trace elements showed the following accumulation scheme: root>rhizome>leaf>stem. The bioaccumulation and transfer factors for nutrients were significantly higher than for trace metals. G. maxima from agricultural fields was characterised by the highest P and K concentrations in leaves, and plants from forested land contained high Zn and Ni amounts. However, the manna grass from small localities showed high accumulation of Ca, Mg and Mn. Positive significant correlations between Fe, Cu, Zn, Cd, Co and Ni concentrations in water or sediments and their concentrations in plant indicate that G. maxima may be employed as a biomonitor of trace element contamination. Moreover, a high degree of similarity was noted between self-organizing feature map (SOFM)-grouped sites of comparable quantities of elements in the water and sediments and sites where G. maxima had a corresponding content of the same elements in its leaves. Therefore, SOFM could be recommended in analysing ecological conditions of the environment from the perspective of nutrients and trace element content in different plant species and their surroundings.
Odigie, Kingsley O.; Flegal, A. Russell
2014-01-01
The amounts of labile trace metals: [Co] (3 to 11 µg g−1), [Cu] (15 to 69 µg g−1), [Ni] (6 to 15 µg g−1), [Pb] (7 to 42 µg g−1), and [Zn] (65 to 500 µg g−1) in ash collected from the 2012 Williams Fire in Los Angeles, California attest to the role of fires in remobilizing industrial metals deposited in forests. These remobilized trace metals may be dispersed by winds, increasing human exposures, and they may be deposited in water bodies, increasing exposures in aquatic ecosystems. Correlations between the concentrations of these trace metals, normalized to Fe, in ash from the fire suggest that Co, Cu, and Ni in most of those samples were predominantly from natural sources, whereas Pb and Zn were enriched in some ash samples. The predominantly anthropogenic source of excess Pb in the ash was further demonstrated by its isotopic ratios (208Pb/207Pb: 206Pb/207Pb) that fell between those of natural Pb and leaded gasoline sold in California during the previous century. These analyses substantiate current human and environmental health concerns with the pyrogenic remobilization of toxic metals, which are compounded by projections of increases in the intensity and frequency of wildfires associated with climate change. PMID:25259524
DOE Office of Scientific and Technical Information (OSTI.GOV)
Wood, K.
The principal study site is the landfill of the Niagara Mohawk Power Corp., Dunkirk, N.Y. Concentrations of dissolved metals are determined in the waters from the site and aquatic invertebrates from ponds and streams at the site are being identified and analyzed for trace metals. Elevated levels of Fe and Mn occur in the runoff from the site and in the aquatic invertebrates. The metals Cd, Zn, Cu, and Cr are found at low levels (ppB range) in the waters and in variable, generally low concentrations in the biota. Taxonomic study is focused primarily on the Chironomidae (10 general) andmore » Ephemeroptera (6 genera) with detailed studies in progress. The rate of leaching of metals from coal ash is also being studied in the laboratory by two methods. Sediments from Lake Erie at Dunkirk, N.Y., are being assessed for textural classification and composition. Attempts are being made to distinguish between coal wastes and other sediment in the silt and finer size range. The dump site is being evaluated for groundwater, surface water, and geological structure, so that trace element cycling can be evaluated.« less
Trace elements in agroecosystems and impacts on the environment.
He, Zhenli L; Yang, Xiaoe E; Stoffella, Peter J
2005-01-01
Trace elements mean elements present at low concentrations (mg kg-1 or less) in agroecosystems. Some trace elements, including copper (Cu), zinc (Zn), manganese (Mn), iron (Fe), molybdenum (Mo), and boron (B) are essential to plant growth and are called micronutrients. Except for B, these elements are also heavy metals, and are toxic to plants at high concentrations. Some trace elements, such as cobalt (Co) and selenium (Se), are not essential to plant growth but are required by animals and human beings. Other trace elements such as cadmium (Cd), lead (Pb), chromium (Cr), nickel (Ni), mercury (Hg), and arsenic (As) have toxic effects on living organisms and are often considered as contaminants. Trace elements in an agroecosystem are either inherited from soil parent materials or inputs through human activities. Soil contamination with heavy metals and toxic elements due to parent materials or point sources often occurs in a limited area and is easy to identify. Repeated use of metal-enriched chemicals, fertilizers, and organic amendments such as sewage sludge as well as wastewater may cause contamination at a large scale. A good example is the increased concentration of Cu and Zn in soils under long-term production of citrus and other fruit crops. Many chemical processes are involved in the transformation of trace elements in soils, but precipitation-dissolution, adsorption-desorption, and complexation are the most important processes controlling bioavailability and mobility of trace elements in soils. Both deficiency and toxicity of trace elements occur in agroecosystems. Application of trace elements in fertilizers is effective in correcting micronutrient deficiencies for crop production, whereas remediation of soils contaminated with metals is still costly and difficult although phytoremediation appears promising as a cost-effective approach. Soil microorganisms are the first living organisms subjected to the impacts of metal contamination. Being responsive and sensitive, changes in microbial biomass, activity, and community structure as a result of increased metal concentration in soil may be used as indicators of soil contamination or soil environmental quality. Future research needs to focus on the balance of trace elements in an agroecosystem, elaboration of soil chemical and biochemical parameters that can be used to diagnose soil contamination with or deficiency in trace elements, and quantification of trace metal transport from an agroecosystem to the environment.
NASA Astrophysics Data System (ADS)
Morales-Villafuerte, M.; Ortega-Osorio, A.; Wheat, G.; Seewald, J.
2004-12-01
Thirteen sediment cores were collected through out direct sampling with the MBARI/ ROV "Tiburon" in the southern trough of the Guaymas Basin in March 2003. Pore water samples from regular 2.5 cm intervals of sediment cores were extracted onboard by centrifugation. The supernatants were collected in clean polystyrene vials and stored at 4° C until analytical work on shore. Dissolved Fe, Mn, Cu, Pb, Zn and Ni concentrations in extracted fluid samples were analyzed by direct injection of atomic absorption spectrometry. Four zones in the hydrothermal field were classified according to their physical characteristics. A core located away from the influence of active vents was recovered as a background site. The second zone is characterized by low temperatures (4.2-80° C) and sediments saturated in hydrocarbons. Sulfides formation and higher temperatures (4-166° C) were observed in the third zone. Precipitation of carbonates on top of the sediment characterizes the fourth zone. Concentration of trace metals at the water-sediment interface appears to be the highest, probably due to metal precipitation from the hydrothermal plume, followed by diffusion into the pore water. A decrease in concentration is observed between 5-12 cm depth, suggesting that biological activity is consuming essential metals (zone of bioturbation). Metal concentrations in zones where sulfide phases are rich, exhibit smaller values in pore water (Fe=2.4-3.8 μ mol/kg, Cu=0.6-0.8 μ mol/kg, Pb=1.2-1.5 μ mol/kg, Zn=0.4-0.5 μ mol/kg and Ni= 3.4-4.4 μ mol/kg) relative to samples located at hydrocarbon sites (Fe= 2.7-11.4, Cu= 0.7-1.0 μ mol/kg, Pb= 1.2-2.2 μ mol/kg, Zn= 0.4-0.7 μ mol/kg and Ni= 3.4-5.2 μ mol/kg). At sulfide zones, pH and Eh conditions help to precipitate their stable sulfides as opposed to the hydrocarbon areas, where conditions are not favorable for sulfide formation due to the absence of H2S. In general, Fe concentrations in pore water are lower than that of Mn, very likely due to the easier precipitation and greater stability of FeS relative to MnS. As an attempt to reconstruct predominant species and their abundance in the system, aqueous chemical models were applied. The codes EQBRM and SUPCRT92 were run with total concentrations to calculate, concentrations, activity coefficients and thermodynamic properties of aqueous species. Experimental data such as total chloride, total sulfur and measured pH were used in the model. According to the prevailing conditions in the Guaymas Basin, all metals studied form chloride complexes. Iron, lead, and zinc exist mainly as hydroxy complexes, manganese as free ion and copper as CuHS. Speciation results are well supported by the Pearson's hard-soft rule which states that soft metal ion Cu++ bonds with soft bisulfide ligand, likewise, borderline metal ions as Fe2+, Mn2+, Pb2+ and Zn2+ bond with chloride, hydroxyl or water ligands. The results reported here provide a greater insight into the behavior of trace metals in pore waters of hydrothermal sediments.
Ivanina, Anna V; Beniash, Elia; Etzkorn, Markus; Meyers, Tiffany B; Ringwood, Amy H; Sokolova, Inna M
2013-09-15
Estuarine and coastal habitats experience large fluctuations of environmental factors such as temperature, salinity, partial pressure of CO2 ( [Formula: see text] ) and pH; they also serve as the natural sinks for trace metals. Benthic filter-feeding organisms such as bivalves are exposed to the elevated concentrations of metals in estuarine water and sediments that can strongly affect their physiology. The effects of metals on estuarine organisms may be exacerbated by other environmental factors. Thus, a decrease in pH caused by high [Formula: see text] (hypercapnia) can modulate the effects of trace metals by affecting metal bioavailability, accumulation or binding. To better understand the cellular mechanisms of interactions between [Formula: see text] and trace metals in marine bivalves, we exposed isolated mantle cells of the hard clams (Mercenaria mercenaria) to different levels of [Formula: see text] (0.05, 1.52 and 3.01 kPa) and two major trace metal pollutants - cadmium (Cd) and copper (Cu). Elevated [Formula: see text] resulted in a decrease in intracellular pH (pHi) of the isolated mantle cells from 7.8 to 7.4. Elevated [Formula: see text] significantly but differently affected the trace metal accumulation by the cells. Cd uptake was suppressed at elevated [Formula: see text] levels while Cu accumulation has greatly accelerated under hypercapnic conditions. Interestingly, at higher extracellular Cd levels, labile intracellular Cd(2+) concentration remained the same, while intracellular levels of free Zn(2+) increased suggesting that Cd(2+) substitutes bound Zn(2+) in these cells. In contrast, Cu exposure did not affect intracellular Zn(2+) but led to a profound increase in the intracellular levels of labile Cu(2+) and Fe(2+). An increase in the extracellular concentrations of Cd and Cu led to the elevated production of reactive oxygen species under the normocapnic conditions (0.05 kPa [Formula: see text] ); surprisingly, this effect was mitigated in hypercapnia (1.52 and 3.01 kPa). Overall, our data reveal complex and metal-specific interactions between the cellular effects of trace metals and [Formula: see text] in clams and indicate that variations in environmental [Formula: see text] may modulate the biological effects of trace metals in marine organisms. Copyright © 2013 Elsevier B.V. All rights reserved.
Thamban, Meloth; Thakur, Roseline C
2013-04-01
To investigate the distribution and source pathways of environmentally critical trace metals in coastal Antarctica, trace elemental concentrations were analyzed in 36 surface snow samples along a coast to inland transect in the Ingrid Christensen Coast of East Antarctica. The samples were collected and analyzed using the clean protocols and an inductively coupled plasma mass spectrometer. Within the coastal ice-free and ice-covered region, marine elements (Na, Ca, Mg, K, Li, and Sr) revealed enhanced concentrations as compared with inland sites. Along with the sea-salt elements, the coastal ice-free sites were also characterized by enhanced concentrations of Al, Fe, Mn, V, Cr, and Zn. The crustal enrichment factors (Efc) confirm a dominant crustal source for Fe and Al and a significant source for Cr, V, Co, and Ba, which clearly reflects the influence of petrological characteristics of the Larsemann Hills on the trace elemental composition of surface snow. The Efc of elements revealed that Zn, Cu, Mo, Cd, As, Se, Sb, and Pb are highly enriched compared with the known natural sources, suggesting an anthropogenic origin for these elements. Evaluation of the contributions to surface snow from the different sources suggests that while contribution from natural sources is relatively significant, local contamination from the increasing research station and logistic activities within the proximity of study area cannot be ignored.
Asa, Subas Chandra; Rath, Prasanta; Panda, Unmesh Chandra; Parhi, Pankaj Kumar; Bramha, Satyanarayan
2013-08-01
In the present study, concentration of some selected trace metals (Fe, Mn, Ni, Co, Pb, Zn, Cu, Cr and Cd) are measured in Brahmani, Baitarani river complex along with Dhamara estuary and its near shore. Chemical partitioning has been made to establish association of metals into different geochemical phases. The exchangeable fraction is having high environmental risk among non-lithogeneous phases due to greater potential for mobility into pore water. The metals with highest bio-availability being Cd, Zn and Cr. The metals like Mn, Zn, Cd and Cu represent an appreciable portion in carbonate phase. Fe-Mn oxides act as efficient scavenger for most of the metals playing a prime role in controlling their fate and transport. Among non-lithogeneous phases apart from reducible, Cr showed a significant enrichment in organic phase. Risk assessment code values indicate that all metals except Fe fall under medium-risk zone. In estuarine zone Cd, Zn, Pb and Cr are released to 32.43, 26.10, 21.81 and 20 %, respectively, indicating their significant bio-availability pose high ecological risk. A quantitative approach has been made through the use of different risk indices like enrichment factor, geo-accumulation index and pollution load index. Factor analysis indicates that in riverine zone, Fe-Mn oxides/hydroxides seem to play an important role in scavenging metals, in estuarine zone, organic precipitation and adsorption to the fine silt and clay particles while in coastal zone, co-precipitation with Fe could be the mechanism for the same. Canonical discriminant function indicates that it is highly successful in discriminating the groups as predicted.
Moyano, Mario F; Mariño-Repizo, Leonardo; Tamashiro, Héctor; Villegas, Liliana; Acosta, Mariano; Gil, Raúl A
2016-07-01
The role of trace elements bound to proteins in the etiology and pathogenesis of rheumatoid arthritis (RA) remains unclear. In this sense, the identification and detection of metalloproteins has a strong and growing interest. Metalloprotein studies are currently carried out by polyacrylamide gel electrophoresis (PAGE) associated to inductively coupled plasma mass spectrometry (ICPMS), and despite that complete information can be obtained for metals such as Fe, Cu and Zn, difficulties due to poor sensitivity for other trace elements such as Sn, As, etc, are currently faced. In the present work, a simple and fast method for the determination of trace metals bound to synovial fluid (SF) proteins was optimized. Proteins from SF (long and short-term RA) were separated in ten fractions by native PAGE, then dissolved in nitric acid and peroxide hydrogen, and analyzed by ICPMS. Fifteen metals were determined in each separated protein fraction (band). Adequate calibration of proteins molecular weight allowed stablishing which protein type were bound to different metals. Copyright © 2016 Elsevier GmbH. All rights reserved.
Park, Jin Hee; Kim, Bong-Soo; Chon, Chul-Min
2018-01-01
Different environmental conditions such as pH and dissolved elements of mine stream induce precipitation of different minerals and their associated microbial community may vary. Therefore, mine precipitates from various environmental conditions were collected and their associated microbiota were analyzed through metagenomic DNA sequencing. Various Fe and Mn minerals including ferrihydrite, schwertmannite, goethite, birnessite, and Mn-substituted δ-FeOOH (δ-(Fe 1-x , Mn x )OOH) were found in the different environmental conditions. The Fe and Mn minerals were enriched with toxic metal(loid)s including As, Cd, Ni and Zn, indicating they can act as scavengers of toxic metal(loid)s in mine streams. Under acidic conditions, Acidobacteria was dominant phylum and Gallionella (Fe oxidizing bacteria) was the predominant genus in these Fe rich environments. Manganese oxidizing bacteria, Hyphomicrobium, was found in birnessite forming environments. Leptolyngbya within Cyanobacteria was found in Fe and Mn oxidizing environments, and might contribute to Fe and Mn oxidation through the production of molecular oxygen. The potential interaction of microbial community with minerals in mine sites can be traced by analysis of microbial community in different Fe and Mn mineral forming environments. Iron and Mn minerals contribute to the removal of toxic metal(loid)s from mine water. Therefore, the understanding characteristics of mine precipitates and their associated microbes helps to develop strategies for the management of contaminated mine water. Copyright © 2017 Elsevier Ltd. All rights reserved.
NASA Astrophysics Data System (ADS)
Hasan Rhaif Al-Sahlanee, Mayyadah; Maizan Ramli, Ramzun; Abdul Hassan Ali, Miami; Fadhil Tawfiq, Nada; Zahirah Noor Azman, Nurul; Abdul Rahman, Azhar; Shahrim Mustafa, Iskandar; Noor Ashikin Nik Abdul Razak, Nik; Zakiah Yahaya, Nor; Mohammed Al-Marri, Hana; Syuhada Ayob, Nur; Zakaria, Nabela
2017-10-01
Trace elements are essential nutritional components in humans and inconvenient tissue content that have a significant influence on infant size. The aim of this study is to evaluate the effects of concentration of elements (uranium (U), lead (Pb) and iron (Fe)) and absorption of Pb and Fe on maternal and umbilical cord blood samples. The concentration and absorption of Pb and Fe in blood samples were determined by using atomic absorption spectrophotometry device, while the uranium concentration was determined by using CR-39 detector. Fifty women of age 16-44 years are involved in this study. Results show that the maximum and minimum values of both concentration and absorption in the maternal samples were for Pb and Fe, respectively. In addition, for umbilical cord, the maximum values of concentration and absorption were for Fe and the minimum concentration and absorption were for U and Pb, respectively. A significant correlation between maternal and umbilical cord blood samples was found. This indicates that the Pb, U and Fe elements can easily transfer from maternal to the fetal body which impacts the growth of fetus.
Mine drainage water from the Sar Cheshmeh porphyry copper mine, Kerman, IR Iran.
Shahabpour, J; Doorandish, M
2008-06-01
This paper presents the results of a study on stream and mine waters in the area of one of the world largest porphyry copper deposit located in the southeastern Iran, the Sar Cheshmeh porphyry copper mine. Trace metals are present as adsorption on Fe and Mn oxide and hydroxide particles, as sulfate, simple metal ions, and scarcely as adsorption on clay particles and hydrous aluminium oxides. Mean pH decreases and the mean concentration of trace elements, EC and SO4(2-) increases from the maximum discharge period (MXDP) during snow melt run off (May), through the moderate discharge period (MDDP; March and July) to the minimum discharge period (MNDP; September). Water samples have sulfatic character essentially, however, from the MNDP through the MDDP towards the MXDP they show a bicarbonate tendency. This study indicates that the surface waters draining the Sar Cheshmeh open pit have a higher pH and lower concentration of trace metals compared with some other porphyry copper deposits.
Sreekanth, Athira; Mrudulrag, S K; Cheriyan, Eldhose; Sujatha, C H
2015-12-30
The geochemical distribution and enrichment of trace metals (Cd, Co, Cu, Fe, Mn, Ni, Pb and Zn) were determined in the surface sediments of Arabian Sea, along southwest India, Kerala coast. The results of geochemical indices indicated that surficial sediments of five transects are uncontaminated with respect to Mn, Zn and Cu, uncontaminated to moderately contaminated with Co and Ni, and moderately to strongly contaminated with Pb. The deposition of trace elements exhibited three different patterns i) Cd and Zn enhanced with settling biodetritus from the upwelled waters, ii) Pb, Co and Ni show higher enrichment, evidenced by the association through adsorption of iron-manganese nodules onto clay minerals and iii) Cu enrichment observed close to major urban sectors, initiated by the precipitation as Cu sulfides. Correlation, principal component analysis (PCA) and cluster analysis (CA) were used to confirm the origin information of metals and the nature of organic matter composition. Copyright © 2015 Elsevier Ltd. All rights reserved.
Muñoz-Vera, Ana; Peñas Castejón, Jose Matías; García, Gregorio
2016-09-15
The effects of an abandoned mining area, exploited for centuries in the mining district of Cartagena-La Union, result in a continuous supply of heavy metals into the Mar Menor coastal lagoon after rain episodes. As a consequence, concentration of trace elements in water column and sediments of this ecosystem is usually higher than in other areas. For monitoring ecosystem health, this study assessed the ability of Rhizostoma pulmo to bioaccumulate trace elements. A total of 57 individuals were sampled at eight different sampling stations during the summer of 2012. Although the concentrations of different analyzed elements (Al, Ti, Cr, Mn, Fe, Ni, Cu, Zn, As, Cd, Sn, and Pb) were moderate, bioconcentration levels in relation to seawater metal concentration were extremely high. In any case, the use or disposal of these organisms should consider their metal content, because of their potential environmental and health implications. Copyright © 2016 Elsevier Ltd. All rights reserved.
Trace metals in sediments of two estuarine lagoons from Puerto Rico.
Acevedo-Figueroa, D; Jiménez, B D; Rodríguez-Sierra, C J
2006-05-01
Concentrations of As, Cd, Cu, Fe, Hg, Pb and Zn were evaluated in surface sediments of two estuaries from Puerto Rico, known as San José Lagoon (SJL) and Joyuda Lagoon. Significantly higher concentrations in microg/g dw of Cd (1.8 vs. 0.1), Cu (105 vs. 22), Hg (1.9 vs. 0.17), Pb (219 vs. 8), and Zn (531 vs. 52) were found in sediment samples from SJL when compared to Joyuda Lagoon. Average concentrations of Hg, Pb, and Zn in some sediment samples from SJL were above the effect range median (ERM) that predict toxic effects to aquatic organisms. Enrichments factors using Fe as a normalizer, and correlation matrices showed that metal pollution in SJL was the product of anthropogenic sources, while the metal content in Joyuda Lagoon was of natural origins. Sediment metal concentrations found in SJL were comparable to aquatic systems classified as contaminated from other regions of the world.
The cosmic evolution of dust-corrected metallicity in the neutral gas
NASA Astrophysics Data System (ADS)
De Cia, Annalisa; Ledoux, Cédric; Petitjean, Patrick; Savaglio, Sandra
2018-04-01
Interpreting abundances of damped Ly-α absorbers (DLAs) from absorption-line spectroscopy has typically been a challenge because of the presence of dust. Nevertheless, because DLAs trace distant gas-rich galaxies regardless of their luminosity, they provide an attractive way of measuring the evolution of the metallicity of the neutral gas with cosmic time. This has been done extensively so far, but typically not taking proper dust corrections into account. The aims of this paper are to: (i) provide a simplified way of calculating dust corrections, based on a single observed [X/Fe], (ii) assess the importance of dust corrections for DLA metallicities and their evolution, and (iii) investigate the cosmic evolution of iron for a large DLA sample. We have derived dust corrections based on the observed [Zn/Fe], [Si/Fe], or [S/Fe], and confirmed their robustness. We present dust-corrected metallicities in a scale of [Fe/H]tot for 236 DLAs over a broad range of z, and assess the extent of dust corrections for different metals at different metallicities. Dust corrections in DLAs are important even for Zn (typically of 0.1-0.2, and up to 0.5 dex), which is often neglected. Finally, we study the evolution of the dust-corrected metallicity with z. The DLA metallicities decrease with redshift, by a factor of 50-100 from today to 12.6 billion years ago (z = 5). When including dust corrections, the average DLA metallicities are 0.4-0.5 dex higher than without corrections. The upper envelope of the relation between metallicity and z reaches solar metallicity at z ≲ 0.5, although some systems can have solar metallicity already out to z 3. Based on observations carried out at the European Organisation for Astronomical Research in the Southern Hemisphere under ESO programmes 065.P-0038, 065.O-0063, 066.A-0624, 067.A-0078, and 068.A-0600.
Szefer, P; Ali, A A; Ba-Haroon, A A; Rajeh, A A; Gełdon, J; Nabrzyski, M
1999-09-01
Concentrations of Cd, Pb, Zn, Cu, Ni, Co, Cr, Mn and Fe in the soft tissue of Turbo coronatus, Acanthopleura haddoni, Ostrea cucullata and Pitar sp., as well as in associated surface sediments (bulk and bioavailable metal concentrations) from the Gulf of Aden, Yemen, were determined by atomic absorption spectrophotometry method. Large differences between size-classes of molluscs in metal concentrations were recorded. Significant spatial differences in metal concentrations in both the soft tissue of the molluscs and associated sediments studied were mostly identified. Statistically significant correlations (p<0.01) between concentrations of selected metals were observed. A slope of the linear regression is significantly higher than unity for Fe (9.91) and Cd (3.45) in A. haddoni and for Ni (4.15) in T. coronatus, suggesting that the bioavailability of these metals is disproportionally increased with a degree of enrichment of the sediments in Fe, Cd and Ni, respectively. A slope constant approximating to unity (1.14) for Cu in A. haddoni relative to its concentration in sediment extract implies that bioavailability of this metal proportionally increased with growing concentrations of its labile forms in the associated sediment. The degree of contamination of Gulf of Aden waters by the metals studied is discussed and the potential ability of molluscs, especially A. haddoni and T. coronatus, as biomonitors of metallic pollutants is postulated.
NASA Astrophysics Data System (ADS)
Bounakhla, M.; Doukkali, A.; Lalaoui, K.; Aguenaou, H.; Mokhtar, N.; Attrassi, B.
2003-05-01
The main purpose of this study is the interaction between nutrition (micronutrients heavy metals: Fe, Zn, Cu) and toxic heavy metals such as Pb in blood of children living in Gharb region of Morocco. This region receives all pollution carried by the Sebou river coming mainly from industrial activities. A rapid and simple analytical procedure was used for the determination of Fe, Cu and Zn trace amounts in blood by total-reflection X-ray fluorescence technique. This method is an energy dispersive XRF technique in a special geometry of primary beam, sample and detector. The sample is deposited on a plane polished surface of a suitable reflector material. It is presented as a few drops (25 μl) from a solution of blood digested in a mixture of HNO3 and H2O2 using a microwaves accelerated reaction system. The accuracy of measurements has been investigated by using certified materials. The concentration of Cu was found to be normal in all samples (\\cong1 ppm) which ruled out any interaction between this element and the others. On the other hand, amounts of Fe and Zn are very variables, suggesting an interaction between Fe and Zn. However, amounts of Pb in blood are inferior to 50 ppb, suggesting that no interaction exist with this metal and micronutrients.
Wu, Zhenggang; Gao, Y. F.; Bei, Hongbin
2015-07-25
To understand the fundamental deformation mechanisms of compositionally complex alloys, single crystals of a multi-component equiatomic FeNiCoCr alloy with face-centered cubic (FCC) structure were grown for mechanical studies. Similarly to typical FCC pure metals, slip trace analyses indicate that dislocation slips take place on (1 1 1) planes along [11¯0] directions. The critical resolved shear stress (CRSS) obeys the Schmid law at both 77 and 293 K, and tension–compression asymmetry is not observed. Although this material slips in a normal FCC manner both at 293 and 77 K, compared to typical FCC metals the CRSS’s strong temperature dependence is abnormal.
Trace elements in fish from Taihu Lake, China: levels, associated risks, and trophic transfer.
Hao, Ying; Chen, Liang; Zhang, Xiaolan; Zhang, Dongping; Zhang, Xinyu; Yu, Yingxin; Fu, Jiamo
2013-04-01
Concentrations of eight trace elements [iron (Fe), manganese (Mn), zinc (Zn), chromium (Cr), mercury (Hg), cadmium (Cd), lead (Pb), and arsenic (As)] were measured in a total of 198 samples covering 24 fish species collected from Taihu Lake, China, in September 2009. The trace elements were detected in all samples, and the total mean concentrations ranged from 18.2 to 215.8 μg/g dw (dry weight). The concentrations of the trace elements followed the sequence of Zn>Fe>Mn>Cr>As>Hg>Pb>Cd. The measured trace element concentrations in fish from Taihu Lake were similar to or lower than the reported values in fish around the world. The metal pollution index was used to compare the total trace element accumulation levels among various species. Toxabramis swinhonis (1.606) accumulated the highest level of the total trace elements, and Saurogobio dabryi (0.315) contained the lowest. The concentrations of human non-essential trace elements (Hg, Cd, Pb, and As) were lower than the allowable maximum levels in fish in China and the European Union. The relationships between the trace element concentrations and the δ(15)N values of fish species were used to investigate the trophic transfer potential of the trace elements. Of the trace elements, Hg might be biomagnified through the food chain in Taihu Lake if the significant level of p-value was set at 0.1. No biomagnification and biodilution were observed for other trace elements. Copyright © 2012 Elsevier Inc. All rights reserved.
NASA Astrophysics Data System (ADS)
Buono, A. S.; Dasgupta, R.; Walker, D.
2011-12-01
Secular cooling of terrestrial planets is known to cause crystallization of a solid inner core from metallic liquid core. Fractionation of light and siderophile elements is important during such crystallization for evolution of outer core and possible core-mantle interaction. Thus far studies focused on a pure Fe inner core in simple binary systems but the effects of possible formation of a carbide inner core component on siderophile element partitioning in a multi-component system has yet to be looked at in detail. We investigated the effects of pressure and S content on partition coefficients (D) between cohenite and liquid in the Fe-Ni-S-C system. Multi-anvil experiments were performed at 3 and 6 GPa at 1150 °C, in an Fe-rich mix containing a constant C and Ni to which S contents of 0, 5, and 14 wt.% were added. All the mixes were doped with W, Re, Os, Pt, and Co. Samples were imaged and analyzed for Fe, Ni, S, and C using an EPMA. Fe, Ni, and trace elements were analyzed using a LA-ICP-MS. All the experiments produced cohenite and Fe-Ni-C±S liquid. Compared to solid-Fe/melt Ds [1-2], cohenite/melt Ds are lower for all elements except W. The light element (S+C) content of the liquid is the dominant controlling factor in siderophile element partitioning between cohenite and liquid as it is between crystalline Fe and liquid. In the cohenite-metallic melt experiments, D Ni decreases as S+C increases. Ni is excluded from the crystallizing solid if the solid is cohenite. We also find that in the Fe-Ni-S-C system, cohenite is stabilized to higher P than in the Fe-S-C system [3-5]. Similar to the Fe-metallic liquid systems the non-metal avoidance model [6] is applicable to the Fe3C-metallic liquid system studied here. Our study has implications for both the cores of smaller planets and the mantles of larger planets. If inner core forms a cohenite layer we would predict that depletions in the outer core will be less than they might be for Fe metal crystallization. For the mantle of the earth, which is thought to become Fe-Ni metal-saturated as shallow as 250 km, the sub-system Fe-Ni + C + S becomes relevant and Fe-Ni carbide rather than metallic Fe-Ni alloy may become the crystalline phase of interest. Our study implies that because the partition coefficients between cohenite and Fe-C-S melts are significantly lower than those between Fe-metal and S-rich liquid, in the presence of cohenite and Fe-C-S melt in the mantle, the mantle budget of Ni, Co, and Pt may be dominated by Fe-C-S liquid. W, Re, and Os will also be slightly enriched in C-rich Fe-Ni liquid over cohenite if the metal sub-system of interest is S-free. [1] Chabot et al., GCA 70, 1322-1335, 2006 [2] Chabot et al., GCA 72, 4146-4158, 2008 [3] Chabot et al., Meteorit. Planet. Sci. 42, 1735-1750, 2007 [4] Stewart et al., EPSL 284, 302-309, 2009 [5] Van Orman et al., EPSL 274, 250-257, 2008 [6] Jones, J.H., Malvin, D.J., Metall Mater Trans B 21, 697-706, 1990
Wang, Bo-Shian; Lee, Chih-Ping; Ho, Tung-Yuan
2014-10-01
A fully automated high pressure pretreatment system with Nobias Chelate-PA1 resin (PA1) was developed for trace metal determination by ICP-MS in natural waters. By varying the concentrations of Mg and Ca to mimic the concentrations in the eluate obtained by PA1 or iminodiacetate type resins, the overall analytical performance of the system was assessed for the determination of Al, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Cd, Ag, Pb and REE. Comparing with the low mM level Mg and Ca (both ranging from 1 to 4mM) eluted by iminodiacetate type resins, the eluate obtained by PA1 contains sub-μM level Mg and Ca, which remarkably decrease matrix effect in ICP-MS analysis and significantly improve the analytical performance. With recovery better than 90% for most the trace metals examined, the accuracy was further verified through the analysis of five natural water reference materials with salinity spanning from 0 to 35‰. We have successfully applied the pretreatment system to determine trace metals in the seawater samples collected in the Western Philippine Sea through Taiwan GEOTRACES cruise. Copyright © 2014 Elsevier B.V. All rights reserved.
Can Dynamic Bubble Templating Play a Role in Corrosion Product Morphology?
2012-02-01
FeOOH (goethite) with moderate amounts of metallic luster Fe304 (magnetite), and trace amounts of CaC03 (calcite). In addition, the core was marbled ...cathodically produced gas bubbles (i.e., H2). By physically separating the anode and cathode. Stone and Goldstein26 generated tubular structures electro...D.A. Stone , RE. Goldstein. Proc. MatL Acad. Set U.S-A. 101 (2004): p. 11537. G. Butler, H.C.K. Ison, Nature 182 (1958): p. 1229. B. McEnaney. D.C
Trace elements and metals in farmed sea bass and gilthead bream from Tenerife Island, Spain.
Rubio, C; Jalilli, A; Gutiérrez, A J; González-Weller, D; Hernández, F; Melón, E; Burgos, A; Revert, C; Hardisson, A
2011-11-01
The aim of this study was to determine the levels of metals (Ca, K, Na, Mg) and trace metals (Ni, Fe, Cu, Mn, Zn, Pb, Cd) in two fish species (gilthead bream [Sparus aurata] and sea bass [Dicentrarchus labrax]) collected from fish farms located along the coast of Tenerife Island. Ca, K, Na, Mg, Fe, Cu, Zn, and Mn were measured by flame atomic absorption spectrometry, whereas Pb, Cd, and Ni were determined using graphite furnace atomic absorption spectrometry. Mean Fe, Cu, Mn, and Zn contents were 3.09, 0.59, 0.18, and 8.11 mg/kg (wet weight) in S. aurata and 3.20, 0.76, 0.24, and 10.11 mg/kg (wet weight) in D. labrax, respectively. In D. labrax, Ca, K, Na, and Mg levels were 1,955, 2,787, 699.7, and 279.2 mg/kg (wet weight), respectively; in S. aurata, they were 934.7, 3,515, 532.8, and 262.8 mg/kg (wet weight), respectively. The Pb level in S. aurata was 7.28 ± 3.64 μg/kg (wet weight) and, in D. labrax, 4.42 ± 1.56 μg/kg (wet weight). Mean Cd concentrations were 3.33 ± 3.93 and 1.36 ± 1.53 μg/kg (wet weight) for D. labrax and S. aurata, respectively. All Pb and Cd levels measured were well below the accepted European Commission limits, 300 and 50 μg/kg for lead and cadmium, respectively.
Wirt, Laurie; Leib, Kenneth J.; Melick, Roger; Bove, Dana J.
2001-01-01
strongly affected by natural acidity from pyrite weathering. Metal content in the water column is a composite of multiple sources affected by hydrologic, geologic, climatic, and anthropogenic conditions. Identifying sources of metals from various drainage areas was determined using a tracer injection approach and synoptic sampling during low flow conditions on September 29, 1999 to determine loads. The tracer data was interpreted in conjunction with detailed geologic mapping, topographic profiling, geochemical characterization, and the occurrence and distribution of trace metals to identify sources of ground-water inflows. For this highly mineralized sub-basin, we demonstrate that SO4, Al, and Fe load contributions from drainage areas that have experienced historical mining?although substantial?are relatively insignificant in comparison with SO4, Al, and Fe loads from areas experiencing natural weathering of highlyaltered, pyritic rocks. Regional weathering of acid-sulfate mineral assemblages produces moderately low pH waters elevated in SO4, Al, and Fe; but generally lacking in Cu, Cd, Ni, and Pb. Samples impacted by mining are also characterized by low pH and large concentrations of SO4, Al, and Fe; but contained elevated dissolved metals from ore-bearing vein minerals such as Cu, Zn, Cd, Ni, and Pb. Occurrences of dissolved trace metals were helpful in identifying ground-water sources and flow paths. For example, cadmium was greatest in inflows associated with drainage from inactive mine sites and absent in inflows that were unaffected by past mining activities and thus served as an important indicator of mining contamination for this environmental setting. The most heavily mine-impacted reach (PG153 to PG800), contributed 8% of the discharge, and 11%, 9%, and 12% of the total SO4, Al, and Fe loads in Prospect Gulch. The same reach yielded 59% and 37% of the total Cu and Zn loads for the subbasin. In contrast, the naturally acidic inflows from the Red Chemotroph iron spring yielded 39% of the discharge and 54%, 73%, and 87% of the SO4, Al, and Fe loads; but only 4% of the total Cu and 30% of the total Zn loads in Prospect Gulch. Base flow from the Prospect Gulch sub-basin contributes about 4.8 percent of the total discharge at the mouth of Cement Creek; compared with sampled instream loads of 1.8%, 8.8%, 15.9%, 28%, and 8.6% for SO4, Al, Fe, Cu and Zn, respectively. Water-shed scale remediation efforts targeted at reducing loads of SO4, Al, and Fe at inactive mine sites are likely to fail because the major sources of these constituents in Prospect Gulch are predominantly discharged from natural sources. Remediation goals aimed at reducing acidity and loads of Cu and other base metals, may succeed, however, because changes in pH and loads are disproportionately greater than increases in discharge over the same reach, and a substantial fraction of the metal loading is from mining-impacted reaches. Whether remediation of abandoned mines in Prospect Gulch can be successful depends on how goals are defined?that is, whether the objective is to reduce loads of SO4, Al, and Fe; or whether loads of Cu and other base metals and pH are targeted.
Status of trace metals in surface seawater of the Gulf of Aqaba, Saudi Arabia.
Al-Taani, Ahmed A; Batayneh, Awni; Nazzal, Yousef; Ghrefat, Habes; Elawadi, Eslam; Zaman, Haider
2014-09-15
The Gulf of Aqaba (GoA) is of significant ecological value with unique ecosystems that host one of the most diverse coral communities in the world. However, these marine environments and biodiversity have been threatened by growing human activities. We investigated the levels and distributions of trace metals in surface seawater across the eastern coast of the Saudi GoA. Zn, Cu, Fe, B and Se in addition to total dissolved solids and seawater temperature exhibited decreasing trends northwards. While Mn, Cd, As and Pb showed higher average levels in the northern GoA. Metal input in waters is dependent on the adjacent geologic materials. The spatial variability of metals in water is also related to wave action, prevailing wind direction, and atmospheric dry deposition from adjacent arid lands. Also, water discharged from thermal desalination plants, mineral dust from fertilizer and cement factories are potential contributors of metals to seawater water, particularly, in the northern GoA. Copyright © 2014 Elsevier Ltd. All rights reserved.
NASA Astrophysics Data System (ADS)
Koukina, S. E.; Vetrov, A. A.
2013-09-01
This study focuses on sediments from small restricted exchange environments along the Karelian shore of Kandalaksha Bay (White Sea, Russian Arctic), which are known as separating basins and are characterised by contrasting oxidising conditions within the water column and the occurrence of anoxia. In the basins that were studied, no significant contamination by trace heavy metals (Pb, Cu, Zn and Cr, in particular) was detected. The comparative study of the two most bioavailable metal forms, namely, labile (acid soluble) and organically bound (alkali soluble) forms, indicated that acetic acid and sodium pyrophosphate released 3-11% and 2-12%, respectively, of the total metal content from sediments. The most bioavailable parts of metals are weakly bound to organic matter and, to a greater extent, associated with easily soluble amorphous Fe-oxides. Among the studied elements, most of the bioavailable Zn and Cu was most likely bound to organic substances, whereas bioavailable Cr and Mn were controlled to a greater extent by the formation of Fe-oxyhydroxide. The elements studied could be arranged in the following decreasing order of average potential bioavailability: Cu > Zn > Mn > Fe > Cr > Pb. In the separating basins, the relative proportion of labile bioavailable metals is enhanced in relation to the neighbouring open coastal sea.
NASA Astrophysics Data System (ADS)
Onojake, M. C.; Sikoki, F. D.; Omokheyeke, O.; Akpiri, R. U.
2017-05-01
Surface water samples from three stations in the Bonny/New Calabar River Estuary were analyzed for the physicochemical characteristics and trace metal level in 2011 and 2012, respectively. Results show pH ranged from 7.56 to 7.88 mg/L; conductivity, 33,489.00 to 33,592.00 µScm-1; salinity, 15.33 to 15.50 ‰; turbidity, 4.35 to 6.65 NTU; total dissolved solids, 22111.00 to 23263.00 gm-3; dissolved oxygen, 4.53 to 6.65 mg/L; and biochemical oxygen demand, 1.72 mg/L. The level of some trace metals (Ca, Mg, K, Zn, Pb, Cd, Co, Cr, Cu, Fe, Ni, and Na) were also analyzed by Atomic absorption spectrometry with K, Zn, and Co being statistically significant ( P < 0.05). The results were compared with USEPA and WHO Permissible Limits for water quality standards. It was observed that the water quality parameters in the Bonny Estuary show seasonal variation with higher values for pH, DO, BOD, temperature, and salinity during the dry season than wet season. Concentrations of trace metals such as Pb, Cd, Zn, Ni, and Cr were higher than stipulated limits by WHO (2006). The result of the Metal Pollution Index suggests that the river was slightly affected and therefore continuous monitoring is necessary to avert possible public health implications of these metals on consumers of water and seafood from the study area.
Wiche, Oliver; Székely, Balazs; Kummer, Nicolai-Alexeji; Moschner, Christin; Heilmeier, Hermann
2016-09-01
This study aims to investigate how intercropping of oat (Avena sativa L.) with white lupin (Lupinus albus L.) affects the mobile fractions of trace metals (Fe, Mn, Pb, Cd, Th, U, Sc, La, Nd, Ge) in soil solution. Oat and white lupin were cultivated in monocultures and mixed cultures with differing oat/white lupin ratios (11% and 33% lupin, respectively). Temporal variation of soil solution chemistry was compared with the mobilization of elements in the rhizosphere of white lupin and concentrations in plant tissues. Relative to the monocrops, intercropping of oat with 11% white lupin significantly increased the concentrations of Fe, Pb, Th, La and Nd in soil solution as well as the concentrations of Fe, Pb, Th, Sc, La and Nd in tissues of oat. Enhanced mobility of the mentioned elements corresponded to a depletion of elements in the rhizosphere soil of white lupin. In mixed cultures with 33% lupin, concentrations in soil solution only slightly increased. We conclude that intercropping with 11% white lupin might be a promising tool for phytoremediation and phytomining research enhancing mobility of essential trace metals as well as elements with relevance for phytoremediation (Pb, Th) and phytomining (La, Nd, Sc) in soil.
Kibria, Golam; Hossain, Md Maruf; Mallick, Debbrota; Lau, T C; Wu, Rudolf
2016-04-15
Using artificial mussels (AMs), this study reports and compares time-integrated level of eleven trace metals (Cd, Co, Cr, Cu, Fe, Hg, Mn, Ni, Pb, U, Zn) in Karnafuli River estuary and coastal area of the Bay of Bengal, Bangladesh. Through this study, "hot spots" of metal pollution were identified. The results may demonstrate that the Karnafuli Estuary, and adjacent coastal area of Chittagong, Bangladesh are highly polluted by high risk metals (cadmium, chromium, copper, mercury, nickel, lead, uranium). Agricultural, domestic and industrial wastes directly discharged into the waterways have been identified as the main causes of metal pollution in Chittagong, Bangladesh. The high level of metal pollution identified may impact on local water quality, and seafood catch, livelihoods of people and public health resulting from seafood consumption. There is a need for regular monitoring to ascertain that local water quality with respect to metal levels are within acceptable levels to safeguards both environmental health and public health. Copyright © 2016 Elsevier Ltd. All rights reserved.
Noble, Abigail E.; Moran, Dawn M.; Allen, Andrew E.; Saito, Mak A.
2013-01-01
Dissolved and particulate metal concentrations are reported from three sites beneath and at the base of the McMurdo Sound seasonal sea ice in the Ross Sea of Antarctica. This dataset provided insight into Co and Mn biogeochemistry, supporting a previous hypothesis for water column mixing occurring faster than scavenging. Three observations support this: first, Mn-containing particles with Mn/Al ratios in excess of the sediment were present in the water column, implying the presence of bacterial Mn-oxidation processes. Second, dissolved and labile Co were uniform with depth beneath the sea ice after the winter season. Third, dissolved Co:PO3−4 ratios were consistent with previously observed Ross Sea stoichiometry, implying that over-winter scavenging was slow relative to mixing. Abundant dissolved Fe and Mn were consistent with a winter reserve concept, and particulate Al, Fe, Mn, and Co covaried, implying that these metals behaved similarly. Elevated particulate metals were observed in proximity to the nearby Islands, with particulate Fe/Al ratios similar to that of nearby sediment, consistent with a sediment resuspension source. Dissolved and particulate metals were elevated at the shallowest depths (particularly Fe) with elevated particulate P/Al and Fe/Al ratios in excess of sediments, demonstrating a sea ice biomass source. The sea ice biomass was extremely dense (chl a >9500 μg/L) and contained high abundances of particulate metals with elevated metal/Al ratios. A hypothesis for seasonal accumulation of bioactive metals at the base of the McMurdo Sound sea ice by the basal algal community is presented, analogous to a capacitor that accumulates iron during the spring and early summer. The release and transport of particulate metals accumulated at the base of the sea ice by sloughing is discussed as a potentially important mechanism in providing iron nutrition during polynya phytoplankton bloom formation and could be examined in future oceanographic expeditions. PMID:24790953
NASA Astrophysics Data System (ADS)
Noble, Abigail; Saito, Mak; Moran, Dawn; Allen, Andrew
2013-10-01
Dissolved and particulate metal concentrations are reported from three sites beneath and at the base of the McMurdo Sound seasonal sea ice in the Ross Sea of Antarctica. This dataset provided insight into Co and Mn biogeochemistry, supporting a previous hypothesis for water column mixing occurring faster than scavenging. Three observations support this: first, Mn-containing particles with Mn/Al ratios in excess of the sediment were present in the water column, implying the presence of bacterial Mn-oxidation processes. Second, dissolved and labile Co were uniform with depth beneath the sea ice after the winter season. Third, dissolved Co:PO43- ratios were consistent with previously observed Ross Sea stoichiometry, implying that over-winter scavenging was slow relative to mixing. Abundant dissolved Fe and Mn were consistent with a winter reserve concept, and particulate Al, Fe, Mn, and Co covaried, implying that these metals behaved similarly. Elevated particulate metals were observed in proximity to the nearby Islands, with particulate Fe/Al ratios similar to that of nearby sediment, consistent with a sediment resuspension source. Dissolved and particulate metals were elevated at the shallowest depths (particularly Fe) with elevated particulate P/Al and Fe/Al ratios in excess of sediments, demonstrating a sea ice biomass source. The sea ice biomass was extremely dense (chl a >9500 μg/L) and contained high abundances of particulate metals with elevated metal/Al ratios. A hypothesis for seasonal accumulation of bioactive metals at the base of the McMurdo Sound sea ice by the basal algal community is presented, analogous to a capacitor that accumulates iron during the spring and early summer. The release and transport of particulate metals accumulated at the base of the sea ice by sloughing is discussed as a potentially important mechanism in providing iron nutrition during polynya phytoplankton bloom formation and could be examined in future oceanographic expeditions.
Portable detection of trace metals in airborne particulates and sediments via μPADs and smartphone.
Jia, Yuan; Dong, Hui; Zheng, Jianping; Sun, Hao
2017-11-01
Particulate matter (PM), a key indicator of air pollution by natural and anthropogenic activities, contributes to a wide spectrum of diseases that lead to a shortening of life expectancy. It has been recognized that trace metals in airborne PM are highly toxic and can be correlated with lesion in respiratory, gastrointestinal, immunological, and hematological systems. Traditional methods for trace metal assay require sophisticated instrumentations and highly trained operators in centralized laboratories. In this work, by integrating the technologies of microfluidic paper-based analytical devices, additive manufacturing, smartphone, and colorimetric sensing, we developed the first smartphone based paper microfluidic platform for portable, disposable, and quantitative measurements of cobalt (Co), copper (Cu), and iron (Fe) in ambient air and street sediments. On a single A4-sized paper, 48 devices were fabricated in under 30 s with a total cost of ∼$1.9. On each device, 12 reaction units were patterned and used for colorimetric tests. Particulate samples from urban ambient air and street sediments were collected, processed, and analyzed. Signals of the on-chip complexation product were recorded using a smartphone camera and processed by a self-developed app on an iOS system. For precisely controlling the object distance, chip position, and luminance, a hand-held 3D cellphone housing was designed and printed. The detection limits of Co, Cu, and Fe were determined to be 8.2, 45.8, and 186.0 ng, while the linear dynamic ranges were calculated to be 8.2-81.6, 45.8-4.58 × 10 2 , and 1.86 × 10 2 -1.86 × 10 3 ng, representing a practically relevant device performance with a significant reduction in the detection cost and time consumption. Trace metals in ambient air and sediments of two cities in China have been quantified portably, thus demonstrating the utility of our system in improving strategies for air pollution control in low-resource settings.
Milatou, Niki; Dassenakis, Manos; Megalofonou, Persefoni
2015-01-01
The objective of this study was to determine the current levels of heavy metals and trace elements in Atlantic bluefin tuna muscle tissues and how they are influenced by the fattening process and various life history parameters to ascertain whether the concentrations in muscle tissue exceed the maximum levels defined by the European Commission Decision and to evaluate the health risk posed by fish consumption. A total of 20 bluefin tuna reared in sea cages, ranging from 160 to 295 cm in length and from 80 to 540 kg in weight, were sampled from a bluefin tuna farm in the Ionian Sea. The condition factor K of each specimen was calculated and their age was estimated. Heavy metal and trace element (Hg, Zn, Fe and Cu) contents were determined in muscle tissue using cold vapour atomic absorption spectrometry and flame and graphite furnace atomic absorption spectrometry. The total Hg concentrations ranged from 0.28 to 1.28 mg kg(-1) w/w, Zn from 5.81 to 76.37 mg kg(-1) w/w, Fe from 12.14 to 39.58 mg kg(-1) w/w, and Cu from 0.36 to 0.94 mg kg(-1) w/w. Only 5% of the muscle samples of tuna contained Hg above the maximum level laid down by the European Commission Decision. Moreover, 15% of the muscle samples contained Zn above the maximum level, while Fe and Cu concentrations were within the acceptable tolerable guideline values. The reared bluefin tuna had lower concentrations of Hg than the wild ones from the Mediterranean Sea. Hg and Fe concentrations showed a positive relationship with size and age of bluefin tuna, whereas negative relationships were found for the concentrations of Zn and Cu. The estimated dietary intake values of the analysed metals were mostly below the derived guidelines.
NASA Astrophysics Data System (ADS)
Al-Said, T. F.; Pokavanich, T.; Al-Hashem, A.; Kedila, R.
2016-02-01
Kuwait is in the northwestern part of the Arabian Gulf and receives flow from Shatt Al-Arab River as the main fresh water input to the Gulf. Kuwait's waters can be described as eutrophic, euphotic, and highly saline waters. The main objective of the study is to assess spatial and temporal distribution of Cu, Co, Zn, Fe and Ni, nutrients such as nitrate and phosphate, chlorophyll-a and physical variables along transects in Kuwait's Waters. No systematic research on bioactive metals has been studied in the region. Concentration of trace metal in the shallow Kuwait Bay was relatively high and decreased towards the southern water. This is attributed to higher sewage input, domestic and industrial effluents, dust storms and human activities. Cu, Ni, Fe, Zn and Co levels were measured using proven tested methodology i.e., Adsorptive Cathodic Stripping Voltammetry (Ad-CSV) and Flow Injection Analyzer (FIA). Surface seawater samples were collected from 26 stations using clean polyethylene sampling devices from four transects during two seasons in 2015. Average concentrations of Copper, Nickel, Cobalt, Zinc and chlorophyll-a corresponded to 14.99, 22.32, 0.74, 14.56 nM and 3.05µg/L during June 2015. These values indicated lower concentrations compared to previously published values from Kuwait's waters: Cu 48.52, Ni 26.12, Co 4.69, Zn 93.86 nM. Two transects conducted during summer 2015 showed positive relationship between metals (Cu, Co and Ni) and chlorophyll. Strong and apparent correlation was observed between cobalt and chlorophyll-a in Kuwait Bay indicating that these micronutrient are abundant and higher than phytoplankton essential requirements. Recent measured Fe concentration 7.95nM in Kuwait Bay was comparable to values found in similar coastal water. Latest results obtained during the transactional surveys and processes involved in Kuwait's waters will be shown and discussed during the presentation.
Characterization of As and trace metals embedded in PM10 particles in Puebla City, México.
Morales-García, S S; Rodríguez-Espinosa, P F; Jonathan, M P; Navarrete-López, M; Herrera-García, M A; Muñoz-Sevilla, N P
2014-01-01
Forty-eight air-filter samples (PM10) were analysed to identify the concentration level of partially leached metals (PLMs; As, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb and V) from Puebla City, México. Samples were collected during 2008 from four monitoring sites: (1) Tecnológico (TEC), (2) Ninfas (NIN), (3) Hermanos Serdán (HS) and (4) Agua Santa (AS). The results indicate that in TEC, As (avg. 424 ng m(-3)), V (avg. 19.2 ng m(-3)), Fe (avg. 1,202 ng m(-3)), Cu (avg. 86.6 ng m(-3)), Cr (41.9 ng m(-3)) and Ni (18.6 ng m(-3)) are on the higher side than other populated regions around the world. The enrichment of PLMs is due to the industrial complexes generating huge dust particles involving various operations. The results are supported by the correlation of metals (Mn, Cd and Co) with Fe indicating its anthropogenic origin and likewise, As with Cd, Co, Fe, Mn, Pb and V. The separate cluster of As, Fe and Mn clearly signifies that it is due to continuous eruption of fumaroles from the active volcano Popocatépetl in the region.
NASA Astrophysics Data System (ADS)
Arruti, A.; Fernández-Olmo, I.; Irabien, A.
2011-07-01
The aim of this study was to determine the major components (Na, Ca, K, Mg, Fe, Al, NH 4+, SO 42-, NO 3-, Cl - and TC) and trace-metal levels (As, Ni, Cd, Pb, Ti, V, Cr, Mn, Cu, Mo, Rh and Hg) in PM 10 and PM 2.5 at an Atlantic coastal city (Santander, Cantabria region, Northern Spain). Additional samples were collected in other urban sites of the Cantabria region to assess the metal content found in different urban environments within the region. To control for the mass attributed to inland regional background particulate matter, samples were also collected in Los Tojos village. The spatial variability of the major PM components shows that PM origins are different at inland and coastal sites. In the coastal city of Santander, the most important contributors are (i) the marine aerosol and (ii) the secondary inorganic aerosol (SIA) and the total carbon (TC) in PM 10 and PM 2.5, respectively. Additionally, the influence of the coastal location on the ionic balance of PM is also studied. The trace metal spatial variability is studied using the coefficient of divergence (COD), which shows that the levels of trace metals at the three studied urban sites are mainly influenced by local emission sources. The main local tracers are identified as follows: Mn in the Santander area; Mo, Cr and Pb at Reinosa; and Ni and V at Castro Urdiales. A more detailed source apportionment study of the local trace metals at Santander is conducted by Principal Component Analysis (PCA) and Positive Matrix Factorisation (PMF); these two receptor models report complementary information. From these statistical analyses, the identified sources of trace metals in PM 10 are urban background sources, industrial sources and traffic. The industrial factor was dominated by Mn, Cu and Pb, which are trace metals used in steel production and manganese-ferroalloy production plant. With respect to PM 2.5, the identified emission sources of trace metals are combustion processes as well as traffic and industrial sources.
Study of inverse magnetostrictive effect in metallic glasses Fe80-x Co x P14B6
NASA Astrophysics Data System (ADS)
Severikov, V. S.; Grishin, A. M.; Ignahin, V. S.
2017-11-01
The paper presents the possibility to build a tension gauge capable to discriminate different kinds of deformations: compression and twisting (induced by torsion strain) based on the magnetoelastic effect in new metallic glasses Fe80-x Co x P14B6. Applied loads increase coercive field H c, saturation induction B s and rectangularity of magnetic hysteresis loop. For example, hysteresis loop traced for 1 mm narrow, 50 cm long and 30 μm thick Fe40Co40P14B6 straight ribbon subjected to longitudinal stress of 346 MPa shown increased B s from 1.24 to 1.7 T and squareness from 0.55 to 0.88 compared to unloaded specimen. For twisting, on the contrary, both squareness and coercive field vary whereas the value of B s remains unchanged.
Macronutrients and trace metals in soil and food crops of Isfahan Province, Iran.
Keshavarzi, Behnam; Moore, Farid; Ansari, Maryam; Rastegari Mehr, Meisam; Kaabi, Helena; Kermani, Maryam
2015-01-01
The distribution of 10 macronutrients and trace metals in the arable soils of Isfahan Province, their phytoavailability, and associated health risks were investigated; 134 plant and 114 soil samples (from 114 crop fields) were collected and analyzed at harvesting time. Calculation of the soil pollution index (SPI) revealed that arable soil polluted by metals was more severe in the north and southwest of the study area. The results of cluster analysis indicated that Pb, Zn, and Cu share a similar origin from industries and traffic. The concentrations of macronutrients and trace metals in the sampled crops were found in the order of K > Ca > S > Mg > P and Fe > Mn > Zn > Cu > Pb, respectively, whereas calculation of the bioconcentration factor (BCF) indicated that the accumulation of the investigated elements in crops was generally in the order of S ≈ K > P > Mg > Ca and Zn > Cu > Mn > Pb > Fe, respectively. Thus, various parameters including crop species and the physical, chemical, and biological properties of soil also affected the bioavailability of the elements besides the total element contents in soil. Daily intake (DI) values of elements were lower than the recommended daily intake (RDI) levels in rice grains except for Fe and Mn, but for wheat grains, all elements displayed DI values higher than the RDI. Moreover, based on the hazard index (HI) values, inhabitants are experiencing a significant potential health risk solely due to the consumption of wheat and rice grains (particularly wheat grains). Mn health quotient (HQ) also indicated a high risk of Mn absorption for crop consumer inhabitants.
A new look at inhalable metalliferous airborne particles on rail subway platforms.
Moreno, Teresa; Martins, Vânia; Querol, Xavier; Jones, Tim; BéruBé, Kelly; Minguillón, Maria Cruz; Amato, Fulvio; Capdevila, Marta; de Miguel, Eladio; Centelles, Sonia; Gibbons, Wes
2015-02-01
Most particles breathed on rail subway platforms are highly ferruginous (FePM) and extremely small (nanometric to a few microns in size). High magnification observations of particle texture and chemistry on airborne PM₁₀ samples collected from the Barcelona Metro, combined with published experimental work on particle generation by frictional sliding, allow us to propose a general model to explain the origin of most subway FePM. Particle generation occurs by mechanical wear at the brake-wheel and wheel-rail interfaces, where magnetic metallic flakes and splinters are released and undergo progressive atmospheric oxidation from metallic iron to magnetite and maghemite. Flakes of magnetite typically comprise mottled mosaics of octahedral nanocrystals (10-20 nm) that become pseudomorphed by maghemite. Continued oxidation results in extensive alteration of the magnetic nanostructure to more rounded aggregates of non-magnetic hematite nanocrystals, with magnetic precursors (including iron metal) still preserved in some particle cores. Particles derived from steel wheel and rails contain a characteristic trace element chemistry, typically with Mn/Fe=0.01. Flakes released from brakes are chemically very distinctive, depending on the pad composition, being always carbonaceous, commonly barium-rich, and texturally inhomogeneous, with trace elements present in nanominerals incorporated within the crystalline structure. In the studied subway lines of Barcelona at least there appears to be only a minimal aerosol contribution from high temperature processes such as sparking. To date there is no strong evidence that these chemically and texturally complex inhalable metallic materials are any more or less toxic than street-level urban particles, and as with outdoor air, the priority in subway air quality should be to reduce high mass concentrations of aerosol present in some stations. Copyright © 2014. Published by Elsevier B.V.
Use of Synchrotron X-ray Fluorescence to Measure Trace Metal Distribution in the Brain
NASA Astrophysics Data System (ADS)
Linkous, D.; Flinn, J. M.; Lanzirotti, A.; Frederickson, C.; Jones, B. F.; Bertsch, P. M.
2002-12-01
X26A, National Synchrotron Light Source, was used to quantitatively evaluate the spatial distribution of trace metals, such as Zn and Cu, in brain tissue. X-ray microprobe techniques offer distinct advantages over other analytical methods by allowing analyses to be done in-situ with little or no chemical pretreatment and low detection limits (about 1 ppm). In the context of neuroscience, SXRF can provide non-destructive measurements of specific metal concentrations and distribution within nerve (brain) tissue. Neuronal tissue from organisms having undergone different normal or experimental conditions may be compared, with analytical capacities not limited by binding states of the metal (i.e., vesicular or enzymatic), as is the case with staining techniques.. Whole regions of tissue may be scanned for detectable trace metals at spatial resolutions of 10um or less using focused monochromatic x-ray beams. Here special attention has been given to zinc because it is the most common trace metal in the brain, and levels have been increasing in the environment. In this investigation, zinc concentrations present within the hilus of a rat hippocampus, and to a lesser extent in the cortex, have been shown to increase following long-term ingestion of zinc-enhanced drinking water that was associated with deficits in spatial memory. Concomitantly, copper concentrations in the internal capsule were comparatively lower. Other first order transition metals, Cr, V, Mn, and Co were not detected. In contrast, elevated levels of Zn, Cu, and Fe have been seen in amyloid plaques associated with Alzheimer's disease.
Ullah, Zia; Ullah, Muhammad Ikram; Hussain, Shabbir; Kaul, Haiba; Lone, Khalid P
2017-01-01
Rheumatoid arthritis (RA) is a chronic autoimmune inflammatory disease, which mainly involves the joints. RA is prevalent worldwide with increasing prevalence in elderly people. The mechanism of RA pathogenesis is still undefined, and it is interplaying between genetic susceptibility and environmental factors. Although risk factors for RA are not fully established, various studies have focused on the role of trace elements in association with RA. Trace elements act as co-factors for most of the enzymes, and their deficiency is associated with many untoward effects on human health. The homeostatic alterations in the metabolism of trace elements may partly be due to inflammatory response in RA. The objective of the present study was to determine the serum concentrations and correlation of zinc, copper, and iron in RA patients and healthy controls. The study comprised of 61 RA patients and 61 age- and sex-related healthy individuals of Pakistani population. Serum levels of Zn, Cu, and Fe were measured in all the participants by atomic absorption spectrophotometer. Serum Zn and Fe were significantly reduced in the RA patients than those in the healthy controls. Serum Cu concentrations were found elevated in the RA patients. Correlation studies of trace elements determine that there was negative correlation between Zn and Cu in the RA patients and no correlation in the control group. It is very important to explore the deficiency of essential trace metals in biological samples of the RA patients in different populations which may be helpful for diagnosis and supplementary management of rheumatoid arthritis patients.
The Influence of Iron on the Cellular Quota of Prochlorococcus
2008-01-01
as chlorosis, is found in many land plants and larger phytoplankton cells but this is the first laboratory documentation of it occurring in...implications for the hybrid-type trace metals. In press Deep Sea Res II. Raven, J.A., 1990. Predictions of Mn and Fe use efficiencies of phototrophic growth as
Donohue, Patrick H; Hill, Eddy; Huss, Gary R
2018-02-01
Pallasite meteorites, which consist primarily of olivine and metal, may be remnants of disrupted core-mantle boundaries of differentiated asteroids or planetesimals. The early thermal histories of pallasites are potentially recorded by minor- and trace-element zonation in olivine. However, constraining this history requires knowledge of element behavior under the conditions of pallasite formation, which is lacking for many of the main elements of interest (e.g., Co, Cr, Mn). In this study, we experimentally determined metal/olivine partition coefficients for Fe, Ni, Co, Cr, and Mn in a pallasite analogue at subsolidus temperatures. Metal/olivine partition coefficients ( K M ) increase in the order K Mn < K Cr < 1 < K Fe < K Co < K Ni , with five orders of magnitude separating K Mn from K Ni . Transition metals also become more siderophile with increasing experimental temperature (900 to 1550°C). The experiments incidentally produced diffusion profiles in olivine for these elements; Our results suggest they diffuse through olivine at similar rates. Core compositions of pallasite olivines are consistent with high-temperature equilibration with FeNi-metal. Olivine zonation toward crystal rims varies significantly for the investigated transition metals. We suggest rim zonation results from partial re-equilibration during late stage crystallization of minor phases (e.g., chromite, phosphates). This re- equilibration occurred over short timescales relative to overall pallasite cooling, likely tied to initial cooling rates on the order of 100-300°C/Myr.
Rapid, Selective Heavy Metal Removal from Water by a Metal-Organic Framework/Polydopamine Composite.
Sun, Daniel T; Peng, Li; Reeder, Washington S; Moosavi, Seyed Mohamad; Tiana, Davide; Britt, David K; Oveisi, Emad; Queen, Wendy L
2018-03-28
Drinking water contamination with heavy metals, particularly lead, is a persistent problem worldwide with grave public health consequences. Existing purification methods often cannot address this problem quickly and economically. Here we report a cheap, water stable metal-organic framework/polymer composite, Fe-BTC/PDA, that exhibits rapid, selective removal of large quantities of heavy metals, such as Pb 2+ and Hg 2+ , from real world water samples. In this work, Fe-BTC is treated with dopamine, which undergoes a spontaneous polymerization to polydopamine (PDA) within its pores via the Fe 3+ open metal sites. The PDA, pinned on the internal MOF surface, gains extrinsic porosity, resulting in a composite that binds up to 1634 mg of Hg 2+ and 394 mg of Pb 2+ per gram of composite and removes more than 99.8% of these ions from a 1 ppm solution, yielding drinkable levels in seconds. Further, the composite properties are well-maintained in river and seawater samples spiked with only trace amounts of lead, illustrating unprecedented selectivity. Remarkably, no significant uptake of competing metal ions is observed even when interferents, such as Na + , are present at concentrations up to 14 000 times that of Pb 2+ . The material is further shown to be resistant to fouling when tested in high concentrations of common organic interferents, like humic acid, and is fully regenerable over many cycles.
da Silva, Yuri Jacques Agra Bezerra; do Nascimento, Clístenes Williams Araújo; Cantalice, José Ramon Barros; da Silva, Ygor Jacques Agra Bezerra; Cruz, Cinthia Maria Cordeiro Atanázio
2015-09-01
Determining heavy metal background concentrations in soils is fundamental in order to support the monitoring of potentially contaminated areas. This is particularly important to areas submitted to high environmental impact where an intensive and local monitoring is required. To this end, the aim of this study was to establish background concentrations and quality reference values (QRVs) for the heavy metals Cd, Cr, Cu, Fe, Mn, Ni, Pb, Zn, As, and Hg in an environmentally impacted watershed from Brazil. Geochemical associations among Fe, Mn, and trace elements were also assessed to provide an alternative tool for establishing background concentrations. A total of one hundred and four samples comprised twenty-six composite soil samples from areas of native forest or minimal anthropic influence. Samples were digested (USEPA method 3051A), and the metals were determined by ICP-OES, except for As and Hg measured by atomic absorption spectrophotometer. Background concentrations of heavy metals in soils had the following decreasing order: Fe > Mn > Zn > Cr > Pb > Ni > Cu > As > Cd > Hg. These values were usually lower than those observed in the international and national literature. The QRVs for Ipojuca watershed followed the order (mg kg(-1)) Fe (13,020.40) > Mn (91.80) > Zn (30.12) > Cr (15.00) > Pb (13.12) > Cu (3.53) > Ni (3.30) > As (0.51) > Cd (0.08) > Hg (0.04). Significant correlation among Fe, Mn, and heavy metals shows that solubilization by the method 3051A provides a reasonable estimate for predicting background concentrations for Cd, Cr, and Cu as well as Zn, Cr, Cu, and Ni.
Smith, C.L.; Motooka, J.M.; Willson, W.R.
1984-01-01
Since concentrations of trace elements in most natural waters seldom exceed the ??g/L level, analysis of trace elements in natural waters by inductively coupled plasma emission spectrometry (ICP) requires a preconcentration procedure. The elements Ag, Bi, Cd, Co, Cu, Fe, Mo, Ni, Pb, Sn, V, W, and Zn were separated and concentrated from 500 mL of water by coprecipitating them with sodium dibenzyldithiocarbamate (NaDBDTC) using nickel or silver as a carrier. The precipitated trace elements were collected on a membrane filter, redissolved from the filter with hot nitric and hydrochloric acids, and analyzed using ICP. Recoveries for all the trace elements except tungsten exceeded 80%. Coprecipitation of trace elements with NaDBDTC eliminated the use of difficult-to-inject organic solvents, and NaDBDTC coprecipitated a wider array of trace elements than ammoniumpyrrolidinedithiocarbamate (APDC), another commonly used coprecipitate.
Boosting Bifunctional Oxygen Electrolysis for N-Doped Carbon via Bimetal Addition.
Wang, Jian; Ciucci, Francesco
2017-04-01
The addition of transition metals, even in a trace amount, into heteroatom-doped carbon (M-N/C) is intensively investigated to further enhance oxygen reduction reaction (ORR) activity. However, the influence of metal decoration on the electrolysis of the reverse reaction of ORR, that is, oxygen evolution reaction (OER), is seldom reported. Moreover, further improving the bifunctional activity and corrosion tolerance for carbon-based materials remains a big challenge, especially in OER potential regions. Here, bimetal-decorated, pyridinic N-dominated large-size carbon tubes (MM'-N/C) are proposed for the first time as highly efficient and durable ORR and OER catalysts. FeFe-N/C, CoCo-N/C, NiNi-N/C, MnMn-N/C, FeCo-N/C, NiFe-N/C, FeMn-N/C, CoNi-N/C, MnCo-N/C, and NiMn-N/C are systematically investigated in terms of their structure, composition, morphology, surface area, and active site densities. In contrast to conventional monometal and N-decorated carbon, small amounts of bimetal (≈2 at%) added during the one-step template-free synthesis contribute to increased pyridinic N content, much longer and more robust carbon tubes, reduced metal particle size, and stronger coupling between the encapsulated metals and carbon support. The synergy of those factors accounts for the dramatically improved ORR and OER activity and stability. By comparison, NiFe-N/C and MnCo-N/C stand out and achieve superior bifunctional oxygen catalytic performance, exceeding most of state-of-the-art catalysts. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
NASA Astrophysics Data System (ADS)
Siefert, Ronald L.; Johansen, Anne M.; Hoffmann, Michael R.
1999-02-01
Atmospheric deposition of iron (Fe) to certain regions of the oceans is an important nutrient source of Fe to the biota, and the ability of the biota to uptake Fe is dependent on the speciation of the Fe. Therefore understanding the speciation of Fe in the atmosphere is critical to understanding the role of Fe as a nutrient source in surface ocean waters. Labile ferrous iron (Fe(II)) concentrations as well as total concentrations for Fe and other important trace metals, cations, and anions were determined over the Arabian Sea for two nonconsecutive months during 1995. Ambient aerosol samples were collected during the Indian Ocean intermonsoon and southwest monsoon seasons over the Arabian Sea. Sampling took place aboard the German research vessel Meteor in the months of May (leg M32/3; intermonsoon) and July/August (leg M32/5; southwest monsoon). Both cruise tracks followed the 65th east meridian, traveling for 30 days each (from north to south during leg M32/3 and from south to north during leg M32/5). A high-volume dichotomous virtual impactor with an aerodynamic cutoff size of 3 μm was used to collect the fine and coarse aerosol fractions for metal analysis. A low volume collector was used to collect aerosol samples for anion and cation analysis. The analysis for labile-Fe(II) was done immediately after sample collection to minimize any possible Fe redox reactions which might occur during sample storage. The analytical procedure involved filter extraction in a formate/formic acid buffered solution at pH 4.2 followed by colorimetric quantification of soluble Fe(II). Metals, anions, and cations were analyzed after the cruise. Total atmospheric aqueous-labile-Fe(II) concentrations during the intermonsoon were between 4.75 and <0.4 ng m-3, of which most (>80%) was present in the fine fraction (<3.0 μm). During the southwest monsoon, atmospheric aqueous-labile-Fe(II) concentrations were consistently below the detection limit (<0.34 to <0.089 ng m-3, depending on the volume of air sampled). Air mass back trajectories (5 day, three dimensional) showed that air masses sampled during the southwest monsoon had advected over the open Indian Ocean, while air masses sampled during the intermonsoon had advected over northeast Africa, the Saudi Arabian peninsula, and southern Asia. These calculations were consistent with the results of the statistical analysis performed on the data set which showed that the variance due to crustal species during the intermonsoon samples was greater than the variance due to crustal species during the southwest monsoon. The factor scores for the crustal components were also greater when the back trajectories had advected over the nearby continental masses. Principal component analysis was also performed with the intermonsoon samples where aqueous labile Fe(II) was above the detection limit. Aqueous labile Fe(II) did not correlate well with other species indicating possible atmospheric processing of the iron during advection.
Cheng, Weizhi; Roessler, Justin; Blaisi, Nawaf I; Townsend, Timothy G
2014-12-01
Drinking water treatment residues (WTR) offer potential benefits when recycled through land application. The current guidance in Florida, US allows for unrestricted land application of lime softening WTR; alum and ferric WTR require additional evaluation of total and leachable concentrations of select trace metals prior to land application. In some cases a mixed WTR is produced when lime softening is accompanied by the addition of a coagulant or other treatment chemical; applicability of the current guidance is unclear. The objective of this research was to characterize the total and leachable chemical content of WTR from Florida facilities that utilize multiple treatment chemicals. Lime and mixed lime WTR samples were collected from 18 water treatment facilities in Florida. Total and leachable concentrations of the WTR were measured. To assess the potential for disposal of mixed WTR as clean fill below the water table, leaching tests were conducted at multiple liquid to solid ratios and under reducing conditions. The results were compared to risk-based soil and groundwater contamination thresholds. Total metal concentrations of WTR were found to be below Florida soil contaminant thresholds with Fe found in the highest abundance at a concentration of 3600 mg/kg-dry. Aluminum was the only element that exceeded the Florida groundwater contaminant thresholds using SPLP (95% UCL = 0.23 mg/L; risk threshold = 0.2 mg/L). Tests under reducing conditions showed elevated concentrations of Fe and Mn, ranging from 1 to 3 orders of magnitude higher than SPLP leachates. Mixed lime WTR concentrations (total and leachable) were lower than the ferric and alum WTR concentrations, supporting that mixed WTR are appropriately represented as lime WTR. Testing of WTR under reducing conditions demonstrated the potential for release of certain trace metals (Fe, Al, Mn) above applicable regulatory thresholds; additional evaluation is needed to assess management options where reducing conditions may develop. Copyright © 2014 Elsevier Ltd. All rights reserved.
Trace metals health risk appraisal in fish species of Arabian Sea.
Yasmeen, Kousar; Mirza, Muhammad Aslam; Khan, Namra A; Kausar, Nazish; Rehman, Atta-Ur; Hanif, Muddasir
2016-01-01
Fish is a vital food for humans and many animals. We report an environmental monitoring study to assess the trace metals in fish species caught from Arabian Sea and commercially available in the coastal city Karachi, Pakistan. Heavy metals such as copper, iron, lead and cadmium were determined in the skin, fillet and heart of the fish species Pampus argenteus, Epinephelus chlorostigma, Rachycentron canadum, Scomberomorus commerson, Johnius belangerii, Labeo rohita, Lutjanus argentimaculatus, Trachinotus blochii, Pomadsys olivaceum and Acanthopagrus berda by the atomic absorption spectrophotometer. The concentration (mg kg(-1), dry weight) range was: Cd (0.00-0.041), Cu (0.006-0.189), Fe (0.413-4.952) and Pb (0.00-0.569). Cadmium, copper and iron levels were below the tolerable limits whereas concentration of lead in the skins of S. commerson, E. chlorostigma, J. belangerii, A. berda; L. argentimaculatus, fillets of J. belangerii, E. chlorostigma and in the heart of J. belangerii exceeded the recommended limits. Therefore fish skin should be discouraged as food for humans or animals. The results indicate that a number of fish species have higher concentration of heavy metals dangerous for human health. Since the fish P. olivaceum (Dhotar) has the lowest level of trace metals therefore we recommend it for breeding and human consumption.
Facilitation of trace metal uptake in cells by inulin coating of metallic nanoparticles
NASA Astrophysics Data System (ADS)
Santillán-Urquiza, Esmeralda; Arteaga-Cardona, Fernando; Torres-Duarte, Cristina; Cole, Bryan; Wu, Bing; Méndez-Rojas, Miguel A.; Cherr, Gary N.
2017-09-01
Trace elements such as zinc and iron are essential for the proper function of biochemical processes, and their uptake and bioavailability are dependent on their chemical form. Supplementation of trace metals through nanostructured materials is a new field, but its application raises concerns regarding their toxicity. Here, we compared the intracellular zinc uptake of different sources of zinc: zinc sulfate, and ZnO and core-shell α-Fe2O3@ZnO nanoparticles, coated or uncoated with inulin, an edible and biocompatible polysaccharide. Using mussel haemocytes, a well-known model system to assess nanomaterial toxicity, we simultaneously assessed zinc accumulation and multiple cellular response endpoints. We found that intracellular zinc uptake was strongly enhanced by inulin coating, in comparison to the uncoated nanoparticles, while no significant effects on cell death, cell viability, mitochondrial membrane integrity, production of reactive oxygen species or lysosome abundance were observed at concentrations up to 20 ppm. Since no significant increments in toxicity were observed, the coated nanomaterials may be useful to increase in vivo zinc uptake for nutritional applications.
Bobrowski, A
1994-05-01
The catalytic adsorptive stripping voltammetric method with alpha-benzil dioxime and nitrite affords numerous advantages in cobalt determination. The detailed conditions of the determination of the cobalt traces in metallic zinc by catalytic adsorptive stripping voltammetry have been investigated. Both the linear sweep and the differential pulse stripping modes can be used with similar sensitivity. Possible interferences by Mn, Pb, Cu, Ni and Fe are evaluated. In the presence of 5 x 10(5) fold excess of Zn the linear dependence of the cobalt CASV peak current on concentration ranged from 0.05 mug/l to 3 mug/l. Optimal conditions include the accumulation potential of -0.65 V and the accumulation time of 10 sec. The results of the determination of 10(-5)% level of Co in the metallic zinc showed good reproducibility (relative standard deviation, RSD = 0.07) and reliability.
Changes in trace metals in Thalassia testudinum after hurricane impacts.
Whelan, T; Van Tussenbroek, B I; Santos, M G Barba
2011-12-01
Major hurricanes Emily and Wilma hit the Mexican Caribbean in 2005. Changes in trace metals in the seagrass Thalassia testudinum prior to (May 2004, 2005) and following passage of these hurricanes (May, June 2006) were determined at four locations along a ≈ 130 km long stretch of coast. Before the hurricanes, essential metals were likely limiting and concentrations of potentially toxic Pb were high in a contaminated lagoon (27.5 μg g(-1)) and near submarine springs (6.10 μg g(-1)); the likely sources were inland sewage disposal or excessive boat traffic. After the hurricanes, Pb decreased to 2.0 μg g(-1) in the contaminated lagoon probably through flushing. At the northern sites, essential Fe increased >2-fold (from 26.8 to 68.3 μg g(-1) on average), possibly from remobilization of anoxic sediments or upwelling of deep seawater during Wilma. Thus, hurricanes can be beneficial to seagrass beds in flushing toxic metals and replenishing essential elements. Copyright © 2011 Elsevier Ltd. All rights reserved.
Endo, Tetsuya; Kimura, Osamu; Hisamichi, Yohsuke; Minoshima, Yasuhiko; Haraguchi, Koichi
2007-02-01
Mercury (Hg), cadmium (Cd), iron (Fe) manganese (Mn), zinc (Zn) and copper (Cu) concentrations in the liver, kidney and muscle of nine killer whales (including three calves) that stranded together in the northern area of Japan were determined. The Hg and Cd concentrations were found at trace levels in the calf organs, and increased with age. The Fe concentration in the muscle was significantly lower in the calves than in the mature whales and also increased with age. In contrast, Mn and Cu concentrations in the muscle were significantly higher in the calves than in the mature whales, and changes in the Zn concentration relative to age were unclear. These results suggest minimal mother-to-calf transfer of the toxic metals Hg and Cd and accumulation of these metals in the organs with age, while the essential metals Mn and Cu were found at higher concentrations in the muscle of calves than in mature whales.
NASA Astrophysics Data System (ADS)
Dias, S.; Cruz, I.; Fonseca, R.; Barriga, F. J.; Pedersen, R.
2010-12-01
The Jan Mayen vent fields were discovered in the Mohns Ridge during an expedition with the Norwegian research vessel "G.O. Sars" in July 2005. They comprise two main active areas: (1) Soria Moria and (2) Gallionella Garden & Trollveggen. The Trollveggen vent field is located at depths of 700-750 m. Venting takes place mainly through white smoker chimneys with fluid temperatures reaching up to 260-270°C. Here we present mineralogical and geochemical data from vent chimneys and metalliferous sediments collected at the Trollveggen vent field with an ROV. Cross-sections of chimneys present evident mineralogical zonation, showing acicular barite crystals in the outer parts and sulfide enrichments in the interior (Sph + Cpy +/- Py - Po). Sediments are mainly formed by vent fragments but also by minerals precipitated by diffuse fluid circulation, showing a mineral assemblage similar to that of chimneys. Microprobe analyses were obtained both in sulfates and sulphides revealing a particular sphalerite composition, characterized by low Fe (< 2%) and high total trace metal contents (up to 4%, including Cu, Ag and Au). Geochemical profiles of gravity cores collected in the area surrounding Jan Mayen were also performed in order to investigate the presence of additional hydrothermal activity in the area. Total geochemical analyses showed a slight enrichment in trace metals, such as Cu, Zn and Fe, with exception of one core that reached 85 ppm for Cu, 150 ppm for Zn and 20% for Fe. The metal enrichment in this core suggests hydrothermal activity in the neighboring area.
Ben Salem, Zohra; Laffray, Xavier; Al-Ashoor, Ahmed; Ayadi, Habib; Aleya, Lotfi
2017-04-01
The uptake of metals in roots and their transfer to rhizomes and above-ground plant parts (stems, leaves) of cattails (Typha latifolia L.) were studied in leachates from a domestic landfill site (Etueffont, France) and treated in a natural lagooning system. Plant parts and corresponding water and sediment samples were taken at the inflow and outflow points of the four ponds at the beginning and at the end of the growing season. Concentrations of As, Cd, Cr, Cu, Fe, Mn, Ni and Zn in the different compartments were estimated and their removal efficiency assessed, reaching more than 90% for Fe, Mn and Ni in spring and fall as well in the water compartment. The above- and below-ground cattail biomass varied from 0.21 to 0.85, and 0.34 to 1.24kgdryweight/m 2 , respectively, the highest values being recorded in the fourth pond in spring 2011. The root system was the first site of accumulation before the rhizome, stem and leaves. The highest metal concentration was observed in roots from cattails growing at the inflow of the system's first pond. The trend in the average trace element concentrations in the cattail plant organs can generally be expressed as: Fe>Mn>As > Zn>Cr>Cu>Ni>Cd for both spring and fall. While T. latifolia removes trace elements efficiently from landfill leachates, attention should also be paid to the negative effects of these elements on plant growth. Copyright © 2016. Published by Elsevier B.V.
Secondary-volatiles linked metallic iron in eucrites: The dual-origin metals of Camel Donga
NASA Astrophysics Data System (ADS)
Warren, Paul H.; Isa, Junko; Ebihara, Mitsuru; Yamaguchi, Akira; Baecker, Bastian
2017-04-01
The unique occurrence of abundant ( 1 vol%) near-pure-Fe metal in the Camel Donga eucrite is more complicated than previously believed. In addition to that component of groundmass metal, scattered within the meteorite are discrete nodules of much higher kamacite abundance. We have studied the petrology and composition of two of these nodules in the form of samples we call CD2 and CD3. The nodules are ovoids 11 (CD2) to 15 (CD3) mm across, with metal, or inferred preweathering metal, abundances of 12-17 vol% (CD2 is unfortunately quite weathered). The CD3 nodule also includes at its center a 5 mm ovoid clumping (6 vol%) of F-apatite. Both nodules are fine-grained, so the high Fe metal and apatite contents are clearly not flukes of inadequate sampling. The metals within the nodules are distinctly Ni-rich (0.3-0.6 wt%) compared to the pure-Fe (Ni generally 0.01 wt%) groundmass metals. Bulk analyses of three pieces of the CD2 nodule show that trace siderophile elements Ir, Os, and Co are commensurately enriched; Au is enriched to a lesser degree. The siderophile evidence shows the nodules did not form by in situ reduction of pyroxene FeO. Moreover, the nodules do not show features such as silica-phase enrichment or pyroxene with reduced FeO (as constrained by FeO/MgO and especially FeO/MnO) predicted by the in situ reduction model. The oxide minerals, even in groundmass samples well away from the nodules, also show little evidence of reduction. Although the nodule boundaries are generally sharp, groundmass-metal Ni content is anti-correlated with distance from the CD3 nodule. We infer that the nodules represent materials that originated within impactors into the Camel Donga portion of the eucrite crust, but probably were profoundly altered during later metamorphism/metasomatism. Origin of the pure-Fe groundmass metal remains enigmatic. In situ reduction probably played an important role, and association in the same meteorite of the Fe-nodules is probably significant. But the fluid during alteration was probably not (as previously modeled) purely S and O, of simple heat-driven internal derivation. We conjecture a two-stage metasomatism, as fluids passed through Camel Donga after impact heating of volatile-rich chondritic masses (survivors of gentle accretionary impacts) within the nearby crust. First, reduction to form troilite may have been triggered by fluids rich in S2 and CO (derived from the protonodules?), and then in a distinct later stage, fluids were (comparatively) H2O-rich, and thus reacted with troilite to form pure-Fe metal along with H2S and SO2. The early eucrite crust was in places a dynamic fluid-bearing environment that hosted complex chemical processes, including some that engendered significant diversity among metal+sulfide alterations.
Zhu, Yu-Min; Zhang, Hua; Fan, Shi-Suo; Wang, Si-Jia; Xia, Yi; Shao, Li-Ming; He, Pin-Jing
2014-07-15
Due to the heterogeneity of metal distribution, it is challenging to identify the speciation, source and fate of metals in solid samples at micro scales. To overcome these challenges single particles of air pollution control residues were detected in situ by synchrotron microprobe after each step of chemical extraction and analyzed by multivariate statistical analysis. Results showed that Pb, Cu and Zn co-existed as acid soluble fractions during chemical extraction, regardless of their individual distribution as chlorides or oxides in the raw particles. Besides the forms of Fe2O3, MnO2 and FeCr2O4, Fe, Mn, Cr and Ni were closely associated with each other, mainly as reducible fractions. In addition, the two groups of metals had interrelations with the Si-containing insoluble matrix. The binding could not be directly detected by micro-X-ray diffraction (μ-XRD) and XRD, suggesting their partial existence as amorphous forms or in the solid solution. The combined method on single particles can effectively determine metallic multi-associations and various extraction behaviors that could not be identified by XRD, μ-XRD or X-ray absorption spectroscopy. The results are useful for further source identification and migration tracing of heavy metals. Copyright © 2014 Elsevier B.V. All rights reserved.
NASA Astrophysics Data System (ADS)
Huang, Xin; Chen, Shuai; Zeng, Zhigang; Pu, Xiaoqiang; Hou, Qinghua
2017-10-01
Sediment samples obtained from the South Mid-Atlantic Ridge were analyzed for the major and trace elements by inductively coupled plasma atomic emission spectroscopy and inductively coupled plasma mass spectrometry. Results revealed that the contents of elements (e.g., Fe, Mn, Cu, Zn, V, Co) were high in samples 22V-TVG10 and 26V-TVG05 from the sites near the hydrothermal areas, and low in sample 22V-TVG14, which was collected far from the hydrothermal areas. The contents of Ca, Sr and Ba in the samples showed opposite trends. A positive correlation between the concentrations of metallic elements (Cu, Zn, Co, Ni, Pb, V) and Fe in the samples were observed. These results are consistent with chemical evolution of the dispersing hydrothermal plume.
NASA Astrophysics Data System (ADS)
Spina, L.; Randich, S.; Magrini, L.; Jeffries, R. D.; Friel, E. D.; Sacco, G. G.; Pancino, E.; Bonito, R.; Bravi, L.; Franciosini, E.; Klutsch, A.; Montes, D.; Gilmore, G.; Vallenari, A.; Bensby, T.; Bragaglia, A.; Flaccomio, E.; Koposov, S. E.; Korn, A. J.; Lanzafame, A. C.; Smiljanic, R.; Bayo, A.; Carraro, G.; Casey, A. R.; Costado, M. T.; Damiani, F.; Donati, P.; Frasca, A.; Hourihane, A.; Jofré, P.; Lewis, J.; Lind, K.; Monaco, L.; Morbidelli, L.; Prisinzano, L.; Sousa, S. G.; Worley, C. C.; Zaggia, S.
2017-05-01
Context. The radial metallicity distribution in the Galactic thin disc represents a crucial constraint for modelling disc formation and evolution. Open star clusters allow us to derive both the radial metallicity distribution and its evolution over time. Aims: In this paper we perform the first investigation of the present-day radial metallicity distribution based on [Fe/H] determinations in late type members of pre-main-sequence clusters. Because of their youth, these clusters are therefore essential for tracing the current interstellar medium metallicity. Methods: We used the products of the Gaia-ESO Survey analysis of 12 young regions (age < 100 Myr), covering Galactocentric distances from 6.67 to 8.70 kpc. For the first time, we derived the metal content of star forming regions farther than 500 pc from the Sun. Median metallicities were determined through samples of reliable cluster members. For ten clusters the membership analysis is discussed in the present paper, while for other two clusters (I.e. Chamaeleon I and Gamma Velorum) we adopted the members identified in our previous works. Results: All the pre-main-sequence clusters considered in this paper have close-to-solar or slightly sub-solar metallicities. The radial metallicity distribution traced by these clusters is almost flat, with the innermost star forming regions having [Fe/H] values that are 0.10-0.15 dex lower than the majority of the older clusters located at similar Galactocentric radii. Conclusions: This homogeneous study of the present-day radial metallicity distribution in the Galactic thin disc favours models that predict a flattening of the radial gradient over time. On the other hand, the decrease of the average [Fe/H] at young ages is not easily explained by the models. Our results reveal a complex interplay of several processes (e.g. star formation activity, initial mass function, supernova yields, gas flows) that controlled the recent evolution of the Milky Way. Based on observations made with the ESO/VLT, at Paranal Observatory, under program 188.B-3002 (The Gaia-ESO Public Spectroscopic Survey).Full Table 1 is only available at the CDS via anonymous ftp to http://cdsarc.u-strasbg.fr (http://130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/601/A70
Sokolowski, A; Wolowicz, M; Hummel, H
2001-10-01
Overlying bottom water samples were collected in the Vistula River plume, southern Baltic Sea, (Poland) and analysed for dissolved and labile particulate (1 M HCl extractable) Cu, Pb, Zn, Mn, Fe and Ni, hydrological parameters being measured simultaneously. Particulate organic matter (POM), chlorophyll a and dissolved oxygen are key factors governing the chemical behaviour of the measured metal fractions. For the dissolved Cu, Pb, Zn, Fe and Ni two maxima, in the shallow and in the deeper part of the river plume, were found. In the shallow zone desorption from seaward fluxing metal-rich riverine particles account for markedly increased metal concentrations, as confirmed also by high particulate metal contents. For Pb, atmospheric inputs were also considered to have contributed to the elevated concentrations of dissolved Pb adjacent to the river mouth. In the deep zone desorption from detrital and/or resuspended particles by aerobic decomposition of organic material may be the main mechanism responsible for enrichment of particle-reactive metals (Cu, Pb, Zn) in the overyling bottom waters. The increased concentrations of dissolved Fe may have been due to reductive dissolution of Fe oxyhydroxides within the deep sediments by which dissolved Ni was released to the water. The distribution of Mn was related to dissolved oxygen concentrations, indicating that Mn is released to the water column under oxygen reduced conditions. However, Mn transfer to the dissolved phase from anoxic sediments in deeper part of the Vistula plume was hardly evidenced suggesting that benthic flux of Mn occurs under more severe reductive regime than is consistent with mobilization of Fe. Behaviour of Mn in a shallower part has been presumably affected by release from porewaters and by oxidization into less soluble species resulting in seasonal removal of this metal (e.g. in April) from the dissolved phase. The particulate fractions represented from about 6% (Ni) and 33% (Mn, Zn, Cu) to 80% (Fe) and 89% (Pb) of the total (labile particulate plus dissolved) concentrations. The affinity of the metals for particulate matter decreased in the following order: Pb > Fe > Zn > or = > Cu > Mn > Ni. Significant relationships between particulate Pb-Zn-Cu reflected the affinity of these metals for organic matter, and the significant relationship between Ni-Fe reflected the adsorption of Ni onto Fe-Mn oxyhydroxides. A comparison of metal concentrations with data from other similar areas revealed that the river plume is somewhat contaminated with Cu, Pb and Zn which is in agreement with previous findings on anthropogenic origin of these metals in the Polish zone of southern Baltic Sea.
Characteristics and environmental aspects of slag: a review
Piatak, Nadine M.; Parsons, Michael B.; Seal, Robert R.
2015-01-01
The composition of ferrous slag is dominated by Ca and Si. Steel slag may contain significant Fe, whereas Mg and Al may be significant in Fe slag. Calcium-rich olivine-group silicates, melilite-group silicates that contain Al or Mg, Ca-rich glass, and oxides are the most commonly reported major phases in ferrous slag. Calcite and trace amounts of a variety of sulfides, intermetallic compounds, and pure metals are typically also present. The composition of non-ferrous slag, most commonly from base-metal production, is dominated by Fe and Si with significant but lesser amounts of Al and Ca. Silicates in the olivine, pyroxene, and melilite groups, as well as glass, spinels, and SiO2 (i.e., quartz and other polymorphs) are commonly found in non-ferrous slag. Sulfides and intermetallic compounds are less abundant than the silicates and oxides. The concentrations of some elements exceed generic USEPA soil screening levels for human contact based on multiple exposure pathways; these elements include Al, Cr, Cu, Fe, Mn, Pb, and Zn based on bulk chemical composition. Each slag type usually contains a specific suite of elements that may be of environmental concern. In general, non-ferrous slag may have a higher potential to negatively impact the environment compared to ferrous slag, and is thus a less attractive material for reuse, based on trace element chemistry, principally for base metals. However, the amount of elements released into the environment is not always consistent with bulk chemical composition. Many types of leaching tests have been used to help predict slag’s long-term environmental behavior. Overall, ferrous slags produce an alkaline leachate due to the dissolution of Ca oxides and silicates derived from compounds originally added as fluxing agents, such as lime. Ferrous slag leachate is commonly less metal-rich than leachate from non-ferrous slag generated during base metal extraction; the latter leachate may even be acidic due to the oxidation of sulfides. Because of its characteristics, ferrous slag is commonly used for construction and environmental applications, whereas both non-ferrous and ferrous slag may be reprocessed for secondary metal recovery. Both types of slag have been a source of some environmental contamination. Research into the environmental aspects of slag will continue to be an important topic whether the goal is its reuse, recycling, or remediation.
The effect of abandoned mining ponds on trace elements dynamics in the soil-plant system
NASA Astrophysics Data System (ADS)
Gabarrón, María; Faz, Ángel; Zornoza, Raúl; Acosta, Jose A.
2017-04-01
In semiarid climate regions lack of vegetation and dryer climate contribute to erosion of abandoned mining surface areas making them up important potential sources of metal pollution into the environment. The objectives of this study were to determine the influence of mine ponds in agriculture and forest soils, and identify the dynamic of metals in the soil-plant system for native plant species (Ballota hirsuta) and crop species (Hordeum vulgare) in two ancient mining districts: La Unión and Mazarrón. To achieve these objectives, wastes samples from mine ponds and soil samples (rhizosphere and non-rhizosphere soils) from natural and agricultural lands were collected. In addition, six plants (Ballota hirsuta) from natural area and 3 plants (Hordeum vulgare) from crops were collected. Physicochemical properties and total, water soluble and bioavailable metals (Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, and Zn) and arsenic were measured in waste/soil samples. The chemical speciation of metals in soil was estimated by a sequential extraction procedure. For plants analyses, each plant were divided in roots, stem and leaves and metal content measured by ICP-MS. Results indicated that mine, natural and agricultural soils were contaminated by As, Cd, Cu, Pb, and Zn. Chemical partitioning revealed higher mobility of metals in mine ponds than natural and agriculture soils while only Fe and As are completely bound to the soil matrix due to the mineralogical compositions of soils. The accumulation of metals in Ballota hirsuta in La Union decrease as Fe>As>Cr>Ni>Cu>Zn>Cd>Mn>Co>Pb while in Mazarrón did as As>Fe>Cr>Pb>Cu>Ni>Co>Mn>Zn>Cd. Ballota hirsuta showed high ability to bio-accumulate Cu, Cr, Fe, Ni, and As, transferring a large amount to edible parts without exceeding the toxicity limits for animals. Results for barley plants (Hordeum vulgare) showed the ability to absorb and accumulate As, Fe, Mn, Pb and Zn, although the transfer ability of As, Cd and Pb was lower. Although the behavior of metals reflects a root barrier effect, the amount of Pb in grain overreached the permissible limit in aliments.
NASA Astrophysics Data System (ADS)
Lazar, C.
2017-12-01
The formation of abiotic alkanes via CO2 reduction during serpentinization is an important process in astrobiology and geochemistry. Aqueous alkane concentrations in natural settings are often non-equilibrated, thus motivating many experimental studies of CO2 reduction kinetics. A well-established result of such studies is the strong catalytic effect of metallic Feo on the conversion rate of CO2 to alkanes. Because alkanogenetic serpentinization experiments often feature Fe-bearing minerals contained in gold vessels, incidental metallic Feo may precipitate during an experiment as Au-Fe alloy. Such alloy may be catalytic, potentially leading to artificially rapid alkanogenesis and an overestimation of the catalytic strength of nominally nonmetallic Fe-bearing minerals, even if isotopically labeled 13C is used. To evaluate this potential for Au-Fe alloying, a thermodynamic analysis of the effect of oxygen fugacity on Au-Fe mixing has been performed at metamorphic grades relevant to experimental alkanogenesis. The results show that even relatively oxidized metal-free mineral assemblages such as the quartz-fayalite-magnetite buffer (QFM) can stably coexist with an Au-Fe alloy containing a few hundred ppm Fe. Given the strong catalytic effect of metallic Fe, any hydrocarbons generated during a hypothetical experiment containing, for example, the QFM assemblage might be catalyzed by trace Fe in an Au-Fe alloy, not by a QFM mineral. The effect is stronger for assemblages more reducing than QFM, which are notably common in serpentinites. This is a source of experimental uncertainty in reusable flexible gold cell apparatus that cannot be assessed by traditional blank experiments, which only demonstrate the effectiveness of post-run acid-cleaning procedures. A more effective approach would be the chemical analysis of a small, recoverable gold chip embedded into the experimental materials. By assuming that the experimental materials interact identically with the Au chip and with the Au vessel wall, it would be possible to explicitly evaluate whether catalytic Au-Fe alloy formed in situ in a given experiment.
Feyisa Bogale, Raji; Ye, Junwei; Sun, Yuan; Sun, Tongxin; Zhang, Siqi; Rauf, Abdul; Hang, Cheng; Tian, Peng; Ning, Guiling
2016-07-05
A luminescent Eu(iii)-based coordination polymer, {[Eu(H2O)5(BTEC)][H(C5H6N2)]·3H2O} () has been synthesized under hydrothermal conditions using 1,2,4,5-benzenetetracarboxylic acid (H4BTEC) as a linker. Compound possesses an anionic zig-zag chain constructed from the BTEC ligands and [EuO4(H2O)5] nodes. The protonated 4-aminopyridine groups as guests are located between chains. exhibits the characteristic sharp emission bands of Eu(3+) at 578, 593, 615, 652 and 693 nm upon excitation at 290 nm. The strong emission of could be quenched effectively by trace amounts of Fe(3+) ions even in the presence of other metal ions including Al(3+), Ca(2+), Cd(2+), Co(2+), Cr(3+), Cu(2+), Fe(2+), K(+), Mg(2+), Mn(2+), Pd(2+) and Zn(2+). Similarly, also exhibits superior selectivity and sensitivity towards 4-nitrophenol (4-NP) compared with other competing interfering analytes, such as 2,4,6-trinitrophenol, 2,6-dinitrotolune, 4-nitrotoluene, nitrobenzene, 1,3-dinitrobenzene, o-xylene, nitromethane, nitropropane, phenol, 4-bromophenol and bromobenzene, through a fluorescence quenching mechanism. The possible fluorescence quenching mechanisms are discussed. Moreover, could be used as a visual fluorescent test paper for selectively detecting trace amounts of Fe(3+) and 4-NP.
Nomngongo, Philiswa N; Catherine Ngila, J; Kamau, Joseph N; Msagati, Titus A M; Marjanovic, Ljiljana; Moodley, Brenda
2013-07-17
Chelex-100, Dowex 50W-x8 and Dowex MAC-3 exchange resins were investigated for separation and pre-concentration of trace amounts of Cd, Cr, Cu, Fe, Mn, Pb, Ti and Zn in alcohols with respect to retention and desorption characteristics. Dowex 50W-x8 was found to be the best sorbent with percentages recoveries >95%. In addition, Chelex-100 appeared to be suitable for the pre-concentration of Cu, Fe and Zn, whereas Dowex MAC-3 was selective for Cu and Fe. Therefore, Dowex 50W-x8 was used for further investigations. The relative standard deviations <4% (n=20), limits of detection and quantification were 0.1-1.2 μg L(-1) and 0.3-1.5 μg L(-1), respectively. The SPE method was validated against a certified reference material and the results were in agreement with certified values. The accuracy of the optimized method was verified by the recovery test in the spiked alcohol samples. The accuracy and spike recovery test for different metal ions were in the range 98-102% and 95-105%, respectively. The optimized method was applied to the separation and pre-concentration of metal ions in different commercial alcohol samples. Copyright © 2013 Elsevier B.V. All rights reserved.
NASA Astrophysics Data System (ADS)
Peterson, Ruth
2017-08-01
Imaging surveys from the ultraviolet to the infrared are recording ever more distant astronomical sources. Needed to interpret them are high-resolution ultraviolet spectral templates at all metallicities for both old and intermediate-age stars, and the atomic physics data essential to model their spectra. To this end we are proposing new UV spectra of four warm and hot stars spanning a wide range of metallicity. These will provide observational templates of old and young metal-poor turnoff stars, and the laboratory source for the identification of thousands of lines of neutral iron that appear in stellar spectra but are not identified in laboratory spectra. By matching existing and new stellar spectra to calculations of energy levels, line wavelengths, and gf-values, Peterson & Kurucz (2015) and Peterson, Kurucz, & Ayres (2017) identified 124 Fe I levels with energies up to 8.4eV. These provided 3000 detectable Fe I lines from 1600A to 5.4mu, and yielded empirical gf-values for 640 of these. Here we propose high-resolution UV spectra reaching 1780A for the first time at the turnoff, to detect and identify the strongest Fe I lines at 1800 - 1850A. This should add 250 new Fe I levels. These spectra, plus one at lower resolution reaching 1620A, will also provide empirical UV templates for turnoff stars at high redshifts as well as low. This is essential to deriving age and metallicity independently for globular clusters and old galaxies out to z 3. It will also improve abundances of trace elements in metal-poor stars, constraining nucleosynthesis at early epochs and aiding the reconstruction of the populations of the Milky Way halo and of nearby globular clusters.
Guo, Zongrang; Niu, Qingfen; Li, Tianduo
2018-07-05
Developing low-cost and efficient sensors for rapid, selective and sensitive detection of the transition metal ions in environmental and food science is very important. In this study, a novel dual-functional fluorescent "turn-on" sensor 3TP based on oligothiophene-phenylamine Schiff base has been synthesized for discrimination and simultaneous detection of both Al 3+ and Fe 3+ ions with high selectivity and anti-interference over other metal ions. Sensor 3TP displayed a very fast fluorescence-enhanced response towards Al 3+ and Fe 3+ ions with low detection limits (0.177μM for Al 3+ and 0.172μM for Fe 3+ ) and wide pH response range (4.0-12.0). The Al 3+ /Fe 3+ sensing mechanisms were investigated by fluorescence experiments, 1 H NMR titrations, FT-IR and ESI-MS spectra. Importantly, sensor 3TP was served as an efficient solid material for the highly sensitive and selective detection of Fe 3+ on TLC plates. Moreover, the sensor 3TP has been successfully used to detect trace Al 3+ and Fe 3+ in environment and food samples with satisfactory results and good recoveries, revealing a convenient, reliable and accurate method for Al 3+ and Fe 3+ analysis in real samples. Copyright © 2018 Elsevier B.V. All rights reserved.
NASA Astrophysics Data System (ADS)
Guo, Zongrang; Niu, Qingfen; Li, Tianduo
2018-07-01
Developing low-cost and efficient sensors for rapid, selective and sensitive detection of the transition metal ions in environmental and food science is very important. In this study, a novel dual-functional fluorescent "turn-on" sensor 3TP based on oligothiophene-phenylamine Schiff base has been synthesized for discrimination and simultaneous detection of both Al3+ and Fe3+ ions with high selectivity and anti-interference over other metal ions. Sensor 3TP displayed a very fast fluorescence-enhanced response towards Al3+ and Fe3+ ions with low detection limits (0.177 μM for Al3+ and 0.172 μM for Fe3+) and wide pH response range (4.0-12.0). The Al3+/Fe3+ sensing mechanisms were investigated by fluorescence experiments, 1H NMR titrations, FT-IR and ESI-MS spectra. Importantly, sensor 3TP was served as an efficient solid material for the highly sensitive and selective detection of Fe3+ on TLC plates. Moreover, the sensor 3TP has been successfully used to detect trace Al3+ and Fe3+ in environment and food samples with satisfactory results and good recoveries, revealing a convenient, reliable and accurate method for Al3+ and Fe3+ analysis in real samples.
Soylak, Mustafa; Erdogan, Nilgun D
2006-09-21
A simple and facile preconcentration procedure based on the coprecipitation of trace heavy metal ions with copper(II)-rubeanic acid complex has been developed. The analytical parameters including pH, amounts of rubeanic acid, sample volume, etc. was investigated for the quantitative recoveries of Pb(II), Fe(III), Cd(II), Au(III), Pd(II) and Ni(II). No interferic effects were observed from the concomitant ions. The detection limits for analyte ions by 3 sigma were in the range of 0.14 microg/l for iron-3.4 microg/l for lead. The proposed coprecipitation method was successfully applied to water samples from Palas Lake-Kayseri, soil and sediment samples from Kayseri and Yozgat-Turkey.
Anal, Jasha Momo H.
2014-01-01
Cymbopogon citratus (DC.) Stapf commonly known as lemon grass is used extensively as green tea and even as herbal tea ingredient across the world. Plants have the ability to uptake metals as nutrient from the soil and its environment which are so essential for their physiological and biochemical growth. Concentrations of these twelve trace elements, namely, Mg, Ca, Cr, Mn, Fe, Ni, Cu, Zn, Mo, As, Cd, and Pb, are analysed by graphite furnace-atomic absorption spectroscopy (GF-AAS) and are compared with the permissible limits of FAO/WHO, ICMR, and NIH, USA, which are found to be within permissible limits. Toxic metals like As, Cd, and Pb, analysed are within the tolerable daily diet limit and at low concentration. PMID:25525430
Ussher, Simon J; Milne, Angela; Landing, William M; Attiq-ur-Rehman, Kakar; Séguret, Marie J M; Holland, Toby; Achterberg, Eric P; Nabi, Abdul; Worsfold, Paul J
2009-10-12
A detailed investigation into the performance of two flow injection-chemiluminescence (FI-CL) manifolds (with and without a preconcentration column) for the determination of sub-nanomolar dissolved iron (Fe(II)+Fe(III)), following the reduction of Fe(III) by sulphite, in seawater is described. Kinetic experiments were conducted to examine the efficiency of reduction of inorganic Fe(III) with sulphite under different conditions and a rigorous study of the potential interference caused by other transition metals present in seawater was conducted. Using 100microM concentrations of sulphite a reduction time of 4h was sufficient to quantitatively reduce Fe(III) in seawater. Under optimal conditions, cobalt(II) and vanadium(IV)/(III) were the major positive interferences and strategies for their removal are reported. Specifically, cobalt(II) was masked by the addition of dimethylglyoxime to the luminol solution and vanadium(IV) was removed by passing the sample through an 8-hydroxyquinoline column in a low pH carrier stream. Manganese(II) also interfered by suppression of the CL response but this was not significant at typical open ocean concentrations.
NASA Astrophysics Data System (ADS)
Tang, Xu; Han, Juan; Wang, Yun; Ni, Liang; Bao, Xu; Wang, Lei; Zhang, Wenli
2017-02-01
Chemosensors play important parts in the selective recognition of ions, which is widely applied in various fields of environment, industry and biological sciences. In this work, a chemosensor for multi-metal ions based on rhodamine B derivative was synthesized, which could selectively recognize various metal ions in different solvent system. The addition of Cu2 + caused the color change from colorless to pink in EtOH/H2O (v/v = 1:1) solvent system, which could be quickly identified by the naked eyes with a detection limit of 8.27 × 10- 8 M. In ethanol solution system, the addition of Fe3 + and Zn2 + caused different fluorescence changes with the detection limit of 2.12 × 10- 7 M and 6.64 × 10- 7 M respectively. The binding ratios are 1:1 (1-Cu2 +), 2:1 (1-Fe3 +) and 1:1 (1-Zn2 +), respectively. Meanwhile, the probe 1 was used to detect the trace metal ions in real water samples. Besides, the probe 1 showed sensitive fluorescence signals for Fe3 + in biological cells. The experimental results further verify the application value of the sensor.
Cation hydrolysis and the regulation of trace metal composition in seawater
NASA Astrophysics Data System (ADS)
Kumar, M. Dileep
1987-08-01
Thermodynamic calculations have been performed for cation hydrolysis, including temperatures from 2°C to the high values of significance near Mid-Oceanic Ridge Systems (MORS). Eighteen elements with wide range of residence times ( t) in seawater (Mn, Th, Al, Bi, Ce, Co, Cr(III), Fe, Nd, Pb, Sc, Sm, Ag, Cd, Cu, Hg, Ni and Zn) have been considered. A model for the regulation of trace metal composition in seawater by cation hydrolytic processes, including those at MORS, is presented. Results show an increase in the abundance of neutral metal hydroxyl species with increase in temperature. During hydrothermal mixing, as the temperature increases, transformation from lower positive hydroxyl complexes to higher or neutral complexes would occur for Cd, Ce, Co, Cr(III), Cu, Mn, Nd, Ni, Pb, Sm and Zn. pH values for adsorption of the metal ion onto solid surfaces have direct relation with pH values of hydrolysis. Co, Mn and Pb could be oxidized to higher states (at Mn-oxide surfaces) that would occur even at MORS. Ce can also be oxidized at 25°C. Solubility calculations show that Al, Bi, Cr(III), Sc, Fe and Th are saturated while Ce, Nd and Sm are not with respect to their oxyhydroxide solids at their concentrations in seawater at 25°C. Cu, Hg, Ni and Zn reach saturation equilibrium at 250°C, whereas Co, Mn and Pb exhibit unsaturation. The results suggest an increase in scavenging capacity of a cation with rise in temperature.
Praveena, S M; Omar, N A
2017-11-15
Heavy metal in rice studies has attracted a greater concern worldwide. However, there have been limited studies on marketed rice samples although it represents a vital ingestion portion for a real estimation of human health risk. This study was aimed to determine both total and bioaccessible of trace elements and heavy metals (Cd, Cr, Cu, Co, Al, Zn, As, Pb and Fe) in 22 varieties of cooked rice using an inductively coupled plasma-optical emission spectroscopy. Both total and bioaccessible of trace elements and heavy metals were digested using closed-nitric acid digestion and Rijksinstituut voor Volksgezondheid en Milieu (RIVM) in vitro digestion model, respectively. Human health risks via Health Risk Assessment (HRA) were conducted to understand exposure risks involving adults and children representing Malaysian population. Zinc was the highest while As was the lowest contents for total and in their bioavailable forms. Four clusters were identified: (1) Pb, As, Co, Cd and Cr; (2) Cu and Al; (3) Fe and (4) Zn. For HRA, there was no any risks found from single element exposure. While potential carcinogenic health risks present for both adult and children from single As exposure (Life time Cancer Risk, LCR>1×10 -4 ). Total Hazard Quotient values for adult and children were 27.0 and 18.0, respectively while total LCR values for adult and children were 0.0049 and 0.0032, respectively. Copyright © 2017 Elsevier Ltd. All rights reserved.
Micronutrient metal speciation is controlled by competitive organic chelation in grassland soils
Boiteau, Rene M.; Shaw, Jared B.; Pasa-Tolic, Ljiljana; ...
2018-03-08
Many elements are scarcely soluble in aqueous conditions found in high pH environments, such as calcareous grassland soils, unless complexed to strong binding organic ligands. To overcome this limitation, some plants and microbes produce chelators that solubilize micronutrient metals such as Fe, Ni, Cu, and Zn from mineral phases. These complexes are taken up by organisms via specific membrane receptors, thereby differentially impacting the bioavailability of these metals to the plant and microbial community. Although the importance of these chelation strategies for individual organisms has been well established, little is known about which pathways coexist within rhizosphere microbiomes or howmore » they interact and compete for metal binding. Identifying these metallophores within natural ecosystems has remained a formidable analytical challenge due to the vast diversity of compounds and poorly defined metabolic processes in complex soil matrices. Herein, we employed recently developed liquid chromatography (LC) mass spectrometry (MS) methods to characterize the speciation of water-soluble dissolved trace elements (Fe, Ni, Cu, and Zn) of soils from native tallgrass prairies in Kansas and Iowa. Both plant and fungal metallophores were identified, revealing compound-specific patterns of chelation to biologically essential metals. Numerous metabolites typically implicated in plant Fe acquisition and homeostasis, including mugineic acids, deoxymugineic acid, nicotianamine, and hydroxynicotianamines, dominated the speciation of divalent metals such as Ni, Cu, and Zn (2–90 pmol/g soil). In contrast, the fungal siderophore ferricrocin was specific for trivalent Fe (7–32 pmol/g soil). These results define biochemical pathways that underpin the regulation of metals in the grassland rhizosphere. They also raise new questions about the competition of these compounds for metal binding and their bioavailability to different members of the rhizosphere population. In conclusion, small structural modifications result in significant differences in metal ligand selectivity, and likely impact metal uptake within the rhizosphere of grassland soils.« less
Micronutrient metal speciation is controlled by competitive organic chelation in grassland soils
DOE Office of Scientific and Technical Information (OSTI.GOV)
Boiteau, Rene M.; Shaw, Jared B.; Pasa-Tolic, Ljiljana
Many elements are scarcely soluble in aqueous conditions found in high pH environments, such as calcareous grassland soils, unless complexed to strong binding organic ligands. To overcome this limitation, some plants and microbes produce chelators that solubilize micronutrient metals such as Fe, Ni, Cu, and Zn from mineral phases. These complexes are taken up by organisms via specific membrane receptors, thereby differentially impacting the bioavailability of these metals to the plant and microbial community. Although the importance of these chelation strategies for individual organisms has been well established, little is known about which pathways coexist within rhizosphere microbiomes or howmore » they interact and compete for metal binding. Identifying these metallophores within natural ecosystems has remained a formidable analytical challenge due to the vast diversity of compounds and poorly defined metabolic processes in complex soil matrices. Herein, we employed recently developed liquid chromatography (LC) mass spectrometry (MS) methods to characterize the speciation of water-soluble dissolved trace elements (Fe, Ni, Cu, and Zn) of soils from native tallgrass prairies in Kansas and Iowa. Both plant and fungal metallophores were identified, revealing compound-specific patterns of chelation to biologically essential metals. Numerous metabolites typically implicated in plant Fe acquisition and homeostasis, including mugineic acids, deoxymugineic acid, nicotianamine, and hydroxynicotianamines, dominated the speciation of divalent metals such as Ni, Cu, and Zn (2–90 pmol/g soil). In contrast, the fungal siderophore ferricrocin was specific for trivalent Fe (7–32 pmol/g soil). These results define biochemical pathways that underpin the regulation of metals in the grassland rhizosphere. They also raise new questions about the competition of these compounds for metal binding and their bioavailability to different members of the rhizosphere population. In conclusion, small structural modifications result in significant differences in metal ligand selectivity, and likely impact metal uptake within the rhizosphere of grassland soils.« less
NASA Astrophysics Data System (ADS)
Rivaro, Paola; Ianni, Carmela; Massolo, Serena; Abelmoschi, M. Luisa; De Vittor, Cinzia; Frache, Roberto
2011-05-01
The distribution of the dissolved labile and of the particulate Fe and Cu together with dissolved oxygen, nutrients, chlorophyll a and total particulate matter was investigated in the surface waters of Terra Nova Bay polynya in mid-January 2003. The measurements were conducted within the framework of the Italian Climatic Long-term Interactions of the Mass balance in Antarctica (CLIMA) Project activities. The labile dissolved fraction was operationally defined by employing the chelating resin Chelex-100, which retains free and loosely bound trace metal species. The dissolved labile Fe ranges from below the detection limit (0.15 nM) to 3.71 nM, while the dissolved labile Cu from below the detection limit (0.10 nM) to 0.90 nM. The lowest concentrations for both metals were observed at 20 m depth (the shallowest depth for which metals were measured). The concentration of the particulate Fe was about 5 times higher than the dissolved Fe concentration, ranging from 0.56 to 24.83 nM with an average of 6.45 nM. The concentration of the particulate Cu ranged from 0.01 to 0.71 nM with an average of 0.17 nM. The values are in agreement with the previous data collected in the same area. We evaluated the role of the Fe and Cu as biolimiting metals. The N:dissolved labile Fe ratios (18,900-130,666) would or would not allow a complete nitrate removal, on the basis of the N:Fe requirement ratios that we calculated considering the N:P and the C:P ratios estimated for diatoms. This finding partially agrees with the Si:N ratio that we found (2.29). Moreover we considered a possible influence of the dissolved labile Cu on the Fe uptake process.
Okuda, Tomoaki; Katsuno, Masayuki; Naoi, Daisuke; Nakao, Shunsuke; Tanaka, Shigeru; He, Kebin; Ma, Yongliang; Lei, Yu; Jia, Yingtao
2008-06-01
Daily observations of hazardous trace metal concentrations in aerosols in Beijing, China were made in the period from 2001 to 2006. We considered coal combustion as a major source of some anthropogenic metals by achieving a correlation analysis and by investigating enrichment factors and relative composition of metals. A possible extra source of some specific metals, such as Cu and Sb, was brake abrasion particles, however, we did not think the transport-related particle was a major source for the hazardous anthropogenic metals even though they could originate from vehicle exhaust and brake/tire abrasion particles. A time-trend model was used to describe temporal variations of chemical constituent concentrations during the five-year period. Several crustal elements, such as Al, Ti, V, Cr, Mn, Fe, and Co, did not show clear increases, with annual rates of change of -15.2% to 3.6%. On the other hand, serious increasing trends were noted from several hazardous trace metals. Cu, Zn, As, Cd, and Pb, which are derived mainly from anthropogenic sources, such as coal combustion, showed higher annual rate of change (4.9-19.8%, p<0.001) according to the regression model. In particular, the Cd and Pb concentrations increased remarkably. We hypothesize that the trend towards increasing concentrations of metals in the air reflects a change that has occurred in the process of burning coal, whereby the use of higher temperatures for coal combustion has resulted in increased emissions of these metals. The increasing use of low-rank coal may also explain the observed trends. In addition, nonferrous metal smelters are considered as a potential, albeit minor, reason for the increasing atmospheric concentrations of anthropogenic hazardous metals in Beijing city.
Mechanisms for chelator stimulation of microbial Fe(III) -oxide reduction
Lovley, D.R.; Woodward, J.C.
1996-01-01
The mechanisms by which nitrilotriacetic acid (NTA) stimulated Fe(III) reduction in sediments from a petroleum-contaminated aquifer were investigated in order to gain insight into how added Fe(III) chelators stimulate the activity of hydrocarbon-degrading, Fe(III)-reducing microorganisms in these sediments, and how naturally occurring Fe(III) chelators might promote Fe(III) reduction in aquatic sediments. NTA solubilized Fe(III) from the aquifer sediments. NTA stimulation of microbial Fe(III) reduction did not appear to be the result of making calcium, magnesium, potassium, or trace metals more available to the microorganisms. Stimulation of Fe(III) reduction could not be attributed to NTA serving as a source of carbon or fixed nitrogen for Fe(III)-reducing bacteria as NTA was not degraded in the sediments. Studies with the Fe(III)-reducing microorganism, Geobacter metallireducens, and pure Fe(III)-oxide forms, demonstrated that NTA stimulated the reduction of a variety of Fe(III) forms, including highly crystalline Fe(III)-oxides such as goethite and hematite. The results suggest that NTA solubilization of insoluble Fe(III)-oxide is an important mechanism for the stimulation of Fe(III) reduction by NTA in aquifer sediments.
Ansari, T M; Marr, I L; Coats, A M
2001-02-01
This study was carried out to characterise the mineralogical forms of barium and the trace heavy metal impurities in commercial barytes of different origins using electron probe microanalysis (EPMA), X-ray diffraction (XRD) and inductively coupled plasma mass spectrometry (ICP-MS). Qualitative EPMA results show the presence of typically eight different minerals in commercial barytes including barite (BaSO4), barium feldspar, galena (PbS), pyrite (FeS2), sphalerite (ZnS), quartz (SiO2), and silicates, etc. Quantitative EPMA confirms that the barite crystals in the barytes contain some strontium and a little calcium, whereas trace heavy metals occur in the associated minerals. Analysis of aqua regia extracts of barytes samples by ICP-MS has shown the presence of a large number of elements in the associated minerals. Arsenic, copper and zinc concentrations correlate closely in all 10 samples. The findings suggest that barytes is not, as traditionally thought, an inert mineral, but is a potentially toxic substance due to its associated heavy metal impurities, which can be determined by an aqua regia digest without the need for complete dissolution of the barite itself. X-ray powder diffraction was not informative as the complex barite pattern masks the very weak lines from the small amounts of associated minerals.
Trace metals in bulk precipitation and throughfall in a suburban area of Japan
NASA Astrophysics Data System (ADS)
Hou, H.; Takamatsu, T.; Koshikawa, M. K.; Hosomi, M.
Throughfall and bulk precipitation samples were collected monthly for 1.5 years over bare land and under canopies of Japanese cedar ( Cryptomeria japonica), Japanese red pine ( Pinus densiflora), Japanese cypress ( Chamaecyparis obtusa), and bamboo-leafed oak ( Quercus myrsinaefolia) in a suburban area of Japan. Samples were analyzed for dissolved Al, Mn, Fe, Cu, Zn, Ag, In, Sn, Sb and Bi by ICP-AES and ICP-MS. The metal concentrations were higher in throughfall, especially that of C. japonica, than bulk precipitation. Enrichment ratios (ERs: ratios of metal concentrations in throughfall to those in bulk precipitation) ranged from 2.5 (Zn) to 5.3 (Ag) (3.9 on average), and ERs for slightly soluble metals were generally higher than those for easily soluble metals. Concentrations of Mn, Fe, Cu, and Zn accounted for 99% of the total concentration of heavy metals in rainwater, whereas those of rare metals such as Ag, In, Sn, and Bi totaled <0.23%. Average concentrations of rare metals were 0.002 and 0.010 μg l -1 for Ag, 0.001 and 0.005 μg l -1 for In, 0.062 and 0.21 μg l -1 for Sn, and 0.006 and 0.023 μg l -1 for Bi in bulk precipitation and throughfall, respectively. The metal concentrations in rainwater were negatively correlated to the volume of rainwater, indicating that washout is the main mechanism that incorporates metals into rainwater. From the enrichment factors, that is, (X/Al) rain/(X/Al) crust, metals other than Fe were shown to be more enriched in rainwater than in the Earth's crust, including those present as a result of leaching from soil dust (Mn) and from anthropogenic sources (Cu, Zn, Ag, In, Sn, Sb, and Bi).
Nondegenerate valleys in the half-metallic ferromagnet Fe/WS 2
NASA Astrophysics Data System (ADS)
Messaoudi, Omar; Ibañez-Azpiroz, Julen; Bouzar, Hamid; Lounis, Samir
2018-01-01
We present a first-principles investigation of the electronic properties of monolayer WS2 coated with an overlayer of Fe. Our ab initio calculations reveal that the system is a half-metallic ferromagnet with a gap of ˜1 eV for the majority spin channel. Furthermore, the combined effect of time-reversal symmetry breaking due to the magnetic Fe overlayer and the large spin-orbit coupling induced by W gives rise to nondegenerate K and K' valleys. This has a tremendous impact on the excited-state properties induced by externally applied circularly polarized light. Our analysis demonstrates that the latter induces a singular hot-spot structure of the transition probability around the K and K' valleys for right and left circular polarization, respectively. We trace back the emergence of this remarkable effect to the strong momentum dependent spin-noncollinearity of the valence band involved. As a main consequence, a strong valley-selective magnetic circular dichroism is obtained, making this system a prime candidate for spintronics and photonics applications.
Essential and toxic elements in honeys from a region of central Italy.
Meli, M A; Desideri, D; Roselli, C; Benedetti, C; Feduzi, L
2015-01-01
Levels of iron (Fe), manganese (Mn), chromium (Cr), copper (Cu), zinc (Zn), mercury (Hg), cadmium (Cd), and lead (Pb) in several types of honey produced in a region of Central Italy were determined by atomic absorption spectroscopy (AAS). The degree of humidity, sugar content, pH, free acidity, combined acidity (lactones), and total acidity were also measured. These elements were found to be present in honey in various proportions depending upon (1) the area foraged by bees, (2) flower type visited for collection of nectar, and (3) quality of water in the vicinity of the hive. Strong positive correlations occurred between Pb and Hg, Pb and Cd, Pb and Fe, Pb and Cr, Hg and Cd, and Hg and Fe. The honey products synthesized in Central Italy were of good quality, but not completely free of heavy metal contamination. Compared with established recommended daily intakes, heavy metals or trace element intoxication following honey consumption in Italy was found not to be a concern for human health.
NASA Astrophysics Data System (ADS)
McKinley, C. C.; Scudder, R.; Thomas, D. J.
2016-12-01
The Neodymium Isotopic composition (Nd IC) of oxide coatings has been applied as a tracer of water mass composition and used to address fundamental questions about past ocean conditions. The leached authigenic oxide coating from marine sediment is widely assumed to reflect the dissolved trace metal composition of the bottom water interacting with sediment at the seafloor. However, recent studies have shown that readily reducible sediment components, in addition to trace metal fluxes from the pore water, are incorporated into the bottom water, influencing the trace metal composition of leached oxide coatings. This challenges the prevailing application of the authigenic oxide Nd IC as a proxy of seawater composition. Therefore, it is important to identify the component end-members that create sediments of different lithology and determine if, or how they might contribute to the Nd IC of oxide coatings. To investigate lithologic influence on the results of sequential leaching, we selected two sites with complete bulk sediment statistical characterization. Site U1370 in the South Pacific Gyre, is predominantly composed of Rhyolite ( 60%) and has a distinguishable ( 10%) Fe-Mn Oxyhydroxide component (Dunlea et al., 2015). Site 1149 near the Izu-Bonin-Arc is predominantly composed of dispersed ash ( 20-50%) and eolian dust from Asia ( 50-80%) (Scudder et al., 2014). We perform a two-step leaching procedure: a 14 mL of 0.02 M hydroxylamine hydrochloride (HH) in 20% acetic acid buffered to a pH 4 for one hour, targeting metals bound to Fe- and Mn- oxides fractions, and a second HH leach for 12 hours, designed to remove any remaining oxides from the residual component. We analyze all three resulting fractions for a large suite of major, trace and rare earth elements, a sub-set of the samples are also analyzed for Nd IC. We use multivariate statistical analyses of the resulting geochemical data to identify how each component of the sediment partitions across the sequential extractions. Here we present results comparing the two sites, and examine how the composition of the sediment impacts the resulting Nd IC.
Rapid, Selective Heavy Metal Removal from Water by a Metal–Organic Framework/Polydopamine Composite
2018-01-01
Drinking water contamination with heavy metals, particularly lead, is a persistent problem worldwide with grave public health consequences. Existing purification methods often cannot address this problem quickly and economically. Here we report a cheap, water stable metal–organic framework/polymer composite, Fe-BTC/PDA, that exhibits rapid, selective removal of large quantities of heavy metals, such as Pb2+ and Hg2+, from real world water samples. In this work, Fe-BTC is treated with dopamine, which undergoes a spontaneous polymerization to polydopamine (PDA) within its pores via the Fe3+ open metal sites. The PDA, pinned on the internal MOF surface, gains extrinsic porosity, resulting in a composite that binds up to 1634 mg of Hg2+ and 394 mg of Pb2+ per gram of composite and removes more than 99.8% of these ions from a 1 ppm solution, yielding drinkable levels in seconds. Further, the composite properties are well-maintained in river and seawater samples spiked with only trace amounts of lead, illustrating unprecedented selectivity. Remarkably, no significant uptake of competing metal ions is observed even when interferents, such as Na+, are present at concentrations up to 14 000 times that of Pb2+. The material is further shown to be resistant to fouling when tested in high concentrations of common organic interferents, like humic acid, and is fully regenerable over many cycles. PMID:29632880
Provenance of fine-grained sediments in the inner shelf of the Korea Strait (South Sea), Korea
NASA Astrophysics Data System (ADS)
Um, In kwon; Choi, Man Sik; Bae, Sung Ho; Song, Yunho; Kong, Gee Soo
2017-12-01
Major metals (Al, Fe, Mg, and Ti), trace metals (Li, Cs, Sc, and Rb), and rare earth elements (REEs) in the fine-grained sediments (< 15 μm) of the central South Sea mud (CSSM) were analyzed to determine the sediment provenance. The spatial distribution of the analyzed elements showed a clear separation between the western (W-CSSM) and eastern (E-CSSM) regions of the CSSM. Concentrations of Fe, Ti, Mg, Sc, and REEs were higher in the WCSSM, whereas concentrations of Al, Cs, Li, and Rb were higher in the E-CSSM. Unlike the ratios of trace metals ((Cs+Sc)/Li and Rb/Li), REEs could not be used to track the provenance of fine-grained sediments because of a grain size effect. The mixing relationships of the provenance indicators showed that the fine-grained sediments of the CSSM comprise a mixture of the sediments discharged from the Seomjin River (SRS) and sediments eroded and transported from the Heuksan mud belt (HMBS) area by the Korean Coastal Current. Sediments originating from the HMB were deposited mostly in the W-CSSM, whereas those from the Seomjin River were deposited mostly in the E-CSSM. This study indicated that sediments from Chinese rivers as well as the Geum River are important even in the inner shelf of the South Sea of Korea.
Provenance of Fine-grained Sediments in the Inner Shelf of the Korea Strait (South Sea), Korea
NASA Astrophysics Data System (ADS)
Um, In kwon; Choi, Man Sik; Bae, Sung Ho; Song, Yunho; Kong, Gee Soo
2018-03-01
Major metals (Al, Fe, Mg, and Ti), trace metals (Li, Cs, Sc, and Rb), and rare earth elements (REEs) in the fine-grained sediments (< 15 μm) of the central South Sea mud (CSSM) were analyzed to determine the sediment provenance. The spatial distribution of the analyzed elements showed a clear separation between the western (W-CSSM) and eastern (E-CSSM) regions of the CSSM. Concentrations of Fe, Ti, Mg, Sc, and REEs were higher in the WCSSM, whereas concentrations of Al, Cs, Li, and Rb were higher in the E-CSSM. Unlike the ratios of trace metals ((Cs+Sc)/Li and Rb/Li), REEs could not be used to track the provenance of fine-grained sediments because of a grain size effect. The mixing relationships of the provenance indicators showed that the fine-grained sediments of the CSSM comprise a mixture of the sediments discharged from the Seomjin River (SRS) and sediments eroded and transported from the Heuksan mud belt (HMBS) area by the Korean Coastal Current. Sediments originating from the HMB were deposited mostly in the W-CSSM, whereas those from the Seomjin River were deposited mostly in the E-CSSM. This study indicated that sediments from Chinese rivers as well as the Geum River are important even in the inner shelf of the South Sea of Korea.
NASA Astrophysics Data System (ADS)
Wilson, Robert F.; Teske, Johanna; Majewski, Steven R.; Cunha, Katia; Smith, Verne; Souto, Diogo; Bender, Chad; Mahadevan, Suvrath; Troup, Nicholas; Allende Prieto, Carlos; Stassun, Keivan G.; Skrutskie, Michael F.; Almeida, Andrés; García-Hernández, D. A.; Zamora, Olga; Brinkmann, Jonathan
2018-02-01
The Apache Point Observatory Galactic Evolution Experiment (APOGEE) has observed ∼600 transiting exoplanets and exoplanet candidates from Kepler (Kepler Objects of Interest, KOIs), most with ≥18 epochs. The combined multi-epoch spectra are of high signal-to-noise ratio (typically ≥100) and yield precise stellar parameters and chemical abundances. We first confirm the ability of the APOGEE abundance pipeline, ASPCAP, to derive reliable [Fe/H] and effective temperatures for FGK dwarf stars—the primary Kepler host stellar type—by comparing the ASPCAP-derived stellar parameters with those from independent high-resolution spectroscopic characterizations for 221 dwarf stars in the literature. With a sample of 282 close-in (P< 100 days) KOIs observed in the APOGEE KOI goal program, we find a correlation between orbital period and host star [Fe/H] characterized by a critical period, {P}{crit}={8.3}-4.1+0.1 days, below which small exoplanets orbit statistically more metal-enriched host stars. This effect may trace a metallicity dependence of the protoplanetary disk inner radius at the time of planet formation or may be a result of rocky planet ingestion driven by inward planetary migration. We also consider that this may trace a metallicity dependence of the dust sublimation radius, but we find no statistically significant correlation with host {T}{eff} and orbital period to support such a claim.
Reiman, Jeremy H; Xu, Y Jun; He, Songjie; DelDuco, Emily M
2018-08-01
Discharging 680 km 3 of freshwater annually to the Northern Gulf of Mexico (NGOM), the Mississippi-Atchafalaya River System (MARS) plays a significant role in transporting major and trace elements to the ocean. In this study, we analyzed total recoverable concentrations of thirty-one metals from water samples collected at five locations along the MARS during 2013-2016 to quantify their seasonal mass exports. The Atchafalaya River flows through a large swamp floodplain, allowing us to also test the hypothesis that floodplains function as a sink for metals. We found that the seven major elements (Ca, Na, Mg, Si, K, Al, and Fe) constituted 99% of the total annual mass load of metals (7.38 × 10 7 tons) from the MARS. Higher concentrations of Al, Ba, B, Ca, Fe, Mg, Mn, Ag, and Ti were found in the Mississippi River, while significantly higher Si and Na concentrations were found in the Atchafalaya River. Significant relationships were found between daily discharge and daily loads of Ba, Ca, Fe, K, Sr, and Ti in both rivers, while significant relationships were also found for Al, Mg, Mn, V, and Zn in the Atchafalaya River and B in the Mississippi River. Overall, the Mississippi River contributed 64-76% of the total annual loading of metals from the MARS to the NGOM. Daily loads of Al, Ba, B, Fe, Li, Mn, P, K, Si, Ag, Ti, V, and Zn regularly decreased upstream to downstream in the Atchafalaya River, partially accepting the initial hypothesis on metals transport in river floodplains. Copyright © 2018 Elsevier Ltd. All rights reserved.
History of Metal Veins in Acapulcoite-Lodranite Clan Meteorite GRA 95209
NASA Technical Reports Server (NTRS)
Herrin, J. S.; Mittlefehldt, D. W.; Humayun, M.
2006-01-01
Graves Nunataks (GRA) 95209 has been hailed as the missing link of core formation processes in the acapulcoitelodranite parent asteroid because of the presence of a complex cm-scale metal vein network. Because the apparent liquid temperature of the metal vein (approximately 1500 C) is higher than inferred for the metamorphic grade of the meteorite, questions regarding the vein s original composition, temperature, and mechanism of emplacement have arisen. We have determined trace siderophile element compositions of metals in veins and surrounding matrix in an effort to clarify matters. We analyzed metals in GRA 95209 in a portion of thick metal vein and adjacent metal-rich (30-40 modal%), sulfide poor (less than 1%) matrix by EPMA and LA-ICP-MS for major and trace siderophile elements using methods described by [3]. We also examined metals from a metal-poor (approximately 15 modal%) and relatively sulfide-rich (2-5 modal%) region of the sample. Kamacite is the dominant metal phase in all portions of the sample. In comparison to matrix metal, vein metal contains more schreibersite and less tetrataenite, and is less commonly associated with Fe,Mn,Mg-bearing phosphates and graphite. Vein kamacite contains higher Co, P, and Cr and lower Cu and Ge. These minor variations aside, all metal types in GRA 95209 are fairly homogeneous in terms of their levels of enrichment of compatible siderophile elements (e.g. Pt, Ir, Os) relative to incompatible siderophile elements (e.g. As, Pd, Au), consistent with the loss of metal-sulfide partial melt that characterizes much of the clan. Whatever compositional differences between matrix and vein metal that may have originally existed, they have since largely co-equilibrated to similar restitic trace element compositions. We agree with [2] that metal veins, in their present state, do not represent a liquid composition. The original vein liquid was much more S-rich and emplaced at correspondingly lower liquid temperatures. Much of the Fe,Ni component solidified in cm scale conduits while S-rich melts were expelled and continued to migrate by percolation. The higher troilite content in metal poor regions of the sample results mostly from trapping of a small portion of these melts. The troilite is not remnant primary sulfide. Strong depletions of W, Mo, and especially Ga (greater than 50%, greater than 60%, and greater than 90% depletion, respectively) in metals of the metalpoor GRA 95209 lithology are localized at scales of 10-100 micrometers in the vicinity of graphite spherules. These depletions must have occurred below the temperatures at which cm-scale equilibration occurred, and future work will seek to determine their cause.
NASA Astrophysics Data System (ADS)
Dias, B.; Barbuy, B.; Saviane, I.; Held, E. V.; Da Costa, G. S.; Ortolani, S.; Gullieuszik, M.; Vásquez, S.
2016-05-01
Context. Globular clusters trace the formation and evolution of the Milky Way and surrounding galaxies, and outline their chemical enrichment history. To accomplish these tasks it is important to have large samples of clusters with homogeneous data and analysis to derive kinematics, chemical abundances, ages and locations. Aims: We obtain homogeneous metallicities and α-element enhancement for 51 Galactic bulge, disc, and halo globular clusters that are among the most distant and/or highly reddened in the Galaxy's globular cluster system. We also provide membership selection based on stellar radial velocities and atmospheric parameters. The implications of our results are discussed. Methods: We observed R ~ 2000 spectra in the wavelength interval 456-586 nm for over 800 red giant stars in 51 Galactic globular clusters. We applied full spectrum fitting with the code ETOILE together with libraries of observed and synthetic spectra. We compared the mean abundances of all clusters with previous work and with field stars. We used the relation between mean metallicity and horizontal branch morphology defined by all clusters to select outliers for discussion. Results: [Fe/H], [Mg/Fe], and [α/Fe] were derived in a consistent way for almost one-third of all Galactic globular clusters. We find our metallicities are comparable to those derived from high-resolution data to within σ = 0.08 dex over the interval -2.5< [Fe/H] < 0.0. Furthermore, a comparison of previous metallicity scales with our values yields σ< 0.16 dex. We also find that the distribution of [Mg/Fe] and [α/Fe] with [Fe/H] for the 51 clusters follows the general trend exhibited by field stars. It is the first time that the following clusters have been included in a large sample of homogeneous stellar spectroscopic observations and metallicity derivation: BH 176, Djorg 2, Pal 10, NGC 6426, Lynga 7, and Terzan 8. In particular, only photometric metallicities were available previously for the first three clusters, and the available metallicity for NGC 6426 was based on integrated spectroscopy and photometry. Two other clusters, HP 1 and NGC 6558, are confirmed as candidates for the oldest globular clusters in the Milky Way. Conclusions: Stellar spectroscopy in the visible at R ~ 2000 for a large sample of globular clusters is a robust and efficient way to trace the chemical evolution of the host galaxy and to detect interesting objects for follow-up at higher resolution and with forthcoming giant telescopes. The technique used here can also be applied to globular cluster systems in nearby galaxies with current instruments and to distant galaxies with the advent of ELTs. Based on observations collected at the European Southern Observatory/Paranal, Chile, under programmes 68.B-0482(A), 69.D-0455(A), 71.D-0219(A), 077.D-0775(A), and 089.D-0493(B).Full Tables 1 and A.2 with the derived average parameters for the 758 red giant stars are only available at the CDS via anonymous ftp to http://cdsarc.u-strasbg.fr (http://130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/590/A9
He, Zhanfei; Geng, Sha; Pan, Yawei; Cai, Chaoyang; Wang, Jiaqi; Wang, Liqiao; Liu, Shuai; Zheng, Ping; Xu, Xinhua; Hu, Baolan
2015-11-15
Nitrite-dependent anaerobic methane oxidation (n-damo) is a potential bioprocess for treating nitrogen-containing wastewater. This process uses methane, an inexpensive and nontoxic end-product of anaerobic digestion, as an external electron donor. However, the low turnover rate and slow growth rate of n-damo functional bacteria limit the practical application of this process. In the present study, the short- and long-term effects of variations in trace metal concentrations on n-damo bacteria were investigated, and the concentrations of trace metal elements of medium were improved. The results were subsequently verified by a group of long-term inoculations (90 days) and were applied in a sequencing batch reactor (SBR) (84 days). The results indicated that iron (Fe(II)) and copper (Cu(II)) (20 and 10 μmol L(-1), respectively) significantly stimulated the activity and the growth of n-damo bacteria, whereas other trace metal elements, including zinc (Zn), molybdenum (Mo), cobalt (Co), manganese (Mn), and nickel (Ni), had no significant effect on n-damo bacteria in the tested concentration ranges. Interestingly, fluorescence in situ hybridization (FISH) showed that a large number of dense, large aggregates (10-50 μm) of n-damo bacteria were formed by cell adhesion in the SBR reactor after using the improved medium, and to our knowledge this is the first discovery of large aggregates of n-damo bacteria. Copyright © 2015 Elsevier Ltd. All rights reserved.
NASA Astrophysics Data System (ADS)
Behrooz, Reza Dahmardeh; Esmaili-Sari, Abbas; Bahramifar, Nader; Kaskaoutis, D. G.; Saeb, Keivan; Rajaei, Fatemeh
2017-04-01
This study analyzes the chemical composition (water-soluble ions and trace elements) of the total suspended particles (TSP) and particulate matter less than 10 and 2.5 μm (PM10 and PM2.5) in the Sistan basin, southeast Iran during the dusty and windy period June - October 2014. Extreme TSP, PM10 and PM2.5 concentrations, means of 1624.8, 433.4 and 320.8 μgm-3, respectively, were recorded in the Zabol sampling site, while the examined water-soluble ions and trace metals constitute small fractions (∼4.1%-17.7%) of the particulate masses. Intense winds on the dust-storm days result in weathering of soil crust and deflation of evaporate minerals from the dried Hamoun lake beds in the Sistan basin. The soil samples are rich in Ca2+, SO42-, Na+ and Cl- revealing the existence of non-sea salts, as well as in Al, Fe and Mg, while the similarity in the chemical composition between soil and airborne samples indicates that the dust events over Sistan are local in origin. In contrast, low concentrations of secondary ions (i.e., nitrate) and heavy metals (i.e., Pb, Cr, Ni, Cu) indicate less anthropogenic and industrial emissions. Enrichment Factor analysis for TSP, PM10 and PM2.5 reveals that the anthropogenic sources contribute a substantial amount in the heavy metals rather than soil crust, while Al, Fe, Sn, Mg are mostly of crustal origin. The results provide essential knowledge in atmospheric chemistry over Sistan and in establishing mitigation strategies for air pollution control.
The Trace Metal Geochemistry of Suspended Oceanic Particulate Matter
1989-08-01
hydrothermal plumes (e.g. TAG, Mid-Atlantic Ridge, 26° N , Nelson et al., 1986; Chapter 6) rise to discrete depth zones of neutral buoyancy...samples from in and near TAG hydrothermal plume . 179 Al vs. Fe (w mat particulate) Ca (A MCOS) s. Fe (P mass Par tla ate) *oI 3c 31 a Sa 2 3 04~ a 21 a...104 42. R.M. Gordon, J.H. Martin and G.A. Knauer, Iron ’ n north- east Pacific waters, Nature 299, 611-612, 1982. 43. J.K.B. Bishop and P.E.
Baysal, Asli; Baltaci, Hakki; Ozbek, Nil; Destanoglu, Orhan; Ustabasi, Gul Sirin; Gumus, Gulcin
2017-06-01
The understanding of the impurities in natural snow is important in realizing its atmospheric quality, soil characteristics, and the pollution caused to the environment. Knowledge of the occurrence of major ions and trace metals in the snow in the megacity of Istanbul is very limited. This manuscript attempts to understand the origin of major soluble ions (fluoride, acetate, formate, chlorite, chloride, nitrite, chlorate, bromide, nitrate, sulfate, phosphate, and perchlorate) and some trace metals (Fe, Mn, Cd, Co, Ni, Pb, Zn, Cu) in winter surface snow, collected in Istanbul, Turkey. The sampling of the surface snow was conducted after each precipitation during the winter of 2015-2016 at three sites in the city. Besides the statistical evaluation of the major ions, and some trace metal concentrations, the chemical variations along with atmospheric circulations, which are important modification mechanisms that influence the concentrations, were investigated in the study. At examined locations and times, 12 major anions were investigated and in these anions fluoride, chlorite, chlorate, bromide, and perchlorate in the snow samples were below the detection limit; only SO 4 2- , NO 3 - , and CI - were found to be in the range of 1.11-17.90, 0.75-4.52, and 0.19-3.01 mg/L. Also, according to the trace element determination, the concentration was found to be 29.2-53.7, 2.0-16.1, 1.0-2.2, 50.1-71.1, 24.2-35.2, ND-7.9, 43.2-106.6, and 3.0-17.7 μg/L for Fe, Mn, Cd, Co, Ni, Pb, Zn, and Cu, respectively. The major anions and investigated trace elements here originated mainly from anthropogenic and atmospheric circulation and mainly influenced by northerly and southerly circulation patterns. While the main limitations in the present study may be the low number of samples that may not be entirely representative, accurately reflect identification, or support other previously observed local measurements, we believe that the type of data presented in this study has the potential to be used in the field of environmental risk assessment and, as result, for human health.
Total reflection X-ray fluorescence analysis of trace-elements in candies marketed in Mexico
NASA Astrophysics Data System (ADS)
Martinez, T.; Lartigue, J.; Zarazua, G.; Avila-Perez, P.; Navarrete, M.; Tejeda, S.
2010-06-01
Trace metals concentrations in food are significant for nutrition, due either to their nature or toxicity. Sweets, including chewing gum and candies, are not exactly a food, but they usually are unwearied consumed by children, the most vulnerable age-group to any kind of metal contamination in the food chain. The presence of relatively high concentrations of heavy metals such as Lead elicits concern since children are highly susceptible to heavy metals poisoning. Trace-metals concentrations were determined for six different flavors of a Mexican candy by means of Total X-ray Fluorescence Spectrometry. Triplicate samples of the various candy's flavours (strawberry, pineapple, lemon, blackberry, orange and chilli) were digested in 8 mL of a mix of supra-pure HNO 3 and H 2O 2 (6 mL: 2 mL) in a microwave oven MARS-X. Results show the presence of essential and toxic elements such as Ti, Cr, Mn, Fe, Ni, Cu, Zn, Br, Rb, Sr, and Pb. All metal concentrations were higher and significantly different ( α = 0.05) in chilli candy, compared to other candy flavours. Lead concentration fluctuated in the range of 0.102 to 0.342 μg g - 1 . A discussion about risk consumption and concentration allowed by Mexican and International Norms is made. As a part of the Quality Control Program, a NIST standard of "Citrus Leaves" and a blank were treated in the same way.
Determination of elements in ayurvedic medicinal plants by AAS
DOE Office of Scientific and Technical Information (OSTI.GOV)
Teerthe, Santoshkumar S.; Kerur, B. R., E-mail: kerurbrk@yahoo.com
India has a rich country for the uses of Ayurvedic medicinal plants for treatment and also the north- Karnataka boasts an unparallel diversity of medicinal plants. The present study attempts to estimate and compare the level of trace and heavy metals in some selected leaves and root samples of Ayurvedic medicinal plants such as Mg, Al, K, Cr, Mn, Fe, Cu, Zn, and Cd. The samples are collected from different places of North-Karnataka regions and sample solutions prepared as the ratio of 1:25:25+950ml=1000ppm.the trace and heavy elemental concentration was estimated using Atomic Absorption Spectrometric (AAS) Method. The average concentrations ofmore » Mg, Mn, Fe and Zn, are ranging from 2ppm to 5250.2ppm and potassium (K) has more concentration as compare to all other. The other elements likes Al, Cr, Cu, and Cd were also estimed and presented in the table. Therefore, these medicinal plants are rich in some essential minerals, especially K, Mg, Mn, Fe and Zn which are essential for human health.« less
Urban and industrial contribution to trace elements in the atmosphere as measured in holm oak bark
NASA Astrophysics Data System (ADS)
Drava, Giuliana; Brignole, Daniele; Giordani, Paolo; Minganti, Vincenzo
2016-11-01
The concentrations of As, Cd, Co, Cu, Fe, Mn, Ni, Pb, V and Zn were measured by ICP-OES in samples of bark of the holm oak (Quercus ilex L.) collected from trees in different urban environments (residential and mixed residential/industrial). The use of tree bark as a bioindicator makes it easy to create maps that can provide detailed data on the levels and on the spatial distribution of each trace element. For most of the elements considered (As, Co, Fe, Mn, Ni, V and Zn), the concentrations in the industrial sites are about twice (from 1.9 to 2.8 times higher) of those in the residential area. Arsenic, Fe and Zn show the highest concentrations near a steel plant (operational until 2005), but for the other elements it is not possible to identify any localized source, as evident from the maps. In areas where urban pollution is summed up by the impact of industrial activities, the population is exposed to significantly higher amounts of some metals than people living in residential areas.
Król, Ewelina; Jeszka-Skowron, Magdalena; Krejpcio, Zbigniew; Flaczyk, Ewa; Wójciak, Rafał W
2016-11-01
Mulberry leaves (Morus alba) have been used in folk medicine to mitigate symptoms of diabetes. The mulberry plant contains phenolic compounds that are able to decrease blood glucose concentration. Since various phenolics have antioxidant and metal binding properties, they can be used to alleviate oxidative stress and chelate trace elements involved in redox reactions. The aim of this study was to evaluate the effects of dietary supplementation with mulberry leaf extracts (acetone-water (AE) and ethanol-water (EE)) on the trace element status (Fe, Zn and Cu) in relation to diabetes management and antioxidant indices in high-fat diet-fed/STZ diabetic rats. The experiment was performed on 38 male Wistar rats with diabetes (induced by high-fat diet (HF) and streptozotocin injection) or the control fed with AIN-93M or high-fat diet. As a result, five experimental groups were used: (1) a healthy control group fed with AIN-93M; (2) an HF control group; (3) a diabetic HF group; (4) a diabetic HF + AE group (6 g/kg diet); (5) a diabetic HF + EE group (6 g/kg diet). The rats were fed with appropriate diets for 4 weeks. The content of trace elements (Fe, Zn and Cu) in the serum and tissues was measured by means of atomic absorption spectrometry (AAS). Biochemical analyses (glucose, TBARS, FRAP) were performed on the blood serum. It was shown that the AE decreased hepatic and renal Fe stores, while the EE increased hepatic Cu levels in diabetic rats and confirmed their ability to regulate the Fe and Cu status in diabetes. The results confirmed a significant hypoglycaemic and antioxidant potential of both mulberry leaf extracts in diabetic rats.
Trace elements in human alveolar macrophages studied by PIXE
NASA Astrophysics Data System (ADS)
Weber, G.; Roelandts, I.; Corhay, J. L.; Radermecker, M.; Delavignette, J. P.
1990-04-01
The purpose of this study is to determine the metal content of alveolar macrophages by PIXE from 94 subjects divided into two groups as follows: group (1) — subjects with non-occupational exposure to industrial dust: 30 healthy volunteers (controls), 16 patients suffering from lung cancer; group (2) — 48 healthy steel workers from the Liège area (blast-furnace [ n=29] and coke oven [ n=19]). We hope to define more precisely the influence of carcinoma, smoking habit, pathology and occupational exposure in the steel industry on the macrophage metal content. This study has shown: (a) an Fe and Sr increase and a Br decrease in the macrophages of smokers (especially in heavy smokers): (b) a significant Fe, Ti, Br and Cu increase and a trend to Pb, Cr, As and Sr increase in macrophages of healthy steel workers (especially blast-furnace workers) in comparison with non-exposed controls; (c) a significant Fe, Br, Cu and Zn increase and a trend to Pb, As and Ni increase in macrophages of non-exposed patients with lung cancer by comparison with non-exposed controls. The mechanism of metal change could be explained by professional exposure and endogenous changes (protein synthesis, inflammation, bronchial bleeding, …)
High heterogeneity in soil composition and quality in different mangrove forests of Venezuela.
Otero, X L; Méndez, A; Nóbrega, G N; Ferreira, T O; Meléndez, W; Macías, F
2017-09-18
Mangrove forests play an important role in biogeochemical cycles of metals, nutrients, and C in coastal ecosystems. However, these functions could be strongly affected by the mangrove soil degradation. In this study, we performed an intensive sampling characterizing mangrove soils under different types of environment (lagoon/gulf) and vegetation (Rhizophora/Avicennia/dead mangrove) in the Venezuelan coast. To better understand the spatial heterogeneity of the composition and characteristics of the soils, a wide range of the soil attributes were analyzed. In general, the soils were anoxic (Eh < 200 mV), with a neutral pH and low concentration in toxic metals; nevertheless, they varied widely in the soil and its quality-defining parameters (e.g., clay contents, total organic carbon, Fe, Al, toxic trace metals). It is noteworthy that the mangroves presented a low Fe Pyrite content due to a limitation in the Fe oxyhydroxide contents, especially in soils with higher organic C content (TOC > 15%). Finally, the dead mangrove showed significantly lower amounts of TOC and fibers (in comparison to the well-preserved mangrove forest), which indicates that the C pools in mangrove soils are highly sensitive also to natural impact, such as ENSO.
Iron Uptake in a Shelf Sea: Seasonality and Stoichiometry
NASA Astrophysics Data System (ADS)
Daniels, C. J.; Poulton, A. J.; Moore, M. M.; Birchill, A.; Mayers, K.; Lohan, M. C.
2016-02-01
Primary production by phytoplankton in shelf seas represents a significant contribution to global carbon cycling. Trace metals, such as Iron (Fe), are essential micronutrients for phytoplankton growth, and may ultimately limit primary production. The uptake of iron within natural phytoplankton communities is poorly understood. Using carrier free 55Fe, we are able to obtain novel estimates of biological uptake of Fe using trace level Fe additions that do not perturb the system. Here we present results from a study measuring the uptake of carrier free Iron (55Fe), in parallel with measurements of Carbon (14C) and Phosphorus (33P) uptake; samples were collected from the Celtic sea in spring (April 2015) and summer (July 2015), on-shelf and off-shelf, and in 2 size fractions (Total, >2µm), thus producing a novel dataset of the seasonality of macronutrient and micronutrient uptake by phytoplankton within a shelf sea. Primary production ranged from 1.0 - 2.2 mmol C m-3 d-1 in April and 0.2 - 1.5 mmol C m-3 d-1 in July, with a corresponding higher biomass in April (0.7 - 3.24 mg Chl m-3) than July (0.3 - 1.6 mg Chl m-3). Significant rates of Fe uptake were measured in all samples (e.g. 21 nmol m-3 d-1, on-shelf, April), with variable stoichiometry (e.g. Fe/C of 16 µmol/mol, and Fe/P of 0.4 mmol/mol, on-shelf, April). The results will be presented and examined in the context of the available nutrient pools, the phytoplankton community structure and the impact on biogeochemical cycling.
Mzoughi, Nadia; Chouba, Lassaad
2011-01-01
Under the framework of the IAEA's Technical Co-operation project RAF7/004, international research cruises were carried out in 2004 to assess the distribution of radionuclides and micropollutants in the south-western Mediterranean Sea. Sediments samples had variable concentrations of total aliphatic hydrocarbons and polycyclic aromatic hydrocarbons ranging from 0.2 to 1.8 microg g(-1) and 26.9 to 364.4 ng g(-1), respectively, in the Sicily Channel and from 0.7 to 2.8 microg g(-1) and 14.7 to 618.1 ng g(-1), respectively, in the open sea of the Gulf of Tunis. Hydrocarbon concentrations changed with depth and were relatively high at 3 cm and 10 cm depths. The use of 'fingerprint' ratios of certain isomeric pairs of polycyclic aromatic hydrocarbons (PAH) and the proportion of 2-3 ring and 4-5 ring PAH concentrations showed that the main origins are characteristic of petroleum sources. The ranges of trace metal concentrations, expressed in microgg(-1), in the Sicily Channel and in the Gulf of Tunis, respectively, were: Hg 0.009-0.2 and 0.02-0.1; Pb 9.9-26.1 and 21.2-32.5; Cd 0.06-0.1 and 0.07-0.33; Fe 23.7-28.1 and 29.9-36.2p; Zn 83-99.5 and 83-104; Mn 309.2-752.5 and 651-814; Cu 17.1-18.5 and 33.5-51.3. Sediment metal abundances were in the order: Mn > Zn > Fe > Cu > Pb > Cd > Hg. The results showed significant differences (p < 0.001) for trace metal and hydrocarbon mean concentrations between the two cores. These concentrations are generally similar to the background levels from the Mediterranean Sea and could be affected by physico-chemical conditions and sedimentation rate as well as biodegradation.
Proximate Composition, Amino Acid, Mineral, and Heavy Metal Content of Dried Laver
Hwang, Eun-Sun; Ki, Kyung-Nam; Chung, Ha-Yull
2013-01-01
Laver, a red algae belonging to the genus Porphyra, is one of the most widely consumed edible seaweeds. The most popular commercial dried laver species, P. tenera and P. haitanensis, were collected from Korea and China, respectively, and evaluated for proximate composition, amino acids, minerals, trace heavy metals, and color. The moisture and ash contents of P. tenera and P. haitanensis ranged from 3.66~6.74% and 8.78~9.07%, respectively; crude lipid and protein contents were 1.96~2.25% and 32.16~36.88%, respectively. Dried lavers were found to be a good source of amino acids, such as asparagine, isoleucine, leucine, and taurine, and γ-aminobutyric acid. K, Ca, Mg, Na, P, I, Fe, and Se minerals were selected for analysis. A clear regional variation existed in the amino acid, mineral, and trace metal contents of lavers. Regular consumption of lavers may have heath benefits because they are relatively low in fat and high in protein, and contain functional amino acids and minerals. PMID:24471123
Proximate composition, amino Acid, mineral, and heavy metal content of dried laver.
Hwang, Eun-Sun; Ki, Kyung-Nam; Chung, Ha-Yull
2013-06-01
Laver, a red algae belonging to the genus Porphyra, is one of the most widely consumed edible seaweeds. The most popular commercial dried laver species, P. tenera and P. haitanensis, were collected from Korea and China, respectively, and evaluated for proximate composition, amino acids, minerals, trace heavy metals, and color. The moisture and ash contents of P. tenera and P. haitanensis ranged from 3.66~6.74% and 8.78~9.07%, respectively; crude lipid and protein contents were 1.96~2.25% and 32.16~36.88%, respectively. Dried lavers were found to be a good source of amino acids, such as asparagine, isoleucine, leucine, and taurine, and γ-aminobutyric acid. K, Ca, Mg, Na, P, I, Fe, and Se minerals were selected for analysis. A clear regional variation existed in the amino acid, mineral, and trace metal contents of lavers. Regular consumption of lavers may have heath benefits because they are relatively low in fat and high in protein, and contain functional amino acids and minerals.
Yao, Qingzhen; Wang, Xiaojing; Jian, Huimin; Chen, Hongtao; Yu, Zhigang
2016-02-15
Suspended particulate matter (SPM) samples were collected along a salinity gradient in the Changjiang Estuary in June 2011. A custom-built water elutriation apparatus was used to separate the suspended sediments into five size fractions. The results indicated that Cr and Pb originated from natural weathering processes, whereas Cu, Zn, and Cd originated from other sources. The distribution of most trace metals in different particle sizes increased with decreasing particle size. The contents of Fe/Mn and organic matter were confirmed to play an important role in increasing the level of heavy metal contents. The Cu, Pb, Zn, and Cd contents varied significantly with increasing salinity in the medium-low salinity region, thus indicating the release of Cu, Pb, Zn, and Cd particles. Thus, the transfer of polluted fine particles into the open sea is probably accompanied by release of pollutants into the dissolved compartment, thereby amplifying the potential harmful effects to marine organisms. Copyright © 2015 Elsevier Ltd. All rights reserved.
Defining appropriate methods for studying toxicities of trace metals in nutrient solutions.
Li, Zhigen; Wang, Peng; Menzies, Neal W; Kopittke, Peter M
2018-01-01
The use of inappropriate experimental conditions for examining trace metal phytotoxicity results in data of questionable value. The present study aimed to identify suitable parameters for study of phytotoxic metals in nutrient solutions. First, the literature was reviewed to determine the concentration of six metals (Cd, Cu, Hg, Ni, Pb, and Zn) from solution of contaminated soils. Next, the effects of pH, P, Cl, NO 3 , and four Fe-chelators were investigated by using thermodynamic modelling and by examining changes in root elongation rate of soybean (Glycine max cv. Bunya). The literature review identified that the solution concentrations of metals in soils were low, ranging from (µM) 0.069-11Cd, 0.19-15.8 Cu, 0.000027-0.000079 Hg, 1.0-8.7 Ni, 0.004-0.55 Pb, and 0.4-36.3 Zn. For studies in nutrient solution, pH should generally be low given its effects on solubility and speciation, as should the P concentration due to the formation of insoluble phosphate salts. The concentrations of Cl, NO 3 , and various chelators also influence metal toxicity through alteration of metal speciation. The nutrient solutions used to study metal toxicity should consider environmentally-relevant conditions especially for metal concentrations, with concentrations of other components added at levels that do not substantially alter metal toxicity. Copyright © 2017 Elsevier Inc. All rights reserved.
Hayzoun, H; Garnier, C; Durrieu, G; Lenoble, V; Le Poupon, C; Angeletti, B; Ouammou, A; Mounier, S
2015-01-01
An annual-basis study of the impacts of the anthropogenic inputs from Fez urban area on the water geochemistry of the Sebou and Fez Rivers was conducted mostly focusing on base flow conditions, in addition to the sampling of industrial wastewater characteristic of the various pressures in the studied environment. The measured trace metals dissolved/particulate partitioning was compared to the ones predicted using the WHAM-VII chemical speciation code. The Sebou River, upstream from Fez city, showed a weakly polluted status. Contrarily, high levels of major ions, organic carbon and trace metals were encountered in the Fez River and the Sebou River downstream the Fez inputs, due to the discharge of urban and industrial untreated and hugely polluted wastewaters. Trace metals were especially enriched in particles with levels even exceeding those recorded in surface sediments. The first group of elements (Al, Fe, Mn, Ti, U and V) showed strong inter-relationships, impoverishment in Fez particles/sediments and stable partition coefficient (Kd), linked to their lithogenic origin from Sebou watershed erosion. Conversely, most of the studied trace metals/metalloids, originated from anthropogenic sources, underwent significant changes of Kd and behaved non-conservatively in the Sebou/Fez water mixing. Dissolved/particulate partitioning was correctly assessed by WHAM-VII modeling for Cu, Pb and Zn, depicting significant differences in chemical speciation in the Fez River when compared to that in the Sebou River. The results of this study demonstrated that a lack of compliance in environmental regulations certainly explained this poor status. Copyright © 2014 Elsevier B.V. All rights reserved.
NASA Astrophysics Data System (ADS)
Rushmer, T.; Corgne, A.
2008-12-01
One important method in which to gain insight into metallic liquid compositions and their ability to control HSE (highly siderophile element) distribution is through experimentation. Deformation experiments can additionally provide information into mechanisms and chemical consequences of dynamic liquid metal segregation under a variety of conditions. We report results on metallic liquid HSE compositions and their distribution from a set of deformation experiments on a natural H6 ordinary chondrite, performed under very reducing conditions and a series of phase equilibria experiments focused on HSE partitioning between Si-rich and S-rich Fe molten alloys. The deformation experiments were conducted at temperatures between 925°C and 950°C, at 1.3 GPa confining pressure with a strain rate of 10-4/s. Major element analyses of both silicate and metal phases show that they are considerably reduced and the typically lithophile elements are behaving like siderophiles. Fe-Ni-Si compositions are found in the shear zones produced during the deformation experiment. Metallic compositions also include (Mg,Fe,Ca)S, Fe-Ni-Si, FeP, and Fe-Ni-S quench metal. Silicate phases include forsterite (Fo92-96) and enstatite (En98). Highly siderophile element (HSE) concentrations have been measured in the sulphide ((Fe,Mg,Ca)S) and metal (Fe- Ni-Si) phases by LA-ICPMS and compared with results from an earlier set of experiments on the same material but which were not performed under reducing conditions. The partitioning of the PGE is modified by the changing conditions with elements such as Ir and Os having higher DMetal/Sulphide values under reducing conditions. Partitioning experiments between molten FeS and Ni-, Si-bearing molten Fe were performed at 1.5-5.0 GPa and 1500-1750° to further investigate this observation. The starting material is synthetic, doped with a range of trace and HSE elements. The results confirm the preference of the HSE for the metallic phase with DMetal/Sulphide > 100 in most cases, in contrast to Cu and Ag, which have D values near or below 1, respectively. Our results also suggest the possibility of significant PGE fractionation since D values are larger for Ir and Os and smaller for Pd and Au, with Pt, Ru, Rh having intermediate values. It is not clear with the present data set whether T and P variations can affect significantly HSE partitioning. These results have been applied to the most naturally reduced material we know, the Enstatite chondrites. Several E chondrites have bulk HSE data available, but no HSE data available on sulphide and metallic phases themselves. We have now a set of HSE data for individual metallic phases in several enstatite chondrites, both EH and ELs. The bulk data show that for elements such as Os and Pd, the abundances are positively correlated and overall Pd is much higher in abundance. We find in the experiments that DPd ranges between 10-100, but do not fully explain the bulk trends. Additional phases, such as FeP have therefore been analyzed and we find that Pd is concentrated in FeP and the presence of schreibersite may help explain the high Pd ratios (e.g. Pd/Ir) observed in the Enstatite chondrites.
Experimental determination of the Mo isotope fractionation factor between metal and silicate liquids
NASA Astrophysics Data System (ADS)
Hin, R. C.; Burkhardt, C.; Schmidt, M. W.; Bourdon, B.
2011-12-01
The conditions and chemical consequences of core formation have mainly been reconstructed from experimentally determined element partition coefficients between metal and silicate liquids. However, first order questions such as the mode of core formation or the nature of the light element(s) in the Earth's core are still debated [1]. In addition, the geocentric design of most experimental studies leaves the conditions of core formation on other terrestrial planets and asteroids even more uncertain than for Earth. Through mass spectrometry, records of mass-dependent stable isotope fractionation during high-temperature processes such as metal-silicate segregation are detectable. Stable isotope fractionation may thus yield additional constrains on core formation conditions and its consequences for the chemical evolution of planetary objects. Experimental investigations of equilibrium mass-dependent stable isotope fractionation have shown that Si isotopes fractionate between metal and silicate liquids at temperatures of 1800°C and pressures of 1 GPa, while Fe isotopes leave no resolvable traces of core formation processes [2,3]. Molybdenum is a refractory and siderophile trace element in the Earth, and thus much less prone to complications arising from mass balancing core and mantle and from potential volatile behaviour than other elements. To determine equilibrium mass-dependent Mo isotope fractionation during metal-silicate segregation, we have designed piston cylinder experiments with a basaltic silicate composition and an iron based metal with ~8 wt% Mo, using both graphite and MgO capsules. Metal and silicate phases are completely segregated by the use of a centrifuging piston cylinder at ETH Zurich, thus preventing analysis of mixed metal and silicate signatures. Molybdenum isotope compositions were measured using a Nu Instruments 1700 MC-ICP-MS at ETH Zurich. To ensure an accurate correction of analytical mass fractionation a 100Mo-97Mo double spike was admixed before chemical purification. Initial results provide an equilibrium 98Mo/95Mo isotope fractionation factor between metal and silicate liquids of -0.18±0.10% (2σ) at 1400°C and 1 GPa. Although the relative mass difference of these Mo isotopes is smaller than for Fe isotopes, this result implies that metal-silicate segregation may have led to mass-dependent stable Mo isotope fractionation, as opposed to Fe isotopes. A possible explanation is that the bonding environment of Mo may counterbalance its relatively small mass separation. At reducing conditions, Mo occurs in 4+ valence state in silicates [4] and thus its bond strength difference between metal and silicate may be more similar to that of Si than Fe. Stable Mo isotopes may thus become an important tool for constraining the conditions of core formation in asteroids and terrestrial planets. [1] Rubie et al. (2011) EPSL 301, 31-42. [2] Shahar et al. (2009) EPSL 288, 228-234. [3] Poitrasson et al. (2009) EPSL 278, 376-385. [4] Farges et al. (2006) Can. Min. 44, 731-753.
Core segregation mechanism and compositional evolution of terretrial planets
NASA Astrophysics Data System (ADS)
Petford, N.; Rushmer, T.
2009-04-01
A singular event in the formation of the earth and terrestrial planets was the separation iron-rich melt from mantle silicate to form planetary cores. On Earth, and by implication other rocky planets, this process induced profound internal chemical fractionation, with siderophile elements (Ni, Co, Au, Pt, W, Re) following Fe into the core, leaving the silicate crust and mantle with strong depletions of these elements relative to primitive planetary material. Recent measurements of radiogenic 182W anomalies in the silicate Earth, Mars and differentiated meteorites imply that planetesimals segregated metallic cores within a few Myr of the origin of the solar system. Various models have been put forward to explain the physical nature of the segregation mechanism (Fe-diapirs, ‘raining' through a magma ocean), and more recently melt flow via fractures. In this contribution we present the initial results of a numerical study into Fe segregation in a deforming silicate matrix that captures the temperature-dependent effect of liquid metal viscosity on the transport rate. Flow is driven by pressure gradients associated with impact deformation in a growing planetesimal and the fracture geometry is constrained by experimental data on naturally deformed H6 chondrite. Early results suggest that under dynamic conditions, fracture-driven melt flow can in principle be extremely rapid, leading to a significant draining of the Fe-liquid metal and siderophile trace element component on a timescale of hours to days. Fluid transport in planetesimals where deformation is the driving force provides an attractive and simple way of segregating Fe from host silicate as both precursor and primary agent of core formation. The potential for flow of metal-rich melt to induce local magnetic anomalies will also be addressed.
NASA Astrophysics Data System (ADS)
Gangloff, Sophie; Stille, Peter; Pierret, Marie-Claire; Weber, Tiphaine; Chabaux, François
2014-04-01
Dissolved Organic Carbon (DOC) plays an important role in the behavior of major and trace elements in the soil and influences their transfer from soil to soil solution. The first objective of this study is to characterize different organic functional groups for the Water Extractable Organic Carbon (WEOC) fractions of a forest soil as well as their evolution with depth. The second objective is to clarify the influence of these organic functional groups on the migration of the trace elements in WEOC fractions compared to those in the soil solution obtained by lysimeter plates. All experiments have been performed on an acidic forest soil profile (five depths in the first meter) of the experimental spruce parcel in the Stengbach catchment. The Infra-red spectra of the freeze-dried WEOC fractions show a modification of the molecular structure with depth, i.e. a decrease of the polar compounds such as polysaccharides and an increase of the less polar hydro-carbon functional groups with a maximum value of the aromaticity at 30 cm depth. A Hierarchical Ascending Classification (HAC) of the evolution of Water Extractable Chemical Elements (WECE) with the evolution of the organic functional groups in the organic matter (OM) enriched soil compartments permits recognition of relationships between trace element behavior and the organic functional group variations. More specifically, Pb is preferentially bound to the carboxylic acid function of DOC mainly present in the upper soil compartment and rare earth elements (REE) show similar behavior to Fe, V and Cr with a good affinity to carboxy-phenolic and phenolic groups of DOC. The experimental results show that heavy REE compared to light REE are preferentially bound to the aromatic functional group. This different behavior fractionates the REE pattern of soil solutions at 30 cm depth due to the here observed aromaticity enrichment of DOC. These different affinities for the organic functional groups of the DOC explain some aspects of the behavior of trace elements in soil solutions and in the soil profile but, also the competition between trace elements in complexation with DOC. The results of this study are important for the understanding of the mobility and the migration of pollutants (as heavy metals or radionuclides) as well as nutrients in natural ecosystems. WE PrN/YbN is constant between 3 and 16 cm depth whereas SS PrN/YbN slightly decreases from 0.80 at 5 cm depth to 0.74 at 10 cm depth. This results from Pr (LREE) enrichment in the soil solution of the upper soil compartment caused by vegetation controlled LREE recycling and/or atmospheric depositions (see above). WE PrN/YbN and SS PrN/YbN show similar depth dependent distributions including the enrichment at 30 cm depth. It results from Yb depletion at this depth and enrichment in the deeper soil compartment compared to Pr. Similar to Marsac et al. (2012, 2013) one might suggest that there is competition between Fe3+, Al3+ and REE for the binding with DOC. They have a high affinity with the same organic functional groups which is confirmed by the classification scheme (Fig. 8). The studies of Marsac et al. suggest that at acidic pH and low metal/DOC ratios, Fe3+and Al3+ compete more with HREE than LREE; moreover, at high metal/DOC ratios and acidic pH, Al3+ competes with LREE. The Fig. 13 showing the variations of WECEN for Al and Fe in function of WECEN LREE and HREE confirms Marsac et al.’s observations. The slope of the extrapolation line resulting from WECEN Al and HREE values remains rather unchanged for the OM depleted and enriched soil compartments; thus, the change in the metal/DOC ratio in the soil does not change the extraction behavior of Al and HREE. However, the WECEN Fe strongly increase compared to the corresponding HREE values in the OM enriched compartment pointing to the competition between Fe and HREE. Alternatively, one observes that the WECEN Fe and LREE values in the OM enriched compartment plot on the extrapolation line derived from OM depleted soil samples. Thus, in this case, the change in the metal/DOC ratio does not affect the extraction behavior of Fe and LREE. However, the WECEN values for Al and corresponding LREE of samples from the OM enriched soil compartment plot below the extrapolation line and point to the competition between Al and LREE. These results are also in agreement with the REE distribution pattern of the soil solutions from the same site which are at greater depth LREE depleted (Stille et al., 2009).
Elemental composition of current automotive braking materials and derived air emission factors
NASA Astrophysics Data System (ADS)
Hulskotte, J. H. J.; Roskam, G. D.; Denier van der Gon, H. A. C.
2014-12-01
Wear-related PM emissions are an important constituent of total PM emissions from road transport. Due to ongoing (further) exhaust emission reduction wear emissions may become the dominant PM source from road transport in the near future. The chemical composition of the wear emissions is crucial information to assess the potential health relevance of these PM emissions. Here we provide an elemental composition profile of brake wear emissions as used in the Netherlands in 2012. In total, 65 spent brake pads and 15 brake discs were collected in car maintenance shops from in-use personal cars vehicles and analyzed with XRF for their metal composition (Fe, Cu, Zn, Sn, Al, Si, Zr, Ti, Sb, Cr, Mo, Mn, V, Ni, Bi, W, P, Pb and Co). Since car, engine and safety regulations are not nationally determined but controlled by European legislation the resulting profiles will be representative for the European personal car fleet. The brake pads contained Fe and Cu as the dominant metals but their ratio varied considerably, other relatively important metals were Sn, Zn and Sb. Overall a rather robust picture emerged with Fe, Cu, Zn and Sn together making up about 80-90% of the metals present in brake pads. Because the XRF did not give information on the contents of other material such as carbon, oxygen and sulphur, a representative selection of 9 brake pads was further analyzed by ICP-MS and a carbon and sulphur analyzer. The brake pads contained about 50% of non-metal material (26% C, 3% S and the remainder mostly oxygen and some magnesium). Based on our measurements, the average brake pad profile contained 20% Fe, 10% Cu, 4% Zn and 3% Sn as the dominant metals. The brake discs consisted almost entirely of metal with iron being the dominant metal (>95%) and only traces of other metals (<1% for individual metals). Non-metal components in the discs were 2-3% Silicon and, according to literature, ∼3% carbon. The robust ratio between Fe and Cu as found on kerbsides has been used to estimate the contribution of brake pads and brake discs to total brake wear. Based on this approach our hypothesis is that 70% of the brake wear originates from the discs and only 30% from the brake pads.
Unravelling metal mobility under complex contaminant signatures.
de Souza Machado, Anderson Abel; Spencer, Kate L; Zarfl, Christiane; O'Shea, Francis T
2018-05-01
Metals are concerning pollutants in estuaries, where contamination can undergo significant remobilisation driven by physico-chemical forcing. Environmental concentrations of metals in estuarine sediments are often higher than natural backgrounds, but show no contiguity to potential sources. Thus, better understanding the metal mobility in estuaries is essential to improve identification of pollution sources and their accountability for environmental effects. This study aims to identify the key biogeochemical drivers of metal mobilisation on contaminated estuarine sediments through (1) evaluation of the potential mobilisation under controlled conditions, and (2) investigation of the relevance of metal mobilisation for in situ pollution levels in an area with multiple contaminant sources. Sediments from a saltmarsh adjacent to a coastal landfill, a marina, and a shipyard on the Thames Estuary (Essex, UK) were exposed in the laboratory (24h, N=96, 20°C) to water under various salinity, pH, and redox potential. Major cations, Fe(II), and trace metal concentrations were analysed in the leachate and sediment. Salinity, pH and redox had a significant effect on metal mobilisation (p<0.001), e.g. under certain conditions Fe(II) leaching was increased ~1000-fold. Measurements in situ of surface and subsurface sediment cores revealed that landfill proximity poorly explained metal spatial distribution. However, physicochemical parameters explained up to 97% of geochemically normalized metal concentrations in sediments. Organic matter and pH were dominant factors for most of the metal concentrations at the sediment surface. At subsurface, major cations (Ca, Na, Mg and K) were determinant predictors of metal concentrations. Applying the empirical model obtained in the laboratory to geochemical conditions of the studied saltmarsh it was possible to demonstrate that Fe mobilisation regulates the fate of this (and other) metal in that area. Thus, present results highlight the importance of metal mobility to control sediment pollution and estuarine fate of metals. Copyright © 2017 Elsevier B.V. All rights reserved.
Badran, M; Morsy, R; Soliman, H; Elnimr, T
2016-01-01
The trace elements metabolism has been reported to possess specific roles in the pathogenesis and progress of diabetes mellitus. Due to the continuous increase in the population of patients with Type 2 diabetes (T2D), this study aims to assess the levels and inter-relationships of fast blood glucose (FBG) and serum trace elements in Type 2 diabetic patients. This study was conducted on 40 Egyptian Type 2 diabetic patients and 36 healthy volunteers (Hospital of Tanta University, Tanta, Egypt). The blood serum was digested and then used to determine the levels of 24 trace elements using an inductive coupled plasma mass spectroscopy (ICP-MS). Multivariate statistical analysis depended on correlation coefficient, cluster analysis (CA) and principal component analysis (PCA), were used to analysis the data. The results exhibited significant changes in FBG and eight of trace elements, Zn, Cu, Se, Fe, Mn, Cr, Mg, and As, levels in the blood serum of Type 2 diabetic patients relative to those of healthy controls. The statistical analyses using multivariate statistical techniques were obvious in the reduction of the experimental variables, and grouping the trace elements in patients into three clusters. The application of PCA revealed a distinct difference in associations of trace elements and their clustering patterns in control and patients group in particular for Mg, Fe, Cu, and Zn that appeared to be the most crucial factors which related with Type 2 diabetes. Therefore, on the basis of this study, the contributors of trace elements content in Type 2 diabetic patients can be determine and specify with correlation relationship and multivariate statistical analysis, which confirm that the alteration of some essential trace metals may play a role in the development of diabetes mellitus. Copyright © 2015 Elsevier GmbH. All rights reserved.
Apparent Trend of the Iron Abundance in NGC 3201: The Same Outcome with Different Data
NASA Astrophysics Data System (ADS)
Kravtsov, Valery V.
2017-08-01
We further study the unusual trend we found at statistically significant levels in some globular clusters, including NGC 3201: a decreasing iron abundance in red giants toward the cluster centers. We first show that recently published new estimates of iron abundance in the cluster reproduce this trend, in spite of the authors’ statement about no metallicity spread due to a low scatter achieved in the [Fe II/H] ratio. The mean of [Fe II/H] within R˜ 2\\prime from the cluster center is lower, by Δ[Fe II/H] = 0.05 ± 0.02 dex, than in the outer region, in agreement with our original estimate for a much larger sample size within R≈ 9\\prime . We found that an older data set traces the trend to a much larger radial distance, comparable with the cluster tidal radius, at Δ[Fe/H] ˜ 0.2 dex, due to higher metallicity of distant stars. We conclude the trend is reproduced by independent data sets and find that it is accompanied by both a notable same-sign trend of oxygen abundance that can vary by up to Δ[O/Fe] ˜ 0.3 dex within R≈ 9\\prime and an opposite-sign trend of sodium abundance.
ChelomEx: Isotope-assisted discovery of metal chelates in complex media using high-resolution LC-MS.
Baars, Oliver; Morel, François M M; Perlman, David H
2014-11-18
Chelating agents can control the speciation and reactivity of trace metals in biological, environmental, and laboratory-derived media. A large number of trace metals (including Fe, Cu, Zn, Hg, and others) show characteristic isotopic fingerprints that can be exploited for the discovery of known and unknown organic metal complexes and related chelating ligands in very complex sample matrices using high-resolution liquid chromatography mass spectrometry (LC-MS). However, there is currently no free open-source software available for this purpose. We present a novel software tool, ChelomEx, which identifies isotope pattern-matched chromatographic features associated with metal complexes along with free ligands and other related adducts in high-resolution LC-MS data. High sensitivity and exclusion of false positives are achieved by evaluation of the chromatographic coherence of the isotope pattern within chromatographic features, which we demonstrate through the analysis of bacterial culture media. A built-in graphical user interface and compound library aid in identification and efficient evaluation of results. ChelomEx is implemented in MatLab. The source code, binaries for MS Windows and MAC OS X as well as test LC-MS data are available for download at SourceForge ( http://sourceforge.net/projects/chelomex ).
Daily intake of trace metals through coffee consumption in India.
Suseela, B; Bhalke, S; Kumar, A V; Tripathi, R M; Sastry, V N
2001-02-01
The trace element contents of five varieties of instant coffee powder available in the Indian market have been analysed. Ca, Cr, Fe, K, Mg, Mn, Ni, Sr, Zn and Pb, Cd, Cu have been determined using atomic absorption spectrophotometry and differential pulse anodic stripping voltammetry, respectively. The metal levels in the coffee powders observed in this study are comparable with those reported for green coffe beans (Arabica and Robusta variety) reported worldwide with the exception of Sr and Zn, which were on the lower side of the reported values. Concentrations of these metals have been converted into intake figures based on coffee consumption. The daily intakes of the above metals through ingestion of coffee are 1.4 mg, 1.58 microg, 124 microg, 41.5 mg, 4.9 mg, 17.9 microg, 2.9 microg, 3.8 microg, 12.5 microg, 0.2 microg, 0.03 microg and 15.5 microg, respectively. The values, which were compared with the total dietary, intake of metals through ingestion by the Mumbai population, indicate that the contribution from coffee is less than or around 1% for most of the elements except for Cr and Ni which are around 3%.
Baalousha, Mohamed; Stoll, Serge; Motelica-Heino, Mikaël; Guigues, Nathalie; Braibant, Gilles; Huneau, Frédéric; Le Coustumer, Philippe
2018-02-10
This study investigates the spatiotemporal variability of major and trace elements, dissolved organic carbon (DOC), total dissolved solids (TDS), and suspended particulate matter (SPM) in surface waters of several hydrosystems of the Loire River watershed in France. In particular, this study aims to delineate the impact of the abovementioned water physicochemical parameters on natural iron and manganese physical speciation (homoaggregation/heteroaggregation) among fine colloidal and dissolved (< 10 nm), colloidal (10-450 nm) and particulate (> 450 nm) phases in Loire River watershed. Results show that the chemistry of the Loire River watershed is controlled by two end members: magmatic and metamorphic petrographic context on the upper part of the watershed; and sedimentary rocks for the middle and low part of the Loire. The percentage of particulate Fe and Mn increased downstream concurrent with the increase in SPM and major cations concentration, whereas the percentage of colloidal Fe and Mn decreased downstream. Transmission electron microscopy analyses of the colloidal and particulate fractions (from the non-filtered water sample) revealed that heteroaggregation of Fe and Mn rich natural nanoparticles and natural organic matter to the particulate phase is the dominant mechanism. The heteroaggregation controls the partitioning of Fe and Mn in the different fractions, potentially due to the increase in the ionic strength, and divalent cations concentration downstream, and SPM concentration. These findings imply that SPM concentration plays an important role in controlling the fate and behavior of Fe and Mn in various sized fractions. Graphical abstract Physical speciation by heteroaggregation of (Fe-Mn) compounds: high [SPM] → [Fe-Mn] particulate faction; low {SPM] → [Fe-Mn] colloid-dissolved fraction.
NASA Astrophysics Data System (ADS)
Johnson, J. E.; Rasmussen, B.; Muhling, J.; Benzerara, K.; Jezequel, D.; Cosmidis, J.; Templeton, A. S.
2016-12-01
In direct contrast to today's oceans, iron-rich chemical precipitates dominate the deep marine sedimentary record > 2.3 billion years ago. The deposition of these minerals resulted in massive iron formations and indicate that the ocean was previously ferruginous and largely anoxic. To precipitate and concentrate iron in the sediments, many hypotheses have centered on the oxidation of soluble Fe(II) to solid Fe(III)-oxyhydroxides; these ideas have stimulated extensive research using iron-oxidizing bacteria to produce Fe(III)-oxides and trace metal sorption experiments on Fe(III)-oxides, leading to inferences of trace metal availability and implications for enzymatic and microbial evolution as well as pO2 levels and seawater chemistry. However, recent discoveries of disseminated iron-silicate nanoparticles in early-silicifying chert indicate that iron-silicates may have instead been the primary precipitates from these Archean ferruginous oceans (Rasmussen et al, 2015). Considering the significant paradigm shift this discovery implies for interpretations of Archean elemental cycling, redox state and potential microbial metabolisms, we investigated these iron-silicate inclusions and their implications for ancient seawater chemistry in a multi-faceted approach using spectroscopic- and diffraction-based techniques. The crystal structure, Fe oxidation state and Fe coordination environment of iron-silicate nanoparticles have been interrogated using microscale X-ray absorption spectroscopy, TEM and nanoscale scanning transmission X-ray microscopy. To further explore the chemical and potential biological controls on iron-silicate formation, we have also performed laboratory experiments to mimic Archean seawater and precipitate iron-bearing silicate minerals under abiotic conditions and in the presence of iron-oxidizing bacteria. In a complementary study, sediments from a natural Archean analogue system were sampled to determine if iron-silicate minerals form in Mexican crater lakes that are variably iron- and silica-rich. As we continue to probe the mechanism of Fe(II/III)-silicate formation, we can constrain the activity of silica, pH, and pO2 on early Earth and describe any potential influence of microbial activity on the precipitation of these phases.
Micronutrient metal speciation is driven by competitive organic chelation in grassland soils.
NASA Astrophysics Data System (ADS)
Boiteau, R.; Shaw, J. B.; Paša-Tolić, L.; Koppenaal, D.; Jansson, J.
2017-12-01
Many elements are scarcely soluble in aqueous conditions found in high pH environments, such as calcareous grassland soils, unless complexed to strong binding organic ligands. To overcome this limitation, some plants and microbes produce chelators that solubilize micronutrient metals such as Fe, Ni, Cu, and Zn from mineral phases. These complexes are taken up by organisms via specific membrane receptors, thereby differentially impacting the bioavailability of these metals to the plant and microbial community. Although the importance of these chelation strategies for individual organisms has been well established, little is known about which pathways coexist within rhizosphere microbiomes or how they interact and compete for metal binding. Identifying these metallo-organic species within natural ecosystems has remained a formidable analytical challenge due to the vast diversity of compounds and poorly defined metabolic processes in complex soil matrix. Herein, we employed recently developed liquid chromatography (LC) mass spectrometry (MS) methods to characterize the speciation of water-soluble dissolved trace elements (Fe, Ni, Cu, and Zn) from Kansas Prairie soil. Both plant and fungal chelators were identified, revealing compound-specific patterns of chelation to biologically essential metals. Numerous metabolites typically implicated in plant iron acquisition and homeostasis, including mugineic acids, deoxymugineic acid, nicotianamine, and hydroxynicotianamine, dominated the speciation of divalent metals such as Ni, Cu, and Zn (2-57 pmol / g soil). In contrast, the fungal siderophore ferricrocine bound comparatively more trivalent Fe (9pmol / g soil). These results define biochemical pathways that underpin the regulation of metals in the grassland rhizosphere. They also raise new questions about the competition of these compounds for metal binding and their bioavailability to different members of the rhizosphere population.
Stillings, L.L.; Foster, A.L.; Koski, R.A.; Munk, L.; Shanks, Wayne C.
2008-01-01
Several abandoned Cu mines are located along the shore of Prince William Sound, AK, where the effect of mining-related discharge upon shoreline ecosystems is unknown. To determine the magnitude of this effect at the former Beatson mine, the largest Cu mine in the region and a Besshi-type massive sulfide ore deposit, trace metal concentration and flux were measured in surface run-off from remnant, mineralized workings and waste. Samples were collected from seepage waters; a remnant glory hole which is now a pit lake; a braided stream draining an area of mineralized rock, underground mine workings, and waste piles; and a background location upstream of the mine workings and mineralized rock. In the background stream pH averaged ???7.3, specific conductivity (SC) was ???40 ??S/cm, and the aqueous components indicative of sulfide mineral weathering, SO4 and trace metals, were at detection limits or lower. In the braided stream below the mine workings and waste piles, pH usually varied from 6.7 to 7.1, SC varied from 40 to 120 ??S/cm, SO4 had maximum concentrations of 32 mg/L, and the trace metals Cu, Ni, Pb, and Zn showed maximum total acid extractable concentrations of 186, 5.9, 6.2 and 343 ??g/L, respectively. With an annual rainfall of ???340 cm (estimated from the 2006 water year) it was expected that rain water would have a large effect on the chemistry of the braided stream draining the mine site. A linear mixing model with two end members, seepage water from mineralized rock and background water, estimated that the braided stream contained 10-35% mine drainage. After rain events the braided stream showed a decrease in pH, SC, Ca + Mg, SO4, and alkalinity, due to dilution. The trace metals Ni and Zn followed this same pattern. Sodium + K and Cl did not vary between the background and braided stream, nor did they vary with rainfall. At approximately 2 and 3 mg/L, respectively, these concentrations are similar to concentrations found in rainfall on the coasts of North America. High concentrations of total acid extractable Al and Fe were found at near-neutral pH in most of the waters collected at the site. Equilibrium solubility simulations, performed with PHREEQC, show that the stream waters are saturated with respect to Al, Fe and SiO2 solid phases. Because the "dissolved" sample fractions (acid preserved and filtered to 0.45 ??m) show significant concentrations of Al and Fe it is presumed that these are present as colloids. The relationship between concentrations of Al and Fe, and rainfall was the opposite of that observed for the major ions Ca + Mg, SO4, and alkalinity, in that Al and Fe concentrations increased with increasing rainfall. Concentrations of Cu and Pb followed the same pattern. Adsorption calculations were performed with Visual MINTEQ, using the diffuse double layer electrostatic model and surface complexation constants for the ferrihydrite surface. These results suggest that 30-93% of Cu and 58-97% of Pb was adsorbed to ferrihydrite precipitates in the stream waters. Ni and Zn showed little adsorption in this pH range. Flux calculations show that the total mass of trace metals transported from the mine site, during the 60 day study period, was ranked as Zn (196 kg) > Cu (87 kg) > Pb(1.9 kg) ??? Ni(1.9 kg). Nickel and Zn were transported mostly as dissolved species while Cu and Pb were transported mostly as adsorbed species. pH control on adsorption was evident when Cu and Pb isotherms were normalized by ferrihydrite flux. Decreased stream water pH due to periods of frequent and high volume rain events would cause desorption of Cu and Pb from the ferrihydrite surface, thus changing not only their speciation in solution but also their mechanism of transport. ?? 2007 Elsevier Ltd. All rights reserved.
Li, Siyue; Zhang, Quanfa
2010-04-15
A data matrix (4032 observations), obtained during a 2-year monitoring period (2005-2006) from 42 sites in the upper Han River is subjected to various multivariate statistical techniques including cluster analysis, principal component analysis (PCA), factor analysis (FA), correlation analysis and analysis of variance to determine the spatial characterization of dissolved trace elements and heavy metals. Our results indicate that waters in the upper Han River are primarily polluted by Al, As, Cd, Pb, Sb and Se, and the potential pollutants include Ba, Cr, Hg, Mn and Ni. Spatial distribution of trace metals indicates the polluted sections mainly concentrate in the Danjiang, Danjiangkou Reservoir catchment and Hanzhong Plain, and the most contaminated river is in the Hanzhong Plain. Q-model clustering depends on geographical location of sampling sites and groups the 42 sampling sites into four clusters, i.e., Danjiang, Danjiangkou Reservoir region (lower catchment), upper catchment and one river in headwaters pertaining to water quality. The headwaters, Danjiang and lower catchment, and upper catchment correspond to very high polluted, moderate polluted and relatively low polluted regions, respectively. Additionally, PCA/FA and correlation analysis demonstrates that Al, Cd, Mn, Ni, Fe, Si and Sr are controlled by natural sources, whereas the other metals appear to be primarily controlled by anthropogenic origins though geogenic source contributing to them. 2009 Elsevier B.V. All rights reserved.
Zhang, Nan; Peng, Hanyong; Hu, Bin
2012-05-30
We report here the preparation of high-magnetization Fe(3)O(4)@SiO(2)@TiO(2) nanoparticles for solid phase extraction of trace amounts of Cd(II), Cr(III), Mn(II) and Cu(II) from environmental waters. The prepared nanoparticles were characterized by scanning electron micrograph (SEM) and transmission electron microscopy (TEM). The high-magnetization nanoparticles carrying the target metals could be easily and fast separated from the aqueous solution simply by applying an external magnetic field while no filtration or centrifugation was necessary. A light-induced hydroxide ion emitter, molecular malachite green carbinol base (MGCB) was applied to adjust pH value of solution for quantitative adsorption instead of the conventional used buffer. In the presence of UV light, MGCB gives out OH(-) ions, and this leads to an increase in the pH value without the aid of buffer solution. Using high-magnetization Fe(3)O(4)@SiO(2)@TiO(2) nanoparticles as the extraction material and the light-induced MGCB for pH adjustment, we developed an efficient and convenient two-step method for separation/preconcentration trace amounts of Cd(II), Cr(III), Mn(II) and Cu(II) in environmental water samples followed by inductively coupled plasma mass spectrometry (ICP-MS) detection. The parameters affecting the extraction such as MGCB concentration, exposal time, sample volume, eluent condition, and interfering ions have been investigated in detail. Under the optimized conditions, the limits of detection for Cd(II), Cr(III), Mn(II) and Cu(II) were 4.0, 2.6, 1.6 and 2.3 ng L(-1), respectively, and the relative standard deviations (RSDs, c=1 μg L(-1), n=7) were 3.6%, 4.5%, 4.0 and 4.1%, respectively. The proposed method has been validated using certified reference materials, and it has been successfully applied in the determination of trace Cd(II), Cr(III), Mn(II) and Cu(II) in environmental water samples. Copyright © 2012 Elsevier B.V. All rights reserved.
Fracture-induced flow and liquid metal transport during core formation
NASA Astrophysics Data System (ADS)
Jones, V.; Petford, N.; Rushmer, T.; Wertheim, D.
2008-12-01
The most important event in the early history of the earth was the separation of its iron-rich core. Core formation induced profound chemical fractionations and extracted into the core most of Earth's iron and siderophile elements (Ni, Co, Au, Pt, W, Re), leaving the silicate crust and mantle with strong depletions of these elements relative to primitive planetary material. Recent measurements of radiogenic 182W anomalies in the silicate Earth, Mars and differentiated meteorites imply that planetesimals segregated metallic cores within a few Myr of the origin of the solar system. Various models have been put forward to explain the physical nature of the segregation mechanism (Fe-diapirs, 'raining' through a magma ocean), and more recently melt flow via fractures. In this contribution we present the initial results of a numerical study into Fe segregation in a deforming silicate matrix that captures the temperature-dependent effect of liquid metal viscosity on the transport rate. Flow is driven by pressure gradients associated with impact deformation in a growing planetesimal and the fracture geometry is constrained by experimental data on naturally deformed H6 chondrite. Early results suggest that under dynamic conditions, fracture-driven melt flow can in principle be extremely rapid, leading to a significant draining of the Fe-liquid metal and siderophile trace element component on a timescale of hours to days. Fluid transport in planetesimals where deformation is the driving force provides an attractive and simple way of segregating Fe from host silicate as both precursor and primary agent of core formation
NASA Astrophysics Data System (ADS)
Sucha, Veronika; Mihaljevic, Martin; Ettler, Vojtech; Strnad, Ladislav
2014-05-01
The release of trace metals and platinum group elements (PGEs) from automobile exhaust catalysts represents a remarkable source of higly dispersed environmental contamination. Especially, PGEs have shown increasing research interest due to their possible bioaccessibility. In our research, we focused on leaching behaviour of trace metals from gasoline and diesel automobile catalysts. While catalysts for gasoline engines contain a mixture of Pt-Pd-Rh or Pd-Rh, catalysts for diesel engines are composed only of Pt. We used dust from two crushed gasoline and two crushed diesel catalysts (new and aged). The dust of gasoline catalysts contains significant concentrations of Pt (700 mg.kg-1), Pd (11 000 mg.kg-1) and Rh (700 mg.kg-1). And the dust of diesel catalysts are composed of Pt (3 900 mg.kg-1) and they contains negligible amounts of Pd dan Rh (< 0.5 mg.kg-1, < 0.1 mg.kg-1, respectively). To evaluate leaching of trace metals from dust we used pH-stat leaching test according to the European standard CEN/TS 14997. The concentrations of cations: PGEs (Pt, Pd a Rh), K, Na, Ca, Mg, Al, Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, Cd, Pb, La and Ce were determined by inductively coupled plasma mass spectrometry (ICP-MS) and atomic absorption spectrometry (AAS), and anions: F-, Cl-, SO42- and NO3- by high-performance liquid chromatography. Although the dusts from catalysts were relatively stable to acid/base influence, the leaching of trace metals from catalysts showed a dependence on pH. Generally, the highest concentrations were released under acidic conditions. The leaching of PGEs was higher for Pt in diesel catalysts and for Pd and Rh in gasoline catalysts. The highest concentrations of Zn and Pb were observed in old catalysts. The rare earth metals were released more from gasoline catalysts. Catalysts particles represent health risk especially with respect to their PGEs contents.
Trace Metal Content of Sediments Close to Mine Sites in the Andean Region
Yacoub, Cristina; Pérez-Foguet, Agustí; Miralles, Nuria
2012-01-01
This study is a preliminary examination of heavy metal pollution in sediments close to two mine sites in the upper part of the Jequetepeque River Basin, Peru. Sediment concentrations of Al, As, Cd, Cu, Cr, Fe, Hg, Ni, Pb, Sb, Sn, and Zn were analyzed. A comparative study of the trace metal content of sediments shows that the highest concentrations are found at the closest points to the mine sites in both cases. The sediment quality analysis was performed using the threshold effect level of the Canadian guidelines (TEL). The sediment samples analyzed show that potential ecological risk is caused frequently at both sites by As, Cd, Cu, Hg, Pb, and Zn. The long-term influence of sediment metals in the environment is also assessed by sequential extraction scheme analysis (SES). The availability of metals in sediments is assessed, and it is considered a significant threat to the environment for As, Cd, and Sb close to one mine site and Cr and Hg close to the other mine site. Statistical analysis of sediment samples provides a characterization of both subbasins, showing low concentrations of a specific set of metals and identifies the main characteristics of the different pollution sources. A tentative relationship between pollution sources and possible ecological risk is established. PMID:22606058
Distribution of Major and Trace Elements in a Tropical Hydroelectric Reservoir in Sarawak, Malaysia.
Sim, Siong Fong; Ling, Teck Yee; Nyanti, Lee; Ean Lee, Terri Zhuan; Mohd Irwan Lu, Nurul Aida Lu; Bakeh, Tomy
2014-01-01
This paper reports the metals content in water, sediment, macroalgae, aquatic plant, and fish of Batang Ai Hydroelectric Reservoir in Sarawak, Malaysia. The samples were acid digested and subjected to atomic absorption spectrometry analysis for Na, K, Mn, Cr, Ni, Zn, Mg, Fe, Sn, Al, Ca, As, Se, and Hg. The total Hg content was analysed on the mercury analyser. Results showed that metals in water, sediment, macroalgae, aquatic plant, and fish are distinguishable, with sediment and biota samples more susceptible to metal accumulation. The distributions of heavy metals in water specifically Se, Sn, and As could have associated with the input of fish feed, boating, and construction activities. The accumulation of heavy metals in sediment, macroalgae, and aquatic plant on the other hand might be largely influenced by the redox conditions in the aquatic environment. According to the contamination factor and the geoaccumulation index, sediment in Batang Ai Reservoir possesses low risk of contamination. The average metal contents in sediment and river water are consistently lower than the literature values reported and well below the limit of various guidelines. For fishes, trace element Hg was detected; however, the concentration was below the permissible level suggested by the Food and Agriculture Organization.
Distribution of Major and Trace Elements in a Tropical Hydroelectric Reservoir in Sarawak, Malaysia
Nyanti, Lee; Ean Lee, Terri Zhuan; Mohd Irwan Lu, Nurul Aida Lu
2014-01-01
This paper reports the metals content in water, sediment, macroalgae, aquatic plant, and fish of Batang Ai Hydroelectric Reservoir in Sarawak, Malaysia. The samples were acid digested and subjected to atomic absorption spectrometry analysis for Na, K, Mn, Cr, Ni, Zn, Mg, Fe, Sn, Al, Ca, As, Se, and Hg. The total Hg content was analysed on the mercury analyser. Results showed that metals in water, sediment, macroalgae, aquatic plant, and fish are distinguishable, with sediment and biota samples more susceptible to metal accumulation. The distributions of heavy metals in water specifically Se, Sn, and As could have associated with the input of fish feed, boating, and construction activities. The accumulation of heavy metals in sediment, macroalgae, and aquatic plant on the other hand might be largely influenced by the redox conditions in the aquatic environment. According to the contamination factor and the geoaccumulation index, sediment in Batang Ai Reservoir possesses low risk of contamination. The average metal contents in sediment and river water are consistently lower than the literature values reported and well below the limit of various guidelines. For fishes, trace element Hg was detected; however, the concentration was below the permissible level suggested by the Food and Agriculture Organization. PMID:27437493
Zduniak, Piotr; Surmacki, Adrian; Erciyas-Yavuz, Kiraz; Chudzińska, Maria; Barałkiewicz, Danuta
2014-09-01
Melanin is the most common pigment in animal integuments including bird plumage. It has been shown that several trace elements may play roles in the production and signaling function of melanin-colored plumage. We investigated coloration and content of various metal elements in the rectrices of two insectivorous passerines, Common Redstarts (Phoenicurus phoenicurus) and Blackcaps (Sylvia atricapilla), which have eumelanin- and pheomelanin-based coloration, respectively. We hypothesized that 1) the two species would differ in concentrations of metals important in melanin synthesis (Ca, Fe, Cu, Zn), 2) differences in metal concentration levels would be related to feather coloration. Our study confirmed the first prediction and provides the first evidence that selected elements may play a greater role in pheomelanin than in eumelanin synthesis. Concentrations of three elements considered as important in melanin synthesis (Ca, Fe, Zn) were 52% to 93% higher in rusty colored Common Redstart feathers compared to the dark gray Blackcap feathers. However, element concentrations were not correlated with feather coloration or sex in either species. Our study suggests that, of the two melanin forms, pheomelanin synthesis may bear higher costs associated with the acquisition of specific elements or limited elements may create trade-offs between ornamentation and other physiological functions. Our findings warrant further investigations designed to better understand the roles of macro- and microelements in the synthesis of both forms of melanin. Copyright © 2014 Elsevier Inc. All rights reserved.
Opposing authigenic controls on the isotopic signature of dissolved iron in hydrothermal plumes
NASA Astrophysics Data System (ADS)
Lough, A. J. M.; Klar, J. K.; Homoky, W. B.; Comer-Warner, S. A.; Milton, J. A.; Connelly, D. P.; James, R. H.; Mills, R. A.
2017-04-01
Iron is a scarce but essential micronutrient in the oceans that limits primary productivity in many regions of the surface ocean. The mechanisms and rates of Fe supply to the ocean interior are still poorly understood and quantified. Iron isotope ratios of different Fe pools can potentially be used to trace sources and sinks of the global Fe biogeochemical cycle if these boundary fluxes have distinct signatures. Seafloor hydrothermal vents emit metal rich fluids from mid-ocean ridges into the deep ocean. Iron isotope ratios have the potential to be used to trace the input of hydrothermal dissolved iron to the oceans if the local controls on the fractionation of Fe isotopes during plume dispersal in the deep ocean are understood. In this study we assess the behaviour of Fe isotopes in a Southern Ocean hydrothermal plume using a sampling program of Total Dissolvable Fe (TDFe), and dissolved Fe (dFe). We demonstrate that δ56Fe values of dFe (δ56dFe) within the hydrothermal plume change dramatically during early plume dispersal, ranging from -2.39 ± 0.05‰ to -0.13 ± 0.06‰ (2 SD). The isotopic composition of TDFe (δ56TDFe) was consistently heavier than dFe values, ranging from -0.31 ± 0.03‰ to 0.78 ± 0.05‰, consistent with Fe oxyhydroxide precipitation as the plume samples age. The dFe present in the hydrothermal plume includes stabilised dFe species with potential to be transported to the deep ocean. We estimate that stable dFe exported from the plume will have a δ56Fe of -0.28 ± 0.17‰. Further, we show that the proportion of authigenic iron-sulfide and iron-oxyhydroxide minerals precipitating in the buoyant plume exert opposing controls on the resultant isotope composition of dissolved Fe passed into the neutrally buoyant plume. We show that such controls yield variable dissolved Fe isotope signatures under the authigenic conditions reported from modern vent sites elsewhere, and so ought to be considered during iron isotope reconstructions of past hydrothermalism from ocean sediment records.
Three-dimensional flow and trace metal mobility in shallow Chalk groundwater, Dorset, United Kingdom
NASA Astrophysics Data System (ADS)
Schürch, Marc; Edmunds, W. Michael; Buckley, David
2004-06-01
The three-dimensional groundwater flow and the hydrogeochemical regime have been determined in the Bere Stream valley, North Dorset Downs, southern England. The dual porosity characteristics of the Portsdown Chalk have been established using geophysical and hydrochemical borehole logging. Chemical properties have been established using major and trace element analyses of depth samples and groundwaters. The study site is located at the unconfined-confined boundary of the Chalk aquifer, where it is overflowing in the observation boreholes. The Chalk dips locally at about 5 m/km to the south-east under Palaeogene confining beds and three distinctive flow horizons may be recognised. The Chalk groundwater is of Ca-HCO 3 type and three separate geochemical groundwater zones were also determined with depth, having different oxygen levels and trace element characteristics. (1) A shallow O 2-rich zone with around 80% dissolved O 2 and low trace element concentrations. (2) A mixing and transition zone with significant concentrations of trace elements and high trace metal concentrations at its base: manganese 29 μg/l, nickel 55 μg/l, cadmium 146 μg/l, and zinc 214 μg/l. (3) A deeper zone with depleted oxygen (5-20% dissolved O 2) and with longer water residence times shown by higher Mg/Ca and K/Na ratios as well as higher Sr and F. The groundwater geochemistry in the Chalk aquifer is dominated by incongruent reactions with the fine-grained carbonate sediments, which release trace element impurities to the water. Some of the metals are co-precipitated with Mn- and Fe-oxide phases on fissure surfaces, whilst producing a purer calcite. During subsequent recrystallisation to purer iron- and manganese-oxides on fissure surfaces under specific geochemical and hydrodynamic conditions, trace metals are released into the fissure water. The results demonstrate the need to monitor quality stratification and the changes in the groundwater baseline chemistry in areas close to the redox boundary which, in the dual porosity Chalk is likely to be a diffuse zone with exchange between oxygen poor matrix waters and more oxic water flowing through the fissures.
Application of petroleum markers to geochemical and environmental investigations
DOE Office of Scientific and Technical Information (OSTI.GOV)
Abu-Elgheit, M.A.; El-Gayar, M.S.; Hegazi, A.H.
1998-01-01
Application of trace-metal and biological markers to geochemical studies has shown that crude oils could be correlated or differentiated according to their geologic age. The V/Ni, V/{Sigma} Ni, Mg, Fe, and pristine to phytane (Pr/Ph) markers were almost uniform in Gulf of Suez crude oils, revealing their same origin, yet showing marked differences in Western Desert crude oils, reflecting varying degrees of their maturity and migrational history. The significance of petroleum markers was extended to monitoring of oil spill sources. Weathering of spills usually renders their source identification questionable by infrared or gas chromatography profiles. Since evaporative loss light petroleummore » fractions does not appreciably affect the high-Molecular Weight components with which trace metals, isoprenoids, hopanes, and steranes are associated, V/Ni, Pr/Ph, m/z 191, and m/z 217 mass chromatogram fragments were found reliable in fingerprinting oil spill sources in Mediterranean waters.« less
NASA Astrophysics Data System (ADS)
Shao, Hongbo; Kukkadapu, Ravi K.; Krogstad, Eirik J.; Newburn, Matt K.; Cantrell, Kirk J.
2014-09-01
To investigate the impact of O2 as an impurity co-injected with CO2 on geochemical interactions, especially trace metal mobilization from a geological CO2 sequestration (GCS) reservoir rock, batch studies were conducted with Eau Claire siltstone collected from CO2 sequestration sites. The rock was reacted with synthetic brines in contact with either 100% CO2 or a mixture of 95 mol% CO2-5 mol% O2 at 10.1 MPa and 75 °C. Both microscopic and spectroscopic measurements, including 57Fe-Mössbauer spectroscopy, Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry, powder X-ray diffraction, scanning electron microscopy-energy dispersive X-ray spectroscopy, and chemical extraction were combined in this study to investigate reaction mechanisms. The Eau Claire siltstone contains quartz (52 wt%), fluorapatite (40%), and aluminosilicate (5%) as major components, and dolomite (2%), pyrite (1%), and small-particle-/poorly-crystalline Fe-oxides as minor components. With the introduction of CO2 into the reaction vessel containing rock and brine, the leaching of small amounts of fluorapatite, aluminosilicate, and dolomite occurred. Trace metals of environmental concern, including Pb, As, Cd, and Cu were detected in the leachate with concentrations up to 400 ppb in the CO2-brine-rock reaction system within 30 days. In the presence of O2, the oxidation of Fe(II) and the consequent changes in the reaction system, including a reduction in pH, significantly enhanced the mobilization of Pb, Cd, and Cu, whereas As concentrations decreased, compared with the reaction system without O2. The presence of O2 resulted in the formation of secondary Fe-oxides which appear to be Fe(II)-substituted P-containing ferrihydrite. Although the rock contained only 1.04 wt% total Fe, oxidative dissolution of pyrite, leaching and oxidation of structural Fe(II) in fluorapatite, and precipitation of Fe-oxides significantly decreased the pH in brine with O2 (pH 3.3-3.7), compared with the reaction system without O2 (pH 4.2-4.4). In the CO2-rock-brine system without O2, the majority of As remained in the rock, with about 1.1% of the total As being released from intrinsic Fe-oxides to the aqueous phase. The release behavior of As to solution was consistent with competitive adsorption between phosphate/fluoride and As on Fe-oxide surfaces. In the presence of O2 the mobility of As was reduced due to enhanced adsorption onto both intrinsic and secondary Fe-oxide surfaces. When O2 was present, the dominant species in solution was the less toxic As(V). This work will advance our understanding of the geochemical reaction mechanisms that occur under GCS conditions and help to evaluate the risks associated with geological CO2 sequestration.
Distribution and source apportionment studies of heavy metals in soil of cotton/wheat fields.
Rafique, Nazia; Tariq, Saadia R
2016-05-01
Heavy metals enriched agricultural soils have been the subject of great concern because these metals have potential to be transferred to the soil solution and afterward accumulated in food chain. To study the trace metal persistence in crop soil, 90 representative soil samples were collected and analyzed for heavy metal (As, Cd, Cu, Fe, Mn, Ni, Pb, and Zn) and anions (chloride, nitrates, phosphates and sulfates). Cluster and factor analysis techniques were used for the source identification of these excessive heavy metal levels and ecological risk was determined with potential ecological risk assessment. The degree of enrichment of eight studied heavy metals in comparison with the corresponding background levels decreased in order: Cd > Pb > Fe > Ni > Mn > As > Cu ~ Zn. Arsenic and cadmium exhibited 1.30- and 1.64-fold exceeded levels than threshold limits set by National environment quality standards, respectively. Cd in cotton field's soil may lead to higher potential risk than other heavy metals. On overall basis, the cumulative mean potential ecological risk for the district (207.75) corresponded to moderate risk level with higher contributions from As and Pb especially from Cd. Cadmium formed strong positive correlation with phosphate content of soil at p < 0.01. Cluster analysis indicated that Cluster 1 (extremely polluted) probably originated from anthropogenic inputs of phosphate fertilizer and past usage of arsenical pesticides.
NASA Astrophysics Data System (ADS)
Conway, Tim M.; John, Seth G.
2015-09-01
Dissolved stable isotope ratios of the transition metals provide useful information, both for understanding the cycling of these bioactive trace elements through the oceans, and tracing their marine sources and sinks. Here, we present seawater dissolved Fe, Zn and Cd concentration and stable isotope ratio (δ56Fe, δ66Zn, and δ114Cd) profiles from two stations in the Pacific Ocean, the SAFe Station (30°N 140°W) in the subtropical North East Pacific from the GEOTRACES IC2 cruise, and the marginal San Pedro Basin (33.8°N 118.4°W) within the South California Bight. These data represent, to our knowledge, the first full-water column profiles for δ66Zn and δ56Fe from the open-ocean North Pacific, and the first observations of dissolved δ66Zn and δ114Cd in a low-oxygen marginal basin. At the SAFe station, δ56Fe is isotopically lighter throughout the water column (-0.6 to +0.1‰, relative to IRRM-014) compared to the North Atlantic, suggesting significant differences in Fe sources or Fe cycling between these two ocean basins. A broad minimum in δ56Fe associated with the North Pacific oxygen minimum zone (OMZ; <75 μmol kg-1 dissolved oxygen; ∼550-2000 m depth) is consistent with reductive sediments along the California margin being an important source of dissolved Fe to the North Pacific. Other processes which may influence δ56Fe at SAFe include biological cycling in the upper ocean, and input of Fe from hydrothermal vents and oxic sediments below the OMZ. Zn and Cd concentration profiles at both stations broadly match the distribution of the macronutrients silicate and phosphate, respectively. At SAFe, δ114Cd increases towards the surface, reflecting the biological preference for assimilation of lighter Cd isotopes, while negative Cd∗ (-0.12) associated with low oxygen waters supports the recently proposed hypothesis of water-column CdS precipitation. In contrast to δ114Cd, δ66Zn at SAFe decreases towards the surface ocean, perhaps due to scavenging of isotopically heavy Zn, while at intermediate depths δ66Zn provides further evidence of a mid-depth dissolved δ66Zn maximum. We suggest this may be a global feature of Zn biogeochemistry related to either regeneration of heavy adsorbed Zn, or to ZnS formation and removal within the water column. Data from San Pedro shows that anoxic sediments can be a source of isotopically light Zn to the water column (δ66Zn of ∼-0.3‰ relative to JMC Lyon), though evidence of this signal is not observed being transported to SAFe. Within North Pacific Intermediate Water at SAFe (NPIW; ∼500 m) elevated Cd∗ and Zn∗ and a focused minimum in δ56Fe suggest possible transport of Fe, Zn, and Cd over thousands of km from subpolar waters, meaning that NPIW may have a strong influence on the subsurface distribution of trace metals throughout the North Pacific.
Authigenesis of trace metals in energetic tropical shelf environments
Breckel, E.J.; Emerson, S.; Balistrieri, L.S.
2005-01-01
We evaluated authigenic changes of Fe, Mn, V, U, Mo, Cd and Re in suboxic, periodically remobilized, tropical shelf sediments from the Amazon continental shelf and the Gulf of Papua. The Cd/Al, Mo/Al, and U/Al ratios in Amazon shelf sediments were 82%, 37%, and 16% less than those in Amazon River suspended sediments, respectively. Very large depletions of U previously reported in this environment were not observed. The Cd/Al ratios in Gulf of Papua sediments were 76% lower than measurements made on several Papua New Guinea rivers, whereas U/Al ratios in the shelf sediments were enriched by approximately 20%. Other metal/Al ratios in the Papua New Guinea river suspended sediments and continental shelf sediments were not distinguishably different. Comparison of metal/Al ratios to grain size distributions in Gulf of Papua samples indicates that our observations cannot be attributed to differences in grain size between the river suspended sediments and continental shelf sediments. These two shelves constitute a source of dissolved Cd to the world ocean equal to 29-100% of the dissolved Cd input from rivers, but only 3% of the dissolved Mo input and 4% of the dissolved U input. Release of Cd, Mo, and U in tropical shelf sediments is likely a result of intense Fe and Mn oxide reduction in pore waters and resuspension of the sediments. Since we do not observe depletions of particulate Fe and Mn in the shelf sediments most of these dissolved metals must reoxidize in the overlying waters and reprecipitate. As Cd exhibits the largest losses on these tropical shelves, we examined the ability of newly formed Fe and Mn oxides to adsorb dissolved Cd using a geochemical diffuse double-layer surface complexation model and found the oxide surfaces are relatively ineffective at readsorbing Cd in seawater due to surface-site competition by Mg and Ca. If the remobilization and reoxidation of Fe and Mn occurs frequently enough before sediment is buried significant amounts of Cd may be removed from the oxide surfaces. Because a much greater percentage of Mn than Fe becomes remobilized in these shelf sediments, metals closely associated with Mn oxides (like Cd) are more likely to show losses during deposition. ?? 2005 Elsevier Ltd. All rights reserved.
Zhou, Qingxiang; Lei, Man; Liu, Yongli; Wu, Yalin; Yuan, Yongyong
2017-12-01
Pollution resulted from heavy metal ions have absorbed much attention, and it is of great importance to develop sensitive and simultaneous determination method for them with common technologies without highly sensitive instruments. We prepared a new and functional core-shell magnetic nano-material, Fe@Ag@dimercaptobenzene (Fe@Ag@DMB), by a one-step method with sodium borohydride as the reducing agent and transmission electron microscopy (TEM) and energy dispersive spectrometer (EDS) were used for characterisation. The mercapto functional groups on the newly synthesised magnetic nanoparticles could interact with Cd 2+ , Pb 2+ , and Hg 2+ ions in water samples and then efficient extraction for Cd 2+ , Pb 2+ , and Hg 2+ ions was achieved. DDTC-Na solution was a good elutent for elution of these ions from Fe@Ag@DMB nanoparticles. Based on these, a sensitive method was developed for simultaneous preconcentration and determination of the aforementioned ions using magnetic Fe@Ag@DMB nanoparticles as the magnetic solid phase extraction adsorbent prior to high performance liquid chromatography coupled with variable wavelength detection. Under the optimal conditions, the detection limits of the three metal ions were in the range of 0.011-0.031μgL -1 , and precisions were below 2.37% (n=6). The proposed method was evaluated with real water samples, and excellent spiked recoveries achieved indicated that the developed method would be a promising tool for monitoring these heavy metal ions in water samples. Copyright © 2017 Elsevier B.V. All rights reserved.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Wu, Yun; Li, Wei; Sparks, Donald L.
2015-10-18
Arsenic (As) mobility in the environment is greatly affected by its oxidation state and the degree to which it is sorbed on metal oxide surfaces. Manganese (Mn) and iron (Fe) oxides are ubiquitous solids in terrestrial systems and have high sorptive capacities for many trace metals, including As. Although numerous studies have studied the effects of As adsorption and desorption onto Fe and Mn oxides individually, the fate of As within mixed systems representative of natural environments has not been resolved. In this research, As(III) was initially reacted with a poorly crystalline phyllomanganate (δ-MnO 2) in the presence of Fe(II)more » prior to desorption. This initial reaction resulted in the sorption of both As(III) and As(V) on mixed Fe/Mn-oxides surfaces. A desorption study was carried out using two environmentally significant ions, phosphate (PO 4 3–) and calcium (Ca 2+). Both a stirred-flow technique and X-ray absorption fine-structure spectroscopy (XAFS) analysis were used to investigate As desorption behavior. Results showed that when As(III)/Fe(II) = 1:1 in the initial reaction, only As(V) was desorbed, agreeing with a previous study showing that As(III) is not associated with the Fe/Mn-oxides. When As(III)/Fe(II) = 1:10 in the initial reaction, both As(III) and As(V) can be desorbed from the Fe/Mn-oxide surface, and more As(III) is desorbed than As(V). Neither of the desorbents used in this study completely removed As(III) or As(V) from the Fe/Mn-oxides surface. However, the As desorption fraction decreases with increasing Fe(II) concentration in the initial reactions.« less
Wu, Yun; Li, Wei; Sparks, Donald L
2015-11-17
Arsenic (As) mobility in the environment is greatly affected by its oxidation state and the degree to which it is sorbed on metal oxide surfaces. Manganese (Mn) and iron (Fe) oxides are ubiquitous solids in terrestrial systems and have high sorptive capacities for many trace metals, including As. Although numerous studies have studied the effects of As adsorption and desorption onto Fe and Mn oxides individually, the fate of As within mixed systems representative of natural environments has not been resolved. In this research, As(III) was initially reacted with a poorly crystalline phyllomanganate (δ-MnO2) in the presence of Fe(II) prior to desorption. This initial reaction resulted in the sorption of both As(III) and As(V) on mixed Fe/Mn-oxides surfaces. A desorption study was carried out using two environmentally significant ions, phosphate (PO4(3-)) and calcium (Ca(2+)). Both a stirred-flow technique and X-ray absorption fine-structure spectroscopy (XAFS) analysis were used to investigate As desorption behavior. Results showed that when As(III)/Fe(II) = 1:1 in the initial reaction, only As(V) was desorbed, agreeing with a previous study showing that As(III) is not associated with the Fe/Mn-oxides. When As(III)/Fe(II) = 1:10 in the initial reaction, both As(III) and As(V) can be desorbed from the Fe/Mn-oxide surface, and more As(III) is desorbed than As(V). Neither of the desorbents used in this study completely removed As(III) or As(V) from the Fe/Mn-oxides surface. However, the As desorption fraction decreases with increasing Fe(II) concentration in the initial reactions.
Low biodegradability of dissolved organic matter and trace metals from subarctic waters.
Oleinikova, Olga V; Shirokova, Liudmila S; Drozdova, Olga Y; Lapitskiy, Sergey A; Pokrovsky, Oleg S
2018-03-15
The heterotrophic mineralization of dissolved organic matter (DOM) controls the CO 2 flux from the inland waters to the atmosphere, especially in the boreal waters, although the mechanisms of this process and the fate of trace metals associated with DOM remain poorly understood. We studied the interaction of culturable aquatic (Pseudomonas saponiphila) and soil (Pseudomonas aureofaciens) Gammaproteobacteria with seven different organic substrates collected in subarctic settings. These included peat leachate, pine crown throughfall, fen, humic lake, stream, river, and oligotrophic lake with variable dissolved organic carbon (DOC) concentrations (from 4 to 60mgL -1 ). The highest removal of DOC over 4days of reaction was observed in the presence of P. aureofaciens (33±5%, 43±3% and 53±7% of the initial amount in fen water, humic lake and stream, respectively). P. saponiphila degraded only 5% of DOC in fen water but did not affect all other substrates. Trace elements (TE) were essentially controlled by short-term (0-1h) adsorption on the surface of cells. Regardless of the nature of organic substrate and the identity of bacteria, the degree of adsorption ranged from 20 to 60% for iron (Fe 3+ ), 15 to 55% for aluminum (Al), 10 to 60% for manganese (Mn), 10 to 70% for nickel (Ni), 20 to 70% for copper (Cu), 10 to 60% for yttrium (Y), 30 to 80% for rare earth elements (REE), and 15 to 50% for uranium (U VI ). Rapid adsorption of organic and organo-mineral colloids on bacterial cell surfaces is novel and potentially important process, which deserves special investigation. The long-term removal of dissolved Fe and Al was generally consistent with solution supersaturation degree with respect to Fe and Al hydroxides, calculated by visual Minteq model. Overall, the biomass-normalized biodegradability of various allochthonous substrates by culturable bacteria is much lower than that of boreal DOM by natural microbial consortia. Copyright © 2017 Elsevier B.V. All rights reserved.
Background concentrations and reference values for heavy metals in soils of Cuba.
Alfaro, Mirelys Rodríguez; Montero, Alfredo; Ugarte, Olegario Muñiz; do Nascimento, Clístenes Williams Araújo; de Aguiar Accioly, Adriana Maria; Biondi, Caroline Miranda; da Silva, Ygor Jacques Agra Bezerra
2015-01-01
The potential threat of heavy metals to human health has led to many studies on permissible levels of these elements in soils. The objective of this study was to establish quality reference values (QRVs) for Cd, Pb, Zn, Cu, Ni, Cr, Fe, Mn, As, Hg, V, Ba, Sb, Ag, Co, and Mo in soils of Cuba. Geochemical associations between trace elements and Fe were also studied, aiming to provide an index for establishing background concentrations of metals in soils. Surface samples of 33 soil profiles from areas of native forest or minimal anthropic influence were collected. Samples were digested (USEPA method 3051A), and the metals were determined by ICP-OES. The natural concentrations of metals in soils of Cuba followed the order Fe > Mn > Ni > Cr > Ba > V > Zn > Cu > Pb > Co > As > Sb > Ag > Cd > Mo > Hg. The QRVs found for Cuban soils were as follows (mg kg(-1)): Ag (1), Ba (111), Cd (0.6), Co (25), Cr (153), Cu (83), Fe (54,055), Mn (1947), Ni (170), Pb (50), Sb (6), V (137), Zn (86), Mo (0.1), As (19), and Hg (0.1). The average natural levels of heavy metals are above the global average, especially for Ni and Cr. The chemical fractionation of soil samples presenting anomalous concentrations of metals showed that Cu, Ni, Cr, Sb, and As have low bioavailability. This suggests that the risk of contamination of agricultural products via plant uptake is low. However, the final decision on the establishment of soil QRVs in Cuba depends on political, economic, and social issues and in-depth risk analyses considering all routes of exposure to these elements.
Guo, Li; Hu, Yunjie; Hu, Qingqing; Lin, Jun; Li, Chunlin; Chen, Jianmin; Li, Lina; Fu, Hongbo
2014-10-15
A campaign was conducted to assess and compare the air quality at the different metro platforms at Shanghai City, focusing on particulate matter (PM) levels, chemical compositions, morphology and mineralogy, as well as species of iron. Our results indicated that the average PM₂.₅ concentrations for the three metro lines were 177.7 μg/m(3), 105.7 μg/m(3) and 82.5 μg/m(3), respectively, and the average PM1 concentrations for the three lines were 122.3 μg/m(3), 84.1 μg/m(3) and 59.6 μg/m(3), respectively. Fe, Mn, Cr, Cu, Sr, Ba and Pb concentrations in all of the sampling sites were significantly higher than that in the urban ambient air, implicating that these trace metals may be associated with the metro systems working. Individual airborne dusts were studied for morphology and mineralogy characteristics. The results revealed that the presence of most individual particles were with no definite shape and most of them were with a large metal content. Furthermore, Fe-rich particles had significantly higher abundance in the metro systems, which were more frequently encountered in the underground lines than the aboveground line. The 2D distribution map of an interested Fe-rich particle showed an uneven Fe distribution, implying that a hollow or core of other substance exists in the particle center during the formation process. Cluster analysis revealed that Fe-rich particles were possibly a mixture of Fe species. Fitting of X-ray absorption near-edge fine structure spectra (XANES) showed the main iron species within the particles collected from the three contrasting metro lines of Shanghai to be hematite, magnetite, iron-metal and mineral Fe. Hematite and mineral Fe were all found in three lines, while magnetite only existed in aboveground metro line. Iron-metal was determined in both the older and younger underground lines, based on the X-ray diffraction (XRD) analysis. As diverse Fe species have different physical-chemical characteristics and toxicity, the speciation of Fe-containing metro particles is important in the context of public health and control measures. Copyright © 2014. Published by Elsevier B.V.
Aloupi, M; Koutrotsios, G; Koulousaris, M; Kalogeropoulos, N
2012-04-01
The objectives of this survey were (1) to assess for the first time the Cd, Cu, Cr, Fe, Mn, Ni, Pb and Zn contents in wild edible mushrooms (Russula delica, Lactarius sanguifluus, Lactarius semisanguifluus, Lactarius deliciosus, Suillus bellinii) from the island of Lesvos, (2) to investigate the metals' variability among the species, as well as in relation to the chemical composition of the underlying soil, comparing mushrooms collected from volcanic and serpentine substrates and (3) to estimate metal intake by the consumption of the mushrooms under consideration. The trace metals in 139 samples were determined by flame or flameless atomic absorption spectroscopy. The median metal concentrations were as follows: Cd: 0.14; Cr: 0.10; Cu: 8.51; Fe: 30.3; Mn: 5.26; Ni: 0.34; Pb: 0.093 and Zn: 64.50, all in mgkg(-1) dry weight. The observed concentrations are among the lowest reported for mushrooms from Europe or Turkey, while Pb and Cd values did not exceed the limits set by the European Union. Significant species- and substrate-related differences in the metal contents were found, but the variability did not follow a uniform pattern for all the metals in all mushroom species. As a general trend, the mushrooms growing in serpentine sites contained higher Cd, Cr and Ni than those from volcanic sites. The calculated bioconcentration factors (BCFs) showed that none of the mushrooms can be regarded as a metal bioaccumulator, although BCF values slightly above unity were found for Zn in the three Lactarius species, and for Cu in R. delica. The studied mushrooms could supply considerable amounts of essential metals such as Zn and Cr. On the other hand, the consumption of R. delica collected from volcanic soils could provide 12% of the Cd daily tolerable intake and as high as 53% when collected from serpentine soils. Nonetheless, our results indicate that the regular consumption of wild edible mushrooms from Lesvos is quite safe for human health. Copyright © 2011 Elsevier Inc. All rights reserved.
Tracing fluid transfer across subduction zones using iron and zinc stable isotopes
NASA Astrophysics Data System (ADS)
Williams, H. M.; Debret, B.; Pons, M. L.; Bouilhol, P.
2016-12-01
In subduction zones, serpentinite devolatilization within the downgoing slab and the fluids released play a fundamental role in volatile transfer as well as the redox evolution of the sub-arc mantle. Constraining subduction-related serpentinite devolatilisation is essential in order to better understand of the nature and composition of slab-derived fluids and fluid/rock interactions. Fe and Zn stable isotopes can trace fluid composition and speciation as isotope partitioning is driven by changes in oxidation state, coordination, and bonding environment. In the case of serpentinite devolatilisation, Fe isotope fractionation should reflect changes in Fe redox state and the formation of Fe-Cl- and SO42- complexes (Hill et al., GCA 2010); Zn isotope fractionation should be sensitive to complexation with CO32-, HS- and SO42- anions (Fujii et al., GCA 2011). We targeted samples from Western Alps ophiolite complexes, interpreted as remnants of serpentinized oceanic lithosphere metamorphosed and devolatilized during subduction (Hattori and Guillot, G3 2007; Debret et al., Chem. Geol. 2013). A striking negative correlation is present between bulk serpentinite Fe isotope composition and Fe3+/Fetot, with the highest grade samples displaying the heaviest Fe isotope compositions and lowest Fe3+/Fetot (Debret et al., Geology, 2016). The same samples also display a corresponding variation in Zn isotopes, with the highest grade samples displaying isotopically light compositions (Pons et al., in revision). The negative correlation between Fe and Zn isotopes and decrease in Fe3+/Fetot can explained by serpentinite sulfide breakdown and the release of fluids enriched in isotopically light Fe and heavy Zn sulphate complexes. The migration of these SOX-bearing fluids from the slab to the slab-mantle interface or mantle wedge has important implications for the redox evolution of the sub-arc mantle and the transport of metals from the subducting slab.
Markich, S J; Brown, P L
1998-07-03
Fresh surface waters from the Hawkesbury-Nepean River, the major river supplying water to the Sydney region in south-eastern Australia, were sampled monthly during 1991 and analysed for major ions (Na, K, Ca, Mg, Cl, SO4 and HCO3), nutrients (NO3 and PO4), organic carbon and trace metals (Al, Fe, Cu, Zn, Pb, Cd, Ni, Co and Mn). The chemical composition of the river during 1991 was consistent with other studies of the river from 1977 to 1996. The major ion composition in the river is predominantly influenced by sea-salt aerosols in rainwater (headwaters) and connate sea-salt in groundwater (mid-lower reaches), with a cationic dominance order of Na > Mg > Ca > K (equivalents) and an anionic order of Cl > HCO3 > SO4. This is typical of the headwaters of other permanent coastal rivers (freshwater) in south-eastern Australia with a similar catchment lithology. These results differ markedly from the most common natural major ion assemblages established for world rivers (i.e. Ca > Mg > Na > K and HCO3 > SO4 > Cl), which tend to be predominantly influenced by chemical weathering of rocks and minerals. The mean concentrations of major ions, nutrients, organic carbon and trace metals in the freshwater reaches of the Hawkesbury-Nepean River increased by factors of 2.5-4.4, 14-18, 2.2 and 1.6-11, respectively, with increasing distance from the headwaters. Increases in major ion concentrations are attributed mainly to the increasing influence of saline groundwater inflows from regions of Wianamatta shale. Conversely, concentrations of nutrients, organic carbon and trace metals (except Fe and Al) increased as a consequence of anthropogenic inputs, particularly point discharges from sewage treatment plants (i.e. showing distinct, but variable, concentration peaks), as well as diffuse urban and/or agricultural runoff during storm events. The temporal variability of the mean concentrations of all measured parameters in this study was related to variability in water discharge. The mean concentrations of the major ions decreased by a factor of 1.5-3.0 with increasing water discharge, whereas the concentrations of nutrients, organic carbon and trace metals increased by a factor of 2.0-3.0, 1.6 and 1.3-2.0, respectively. This study provides the first survey of trace metal concentrations in the freshwater reaches of a permanent coastal river in Australia using 'clean' sampling and handling techniques. The concentrations of Cu, Zn, Pb, Cd and Ni measured in the headwaters of the Hawkesbury-Nepean River were amongst the lowest reported in the literature for riverine (freshwater) systems, and will form a benchmark for assessing the effects of increasing urbanisation in the catchment.
NASA Astrophysics Data System (ADS)
Scholz, Florian; Siebert, Christopher; Dale, Andrew W.; Frank, Martin
2017-09-01
The concentration and isotope composition of molybdenum (Mo) in sediments and sedimentary rocks are widely used proxies for anoxic conditions in the water column of paleo-marine systems. While the mechanisms leading to Mo fixation in modern restricted basins with anoxic and sulfidic (euxinic) conditions are reasonably well constrained, few studies have focused on Mo cycling in the context of open-marine anoxia. Here we present Mo data for water column particulate matter, modern surface sediments and a paleo-record covering the last 140,000 years from the Peruvian continental margin. Mo concentrations in late Holocene and Eemian (penultimate interglacial) shelf sediments off Peru range from ∼70 to 100 μg g-1, an extent of Mo enrichment that is thought to be indicative of (and limited to) euxinic systems. To investigate if this putative anomaly could be related to the occasional occurrence of sulfidic conditions in the water column overlying the Peruvian shelf, we compared trace metal (Mo, vanadium, uranium) enrichments in particulate matter from oxic, nitrate-reducing (nitrogenous) and sulfidic water masses. Coincident enrichments of iron (Fe) (oxyhydr)oxides and Mo in the nitrogenous water column as well as co-variation of dissolved Fe and Mo in the sediment pore water suggest that Mo is delivered to the sediment surface by Fe (oxyhydr)oxides. Most of these precipitate in the anoxic-nitrogenous water column due to oxidation of sediment-derived dissolved Fe with nitrate as a terminal electron acceptor. Upon reductive dissolution in the surface sediment, a fraction of the Fe and Mo is re-precipitated through interaction with pore water sulfide. The Fe- and nitrate-dependent mechanism of Mo accumulation proposed here is supported by the sedimentary Mo isotope composition, which is consistent with Mo adsorption onto Fe (oxyhydr)oxides. Trace metal co-variation patterns as well as Mo and nitrogen isotope systematics suggest that the same mechanism of Mo delivery caused the 'anomalously' high interglacial Mo accumulation rates in the paleo-record. Our findings suggest that Fe- and nitrate-dependent Mo shuttling under nitrogenous conditions needs to be considered a possible reason for sedimentary Mo enrichments during past periods of widespread anoxia in the open ocean.
Polechońska, Ludmiła; Samecka-Cymerman, Aleksandra
2016-02-01
The aim of present study was to investigate the level of trace metals and macroelements in Hydrocharis morsus-ranae collected from regions differing in the degree and type of pollution. Concentrations of 17 macro- and microelements were determined in roots and shoots of European frogbit as well as in water and bottom sediments from 30 study sites. Plants differed in concentrations of elements and bioaccumulation capacity depending on the characteristics of dominant anthropogenic activities in the vicinity of the sampling site. Shoots of H. morsus-ranae growing in the vicinity of organic chemistry plants and automotive industry contained particularly high levels of Cd, Co, and S. Plants from area close to heat and power plant, former ferrochrome industry and new highway, were distinguished by the highest concentrations of Cr, Cu, and Pb. European frogbit from both these regions contained more Fe, Hg, Mn, Ni, and Zn than plants from agricultural and recreational areas. The concentrations of alkali metals and Co, Fe, and N in H. morsus-ranae were elevated in relation to the natural content in macrophytes irrespectively to their content in the environment. Based on the values of Bioaccumulation and Translocation Factors, European frogbit is an accumulator for Co, Cr, Cu, Fe, K, Mn, Ni, Pb, and Zn and a good candidate for phytoremediation of water polluted with Co, Cu, Hg, K, Mn, and Ni. The amount of Co and Mn removed from water and accumulated in the plant biomass during the vegetation season was considerably high.
Gao, Hong-Wen; Chen, Fang-Fang; Chen, Ling; Zeng, Teng; Pan, Lu-Ting; Li, Jian-Hua; Luo, Hua-Fei
2007-03-21
A novel detection approach named chromophore-decolorizing with free radicals is developed for determination of trace heavy metal. The hydroxyl radicals (HO) generated from Fe(III) and hydrogen peroxide will oxidize the free chromophore into almost colorless products. The copper-acid chrome dark blue (ACDB) complexation was investigated at pH 5.07. In the presence of Fe(III) and hydrogen peroxide, the excess ACDB was decolorized in the Cu-ACDB reaction solution, and the final solution contained only one color compound, the Cu-ACDB complex. After oxidation of free hydroxyl radicals, the complexation becomes sensitive and selective and it has been used for the quantitation of trace amounts of Cu(II) dissolved in natural water. Beer's law is obeyed in the range from 0 to 0.500 microg mL(-1) Cu(II) and the limit of detection is only 6 microg L(-1) Cu(II). Besides, the Cu-ACDB complex formed was characterized.
Bacterially Induced Weathering of Ultramafic Rock and Its Implications for Phytoextraction
Kidd, Petra; Kuffner, Melanie; Prieto-Fernández, Ángeles; Hann, Stephan; Monterroso, Carmela; Sessitsch, Angela; Wenzel, Walter; Puschenreiter, Markus
2013-01-01
The bioavailability of metals in soil is often cited as a limiting factor of phytoextraction (or phytomining). Bacterial metabolites, such as organic acids, siderophores, or biosurfactants, have been shown to mobilize metals, and their use to improve metal extraction has been proposed. In this study, the weathering capacities of, and Ni mobilization by, bacterial strains were evaluated. Minimal medium containing ground ultramafic rock was inoculated with either of two Arthrobacter strains: LA44 (indole acetic acid [IAA] producer) or SBA82 (siderophore producer, PO4 solubilizer, and IAA producer). Trace elements and organic compounds were determined in aliquots taken at different time intervals after inoculation. Trace metal fractionation was carried out on the remaining rock at the end of the experiment. The results suggest that the strains act upon different mineral phases. LA44 is a more efficient Ni mobilizer, apparently solubilizing Ni associated with Mn oxides, and this appeared to be related to oxalate production. SBA82 also leads to release of Ni and Mn, albeit to a much lower extent. In this case, the concurrent mobilization of Fe and Si indicates preferential weathering of Fe oxides and serpentine minerals, possibly related to the siderophore production capacity of the strain. The same bacterial strains were tested in a soil-plant system: the Ni hyperaccumulator Alyssum serpyllifolium subsp. malacitanum was grown in ultramafic soil in a rhizobox system and inoculated with each bacterial strain. At harvest, biomass production and shoot Ni concentrations were higher in plants from inoculated pots than from noninoculated pots. Ni yield was significantly enhanced in plants inoculated with LA44. These results suggest that Ni-mobilizing inoculants could be useful for improving Ni uptake by hyperaccumulator plants. PMID:23793627
NASA Astrophysics Data System (ADS)
Donohue, Patrick H.; Hill, Eddy; Huss, Gary R.
2018-02-01
Pallasite meteorites, which consist primarily of olivine and metal, may be remnants of disrupted core-mantle boundaries of differentiated asteroids or planetesimals. The early thermal histories of pallasites are potentially recorded by minor- and trace-element zonation in olivine. However, constraining this history requires knowledge of element behavior under the conditions of pallasite formation, which is lacking for many of the main elements of interest (e.g., Co, Cr, Mn). In this study, we experimentally determined metal/olivine partition coefficients for Fe, Ni, Co, Cr, and Mn in a pallasite analogue at subsolidus temperatures. Metal/olivine partition coefficients (KM) increase in the order KMn < KCr < 1 < KFe < KCo < KNi, with five orders of magnitude separating KMn from KNi. Transition metals also become more siderophile with increasing experimental temperature (900-1550 °C). The experiments incidentally produced diffusion profiles in olivine for these elements; our results suggest they diffuse through olivine at similar rates. Core compositions of pallasite olivines are consistent with high-temperature equilibration with FeNi-metal. Olivine zonation toward crystal rims varies significantly for the investigated transition metals. We suggest rim zonation results from partial re-equilibration during late stage crystallization of minor phases (e.g., chromite, phosphates). This re-equilibration occurred over short timescales relative to overall pallasite cooling, likely tied to initial cooling rates on the order of 100-300 °C/Myr.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Hlawatsch, S.; Garbe-Schonberg, C.D.; Lechtenberg, F.
Trace element profiles in ferromanganese nodules from the western Baltic Sea were analyzed with laser ablation inductively coupled plasma mass spectroscopy (LA-ICP-MS) and synchrotron-based micro-X-ray radiation techniques (fluorescence: mSXRF, and diffraction: mXRD) at high spatial resolution in growth direction. Of the trace elements studied (Zn, Cu, Cd, Ni, Co, Mo, Ba), Zn showed the most significant enrichment, with values in the outermost surface layers of up to six-fold higher than those found in older core parts. The high-resolution Zn profiles provide the necessary temporal resolution for a dating method analogous to dendrochronology. Profiles in various samples collected during two decadesmore » were matched and the overlapping sections used for estimation of the accretion rates. Assuming a continuous accretion of these relatively fast growing nodules (on average 20 mm a-1) over the last century, the Zn enrichment was thus assessed to have commenced around 1860/70 in nodules from the Kiel Bight and in 1880/90 from Mecklenburg Bight, reflecting the enhanced heavy metal emissions with rising industrialization in Europe. Apart from the obvious success with Zn, only As and Co show significant but only 1.5-fold enrichments in the most recent growth layers of the nodules. Other anthropogenic trace metals like Cu and Cd are not at all enriched, which, together with the distinct early-diagenetic Fe/Mn banding, weakens the potential of the nodules for retrospective monitoring.« less
Distribution of Heavy Metals in Surface Sediments of the Bay of Bengal Coast
Hasan, M. R.; Khan, M.; Aktar, S.; Fatema, K.
2017-01-01
The concentrations of major (Si, Al, Ca, Fe, and K) and minor (Cd, Mn, Ni, Pb, U, Zn, Co, Cr, As, Cu, Rb, Sr, and Zr,) elements in the surficial sediments were studied in an attempt to establish their concentration in the Bengal coast. It was revealed that the majority of the trace elements have been introduced into the Bengal marine from the riverine inflows that are also affected by the impact of industrial, ship breaking yard, gas production plant, and urban wastes. The concentration of heavy metals was measured using Atomic Absorption Spectroscopy and Energy Dispersive X-ray fluorescence instruments. The highest concentrations for several trace elements were thus recorded which generally decrease with distance from the coast. It was observed that the heavy metal concentrations in the sediments generally met the criteria of international marine sediment quality. However, both the contamination factor and pollution load index values suggested the elevation of some metals' concentrations in the region. Constant monitoring of the Bengal coast water quality needs to be recorded with a view to minimizing the risk of health of the population and the detrimental impacts on the aquatic ecosystem. PMID:28255298
Flanagan, Sarah M.; Belaval, Marcel; Ayotte, Joseph D.
2014-01-01
Trace metals, such as arsenic, iron, lead, manganese, and uranium, in groundwater used for drinking have long been a concern because of the potential adverse effects on human health and the aesthetic or nuisance problems that some present. Moderate to high concentrations of the trace metal arsenic have been identified in drinking water from groundwater sources in southeastern New Hampshire, a rapidly growing region of the State (Montgomery and others, 2003). During the past decade (2000–10), southeastern New Hampshire, which is composed of Hillsborough, Rockingham, and Strafford Counties, has grown in population by nearly 48,700 (or 6.4 percent) to 819,100. These three counties contain 62 percent of the State’s population but encompass only about 22 percent of the land area (New Hampshire Office of Energy and Planning, 2011). According to a 2005 water-use study (Hayes and Horn, 2009), about 39 percent of the population in these three counties in southeastern New Hampshire uses private wells as sources of drinking water, and these wells are not required by the State to be routinely tested for trace metals or other contaminants. Some trace metals have associated human-health benchmarks or nonhealth guidelines that have been established by the U.S. Environmental Protection Agency (EPA) to regulate public water supplies. The EPA has established a maximum contaminant level (MCL) of 10 micrograms per liter (μg/L) for arsenic (As) and a MCL of 30 μg/L for uranium (U) because of associated health risks (U.S. Environmental Protection Agency, 2012). Iron (Fe) and manganese (Mn) are essential for human health, but Mn at high doses may have adverse cognitive effects in children (Bouchard and others, 2011; Agency for Toxic Substances and Disease Registry, 2012); therefore, the EPA has issued a lifetime health advisory (LHA) of 300 μg/L for Mn. Recommended secondary maximum contaminant levels (SMCLs) for Fe (300 μg/L) and Mn (50 μg/L) were established primarily as nonhealth guidelines—based on aesthetic considerations, such as taste or the staining of laundry and plumbing fixtures—because these contaminants, at the SMCLs, are not considered to present risks to human health. Because lead (Pb) contamination of drinking water typically results from corrosion of plumbing materials belonging to water-system customers but still poses a risk to human health, the EPA established an action level (AL) of 15 μg/L for Pb instead of an MCL or SMCL (U.S. Environmental Protection Agency, 2012). The 15-μg/L AL for Pb has been adopted by the New Hampshire Department of Environmental Services for public water systems, and if exceeded, the public water system must inform their customers and undertake additional actions to control corrosion in the pipes of the distribution system (New Hampshire Department of Environmental Services, 2013). Unlike the quality of drinking water provided by public water suppliers, the quality of drinking water obtained from private wells in New Hampshire is not regulated; consequently, private wells are sampled only when individual well owners voluntarily choose to sample them. The U.S. Geological Survey (USGS), in cooperation with the EPA New England, conducted an assessment in 2012–13 to provide private well owners and State and Federal health officials with information on the distribution of trace-metal (As, Fe, Pb, Mn, and U) concentrations in groundwater from bedrock aquifers in the three counties of southeastern New Hampshire. This fact sheet analyzes data from water samples collected by a randomly selected group of private well owners from the three-county study area and describes the major findings for trace-metal concentrations.
Oxygen Fugacity at High Pressure: Equations of State of Metal-Oxide Pairs
NASA Technical Reports Server (NTRS)
Campbell A. J.; Danielson, L.; Righter, K.; Wang, Y.; Davidson, G.; Wang, Y.
2006-01-01
Oxygen fugacity (fO2) varies by orders of magnitude in nature, and can induce profound changes in the chemical state of a substance, and also in the chemical equilibrium of multicomponent systems. One prominent area in high pressure geochemistry, in which fO2 is widely recognized as a principal controlling factor, is that of metal-silicate partitioning of siderophile trace elements (e.g., [1]). Numerous experiments have shown that high pressures and temperatures can significantly affect metal/silicate partitioning of siderophile and moderately siderophile elements. Parameterization of these experimental results over P, T, X, and fO2 can allow the observed siderophile element composition of the mantle to be associated with particular thermodynamic conditions [2]. However, this is best done only if quantitative control exists over each thermodynamic variable relevant to the experiments. The fO2 values for many of these partitioning experiments were determined relative to a particular metal-oxide buffer (e.g., Fe-FeO (IW), Ni-NiO (NNO), Co-CoO, Re-ReO2 (RRO)), but the parameterization of all experimental results is weakened by the fact that the pressure-induced relative changes between these buffer systems are imprecisely known.
NASA Astrophysics Data System (ADS)
Spradlin, J.; Fiorentino, A. J., II; Siegel, D. I.
2014-12-01
We report the results of an evaluation of the trace and major metal composition of shallow sedimentary rock formations in the Appalachian Basin that control the quality of potable water produced in domestic and other wells. In particular, we quantify the mobile and total metals for which there are health concerns related to unconventional gas exploitation; Fe, Mn, Sr, Ba, As, and Pb. To do this, we sampled the upper 400 feet of Devonian to Pennsylvanian aged bedrock from Marcellus, NY to State College, PA. We used a variation of the U.S. Geological Survey Field Leach Test to assess water reactivity and leaching potential. Al, Zn, and U potentially can be leached from aquifer rocks naturally under acidic conditions, such as where pyrite might oxidize, to above current allowable regulatory values for these metals (2 mg/L, 5 mg/L, and 0.03 mg/L respectively) from some of the clay-rich formations. Groundwater analyses from both New York and Pennsylvania show that natural ion exchange occurs along flow paths from ridges to valleys. We find the laboratory cation exchange capacity (CEC) spans what might be expected for illite and chlorite commonly found in these rocks. Given the low surface area of the mineral surfaces of the fractures through which most of the water moves, the observed ion exchange in these rocks is not well understood. Along with this broad scale study area we investigated a Devonian outcrop 4 miles North of Cortland, NY to evaluate small-scale trace metal heterogeneity within a single stratigraphic section. Together these two studies provide important information to determine the extent to which ground water might be naturally high in trace metal composition, either because of geochemical conditions or entrainment of suspended material not removed prior to sampling.
Coxon, T M; Odhiambo, B K; Giancarlo, L C
2016-10-15
The progressively declining ecological condition of the Chesapeake Bay is attributed to the influx of contaminants associated with sediment loads supplied by its largest tributaries. The continued urban expansion in the suburbs of Virginia cities, modern agricultural activities in the Shenandoah Valley, the anthropogenic and climate driven changes in fluvial system hydrodynamics and their potential associated impacts on trace metals enrichment in the bay's tributaries necessitate constant environmental monitoring of these important water bodies. Eight (210)Pb and (137)Cs dated sediment cores and seventy two sediment grab samples were used to analyze the spatial and temporal distributions of Al, Ca, Mg, Cr, Cd, As, Se, Pb, Cu, Zn, Mn, and Fe in the waterways of the Virginia portion of the Chesapeake Bay basin. The sediment cores for trace metal historical fluctuation analysis were obtained in lower fluvial-estuarine environments and reservoirs in the upper reaches of the basin. The trace metal profiles revealed high basal enrichment factors (EF) of between 0.05 and 40.24, which are interpreted to represent early nineteenth century agricultural activity and primary resource extraction. Surficial enrichment factors on both cores and surface grab samples ranged from 0.01 (Cu) to 1421 (Cd), with Pb, Cu, Zn, and Cd enrichments a plausible consequence of modern urban expansion and industrial development along major transportation corridors. Contemporary surficial enrichments of As, Se, and Cr also ranged between 0 and 137, with the higher values likely influenced by lithological and atmospheric sources. Pearson correlation analyses suggest mining and agricultural legacies, coupled with aerosol deposition, are responsible for high metal concentrations in western lakes and headwater reaches of fluvial systems, while metal accumulation in estuarine reaches of the major rivers can be attributed to urban effluence and the remobilization of legacy sediments. Copyright © 2016 Elsevier B.V. All rights reserved.
NASA Astrophysics Data System (ADS)
Antcibor, I.; Eschenbach, A.; Kutzbach, L.; Bolshiyanov, D.; Pfeiffer, E.-M.
2012-04-01
Arctic regions are one of the most sensitive areas with respect to climatic changes and human impacts. Research is required to discover how the function of permafrost soils as a buffering system for metal pollutants could change in response to the predicted changes. The goal of this work is to determine the background levels of trace metals in the pristine arctic ecosystems of the Lena River Delta in Northeastern Siberia and to evaluate the possible effect of human impacts on this arctic region. The Lena River Delta represents areas with different dominating geomorphologic processes that can generally be divided between accumulation and erosion sites. Frequent changes of the river water level create different periods of sedimentation and result in the formation of stratified soils and sediment layers which are dominated either by mineral substrates with allochthonous organic matter or pure autochthonous peat. The deposited sediments that have formed the delta islands are mostly composed of sand fractions; therefore the buffering effects of clay materials can be neglected. Samoylov Island is representative of the south-central and eastern modern delta surfaces of the Lena River Delta and is selected as a pilot study site. We determined total element contents of Fe, Mn, Zn, Cd, Ni, Cu, As, Pb, Co and Hg in soil horizons from different polygonal elevated rims, polygonal depressed centers and the middle floodplain. High gravimetric concentrations (related to dry mass of soil material) of Mn and Fe are found within all soil profiles and vary from 0.14 to 1.39 g kg-1 and from 10.7 to 41.2 g kg-1, respectively. While the trace element concentrations do not exceed typical crustal abundances, the maximum values of most of the metals are observed within the soil profile situated at the middle floodplain. This finding suggests that apart from the parent material the second potential source of trace metals is due to allochthonous substance input during annual flooding of the middle floodplain. Correlation analysis between element concentrations, grain-size distribution and carbon content revealed a direct dependence of the element distribution within all soil profiles on its mineralogical composition. Based on the obtained results we suggest that there are negligible atmospheric depositions caused by human activity on the investigation site. Therefore this data can provide a point of comparison against man-made influences on permafrost-affected landscapes and also on similar pristine areas in the Arctic region.
Redox systematics of a magma ocean with variable pressure-temperature gradients and composition.
Righter, K; Ghiorso, M S
2012-07-24
Oxygen fugacity in metal-bearing systems controls some fundamental aspects of the geochemistry of the early Earth, such as the FeO and siderophile trace element content of the mantle, volatile species that influence atmospheric composition, and conditions for organic compounds synthesis. Redox and metal-silicate equilibria in the early Earth are sensitive to oxygen fugacity (fO(2)), yet are poorly constrained in modeling and experimentation. High pressure and temperature experimentation and modeling in metal-silicate systems usually employs an approximation approach for estimating fO(2) that is based on the ratio of Fe and FeO [called "ΔIW (ratio)" hereafter]. We present a new approach that utilizes free energy and activity modeling of the equilibrium: Fe + SiO(2) + O(2) = Fe(2)SiO(4) to calculate absolute fO(2) and relative to the iron-wüstite (IW) buffer at pressure and temperature [ΔIW (P,T)]. This equilibrium is considered across a wide range of pressures and temperatures, including up to the liquidus temperature of peridotite (4,000 K at 50 GPa). Application of ΔIW (ratio) to metal-silicate experiments can be three or four orders of magnitude different from ΔIW (P,T) values calculated using free energy and activity modeling. We will also use this approach to consider the variation in oxygen fugacity in a magma ocean scenario for various thermal structures for the early Earth: hot liquidus gradient, 100 °C below the liquidus, hot and cool adiabatic gradients, and a cool subsolidus adiabat. The results are used to assess the effect of increasing P and T, changing silicate composition during accretion, and related to current models for accretion and core formation in the Earth. The fO(2) in a deep magma ocean scenario may become lower relative to the IW buffer at hotter and deeper conditions, which could include metal entrainment scenarios. Therefore, fO(2) may evolve from high to low fO(2) during Earth (and other differentiated bodies) accretion. Any modeling of core formation and metal-silicate equilibrium should take these effects into account.
NASA Astrophysics Data System (ADS)
Muth, M.; Wallace, P. J.; Walowski, K. J.
2017-12-01
Arc magmas have an oxidized signature (higher Fe3+/∑Fe) relative to MORB. This oxidized signature could be developed during crustal differentiation or be derived from slab components such as hydrous melts and fluids. Previous work in the Lassen region of the Cascade arc shows evidence for the addition of a hydrous slab component to the mantle wedge beneath the southern Cascades [1]. Here we investigate whether this hydrous slab component is linked to the oxidation state of primitive magmas using the sulfur, metal, and trace element concentrations of olivine-hosted melt inclusions. Melt inclusions were selected from the tephra of three cinder cones in Lassen volcanic field and analyzed for trace elements and metals (Cu, Zn, Sn) using LA-ICPMS and for major elements, S, and Cl using EMPA. Sulfur concentrations in individual melt inclusions range from 900 to 2200 ppm. Cu, Zn, and Sn concentrations in individual melt inclusions range from 17 to 167 ppm, 65 to 127 ppm, and 0.4 to 1.4 ppm, respectively. Average sulfur concentrations are different for each of the three cinder cones, and individual melt inclusion S/Dy values correlate well with Sr/Nd values. This is an indication that, like other volatiles, sulfur is supplied to the mantle wedge by a slab-derived component. To assess whether this sulfur-carrying slab component affects the oxidation state of the mantle wedge during melting, we used estimates of sulfur content at sulfide saturation to place a minimum bound on fO2 values for the primitive magmas at each cinder cone. These values range from QFM to QFM + 1.5. Despite this wide range of fO2 values, the concentrations of Cu and other metals are low relative to values predicted by partial melting of the mantle wedge during relatively oxidized (greater than QFM + 1.3) conditions [2], and do not vary systematically with indicators of slab component addition such as Sr/Nd. This suggests that metals are not derived from the slab component and/or that residual sulfide is present during melting across the wide range of fO2 values. This observation is also consistent with the addition of a sulfur-carrying slab component to the mantle wedge. Future work will compare these observations to direct measurement of Fe3+/∑Fe and S6+/∑S using XANES. [1] Walowski et al. 2016, EPSL. [2] Lee et al. 2012, Science.
Kemp, M; Wepener, V; de Kock, K N; Wolmarans, C T
2017-12-01
The Marico River is relatively unaffected by anthropogenic activities. However, metal concentrations-mainly from natural sources-occasionally exceed environmental quality guidelines. Macroinvertebrates are capable to react to these metals through processes such as the induction of metallothioneins (MTs). The aims of this study were to determine whether the induction of MTs can be used as indicator of natural metal exposure in not anthropogenically impacted systems and whether there are relationships between metal concentrations in water, sediment and macroinvertebrates and concomitant MT levels. Positive correlations were found between metals in sediment and macroinvertebrates, while there were no correlations between metal concentrations in water and macroinvertebrates. Even in a not anthropogenically impacted system, a positive correlation existed between trace metal bioaccumulation (e.g. Ni, Pb, Zn) in macroinvertebrates and the induction of MTs. There were, however, no correlations between MTs and bioaccumulation of earth metals (e.g. Al, Fe, Mn, Ti).
Matong, Joseph M; Nyaba, Luthando; Nomngongo, Philiswa N
2016-07-01
The main objectives of this study were to determine the concentration of fourteen trace elements and to investigate their distribution as well as a contamination levels in selected agricultural soils. An ultrasonic assisted sequential extraction procedure derived from three-step BCR method was used for fractionation of trace elements. The total concentration of trace elements in soil samples was obtained by total digestion method in soil samples with aqua regia. The results of the extractable fractions revealed that most of the target trace elements can be transferred to the human being through the food chain, thus leading to serious human health. Enrichment factor (EF), geo-accumulation index (Igeo), contamination factor (CF), risk assessment code (RAC) and individual contamination factors (ICF) were used to assess the environmental impacts of trace metals in soil samples. The EF revealed that Cd was enriched by 3.1-7.2 (except in Soil 1). The Igeo results showed that the soils in the study area was moderately contaminated with Fe, and heavily to extremely polluted with Cd. The soil samples from the unplanted field was found to have highest contamination factor for Cd and lowest for Pb. Soil 3 showed a high risk for Tl and Cd with RAC values of greater than or equal to 50%. In addition, Fe, Ni, Cu, V, As, Mo (except Soil 2), Sb and Pb posed low environmental risk. The modified BCR sequential extraction method provided more information about mobility and environmental implication of studied trace elements in the study area. Copyright © 2016 Elsevier Ltd. All rights reserved.
Micronutrient metal speciation is controlled by competitive organic chelation in grassland soils
DOE Office of Scientific and Technical Information (OSTI.GOV)
Boiteau, Rene M.; Shaw, Jared B.; Pasa-Tolic, Ljiljana
Many elements are scarcely soluble in aqueous conditions found in high pH environments, such as calcareous grassland soils, unless complexed to strong binding organic ligands. To overcome this limitation, some plants and microbes produce chelators that solubilize micronutrient metals such as Fe, Ni, Cu, and Zn from mineral phases. These complexes are taken up by organisms via specific membrane receptors, thereby differentially impacting the bioavailability of these metals to the plant and microbial community. Although the importance of these chelation strategies for individual organisms has been well established, little is known about which pathways coexist within rhizosphere microbiomes or howmore » they interact and compete for metal binding. Identifying these metallo-organic species within natural ecosystems has remained a formidable analytical challenge due to the vast diversity of compounds and poorly defined metabolic processes in complex soil matrix. Herein, we employed recently developed liquid chromatography (LC) mass spectrometry (MS) methods to characterize the speciation of water-soluble dissolved trace elements (Fe, Ni, Cu, and Zn) from Kansas Prairie soil. Both plant and fungal chelators were identified, revealing compound-specific patterns of chelation to biologically essential metals. Numerous metabolites typically implicated in plant iron acquisition and homeostasis, including mugineic acids, deoxymugineic acid, nicotianamine, and hydroxynicotianamine, dominated the speciation of divalent metals such as Ni, Cu, and Zn (2-57 pmol / g soil). In contrast, the fungal siderophore ferricrocine bound comparatively more trivalent Fe (9pmol / g soil). These results define biochemical pathways that underpin the regulation of metals in the grassland rhizosphere. They also raise new questions about the competition of these compounds for metal binding and their bioavailability to different members of the rhizosphere population. Even small structural differences result in significant differences in their environmental metal speciation, and likely impact metal uptake within the rhizosphere of calcareous soils.« less
Farkas, Attila; Bidló, András; Bolodár-Varga, Bernadett; Jánoska, Ferenc
2017-04-01
Several previous study results have already demonstrated that golden jackal and red fox may serve as biological indicators of trace elements and heavy metal concentrations in the various regions they inhabit. The aim of this study was to evaluate accumulation patterns of targeted elements (Al, Ca, Cr, Cu, Fe, Mg, Mn, Ni and Pb) in liver samples of red foxes and golden jackals collected during the same period in the southern part of Romania. The accumulation patterns of trace elements in the livers of sympatric golden jackal and red fox were practically the same. To date, separate studies of the species individually in different habitats have shown that either of the species can be used for ecotoxicological and biomonitoring studies. Moreover, in general gender related studies, no significant differences in the concentrations of the investigated elements were found in either jackals or foxes. Also, average metal concentrations in liver samples do not show significant differences between groups under and above 12 months of age.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Coussy, Samuel; Grangeon, Sylvain; Bataillard, Philippe
The prediction of the long term trace element mobility in anthropogenic soils would be a way to anticipate land management and should help in reusing slightly contaminated materials. In the present study, iron (Fe) and zinc (Zn) status evolution was investigated in a 100-year old Technosol. The site of investigation is an old brownfield located in the Nord-Pas-de-Calais region (France) which has not been reshaped since the beginning of the last century. The whole soil profile was sampled as a function of depth, and trace elements mobility at each depth was determined by batch leaching test. A specific focus onmore » Fe and Zn status was carried out by bulk analyses, such as selective dissolution, X-ray diffraction (XRD) and X-ray absorption spectroscopy (XAS). Fe and Zn status in the profile samples was also studied using laterally resolved techniques such as μ-particle induced X-ray emission (μ-PIXE) and μ-Rutherford backscattering spectroscopy (μ-RBS). The results indicate that (i) Fe is mainly under Fe(III) form, except a minor contribution of Fe(II) in the deeper samples, (ii) some Fe species inherited from the past have been weathered and secondary minerals are constituted of metal-bearing sulphates and Fe (hydr)oxides, (iii) ferrihydrite is formed during pedogenesis (iv) 20 to 30% more Fe (hydr)oxides are present in the surface than in depth and (v) Zn has tetrahedral coordination and is sorbed to phases of increasing crystallinity when depth increases. Zn-bearing phases identified in the present study are: complex Fe, Mn, Zn sulphides, sulphates, organic matter, and ferrihydrite. Soil formation on such material does not induce a dramatic increase of Zn solubility since efficient scavengers are concomitantly formed in the system. However, Technosols are highly heterogeneous and widely differ from one place to another. The behavior examined in this study is not generic and will depend on the type of Technosol and on the secondary minerals formed as well as on the nature and amount of organic matter.« less
NASA Astrophysics Data System (ADS)
Oleinikova, Olga V.; Drozdova, Olga Yu.; Lapitskiy, Sergey A.; Demin, Vladimir V.; Bychkov, Andrey Yu.; Pokrovsky, Oleg S.
2017-08-01
Photochemical degradation of dissolved organic matter (DOM) is recognized as the major driver of CO2 emission to the atmosphere from the inland waters of high latitudes. In contrast to numerous studies of photo-induced DOM transformation, the behavior of trace element (TE) during photodegradation of boreal DOM remains virtually unknown. Towards a better understanding of concentration, size fractionation and speciation change of DOM and TE in boreal waters subjected to solar radiation, we conducted on-site photo-degradation experiments in stream and bog water collected from a pristine zone of the Northern Karelia (Russian subarctic). The removal of Fe and Al occurred only in the bog water (90% and 50% respectively, over 5 days of reaction), whereas no detectable decrease of dissolved (<0.22 μm) Al and Fe concentration was observed in the boreal stream. A number of low-soluble TE linked to Fe-rich organo-mineral colloids followed the behavior of Fe during bog water exposure to sunlight: Al, P, Ti, V, Cr, As, Y, Zr, REEs, Hf, Th, Pb and U. The second group of elements (Li, B, Mg, Ca, Sr, Ba, Na, K, Rb, Si, Mn, Ni, Cu, Co, Cd, Sb) was indifferent to photodegradation of DOM and exhibited a non-systematic variation (±10-15% from the control) of <0.22 μm fraction in the course of sunlight exposure. The bog water insolation yielded a factor of 3 ± 1 increase of low molecular weight (LMW < 1 kDa) fraction of organic carbon, Al, Fe, U, Mg, Ca, Mn, Co, Ni, Sr, Cd and Ba after 200 h of sunlight exposure compared to the dark control. The LMW< 1 kDa fraction was preferentially enriched in Fe, Al, Ca, Mg and other divalent metals relative to Corg. The climate warming leading to water temperature rise in the boreal zone will intensify the Fe and Al hydroxide coagulation while increasing the production of LMW organic ligands and free metals and metal - organic complexes.
Diffusion-reaction modelling of early diagenesis of sediments affected by acid mine drainage.
NASA Astrophysics Data System (ADS)
Torres, E.; Ayora, C.; Arias, J. L.; Garcia Robledo, E.; Papaspyrou, S.; Corzo, A.
2012-04-01
The Sancho Reservoir (SW Spain) is a monomictic water reservoir affected by acid mine drainage. It has a pH of ~4, with high sulfate (200 ppm) and heavy metal concentrations in the water column. The reservoir develops reducing conditions at the bottom during the stratification period. A laboratory experiment was carried out to study the effect of this oxygen variation on the early diagenesis processes and the cycling of metals. Sediment cores and bottom water were collected during the stratification period and brought to the laboratory. The cores were maintained in an aquarium bubbled with nitrogen gas to maintain hypoxic conditions (~10 µmol O2 L-1) for 1 day. Then, oxic conditions were induced by bubbling with air and maintained for 50 days. Finally, hypoxia was re-established for 10 days. Triplicate cores were sliced in a anaerobic glove box at each stage. Pore water was extracted by centrifugation and: Eh, pH, DO, DOC, sulfate, Fe and trace metals were analyzed. The sediment was freeze-dried and a sequential extraction protocol was applied to determine the exchangeable, AVS, Fe-(oxy)hydroxides, Fe-oxides, organic matter, pyrite sulfur and residual phase iron fractions. Organic carbon and total C, N, H and S were also analyzed in the sediment. A reactive diffusion model has been used to obtain the rates of biogeochemical reactions by fitting to the experimental data. During hypoxic conditions sulfate and Fe-(oxy)hydroxides are reduced, due to the anaerobic oxidation of organic matter, at the very first few cm, releasing sulfide and Fe(II) which precipitate as iron sulfide. When oxygen diffuses in the sediment, sulfate-reduction and the sulfide peaks are displaced deeper into the sediment. Oxygen penetration depth and its consumption rates in the sediment increase quickly, resulting in the reoxidation of the iron sulfides that had precipitated during hypoxic conditions. Sulfide and Fe(II) are released and are again oxidized to Fe(III) and sulfate respectively. Arsenic can be adsorbed onto the iron sulfides and pyrite. During the dissolution of the iron sulfide As will be released and will diffuse to the water column. Copper and zinc can also precipitate as metal sulfides.
NASA Astrophysics Data System (ADS)
Gao, Wenyuan; Ciobanu, Cristiana L.; Cook, Nigel J.; Huang, Fei; Meng, Lin; Gao, Shang
2017-12-01
Permian mafic-ultramafic layered intrusions in the central part of the Emeishan Large Igneous Province (ELIP), Southwestern China, host Fe-Ti-V-oxide ores that have features which distinguish them from other large layered intrusion-hosted deposits. The origin of these ores is highly debated. Careful petrographic examination, whole rock analysis, electron probe microanalysis, and measurement and mapping of trace element concentrations by laser ablation inductively coupled plasma mass spectrometry in all major and minor minerals (clinopyroxene, plagioclase, olivine, amphibole, titanomagnetite, ilmenite, pleonaste and pyrrhotite) has been undertaken on samples from the Lanjiahuoshan deposit, representing the Middle, Lower and Marginal Zone of the Panzhihua intrusion. Features are documented that impact on interpretation of intrusion petrology and with implications for genesis of the Fe-Ti-V-oxide ores. Firstly, there is evidence, as symplectites between clinopyroxene and plagioclase, for introduction of complex secondary melts. Secondly, reaction between a late hydrothermal fluid and clinopyroxene is recognized, which has led to formation of hydrated minerals (pargasite, phlogopite), as well as a potassium metasomatic event, postdating intrusion solidification, which led to formation of K-feldspar. Lastly, partitioning of trace elements between titanomagnetite and silicates needs to consider scavenging of metals by ilmenite (Mn, Sc, Zr, Nb, Sn, Hf and Ta) and sulfides, as well as the marked partitioning of Co, Ni, Zn, Ga, As and Sb into spinels exsolved from titanomagnetite. The role of these less abundant phases may have been understated in previous studies, highlighting the importance of petrographic examination of complex silicate-oxide-sulfide assemblages, as well as the need for a holistic approach to trace element analysis, acknowledging all minerals within the assemblage.
Trace element accumulation in bivalve mussels Anodonta woodiana from Taihu Lake, China.
Liu, Hongbo; Yang, Jian; Gan, Juli
2010-11-01
Data are presented for 13 trace metals (Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Mo, Ag, Cd, and Pb) in 38 bivalve mussels Anodonta woodiana from four separate sites (Huzhou, Dapu, Sansandao, and Manshan) around the Taihu Lake of China. All elemental concentrations generally ranked in decreasing order, Mn > Fe > Zn > As ≈ Cu ≈ Cd ≈ Se > Pb > Mo ≈ Ag, except that Cr, Co, and Ni were not detected. Anodonta woodiana was able to bioaccumulate essential Mn and toxic Cd to the extremely high level of 19,240 and 53 mg/kg dry weight, respectively. Geographical differences in the concentrations of trace elements were usually significant between sampling sites except for As and Pb, and the mussels from Sanshandao site had mostly accumulated or were contaminated with essential and toxic elements. The residue level of Cd in A. woodiana from the Sanshandao and Manshan sites appeared to be even higher than those of the essential elements Cu and Se, and exceeded the corresponding maximum residue limits of China. The present study provides the most recent information on trace element bioaccumulation or contamination in Taihu Lake and, further, suggests that A. woodiana can be used as a suitable bioindicator for inland water environmental monitoring.
Sources and fluxes of atmospheric trace elements to the Gulf of Aqaba, Red Sea
NASA Astrophysics Data System (ADS)
Chen, Ying; Paytan, Adina; Chase, Zanna; Measures, Christopher; Beck, Aaron J.; SañUdo-Wilhelmy, Sergio A.; Post, Anton F.
2008-03-01
We present the first comprehensive investigation of the concentrations, fluxes and sources of aerosol trace elements over the Gulf of Aqaba. We found that the mean atmospheric concentrations of crustally derived elements such as Al, Fe and Mn (1081, 683, and 16.7 ng m-3) are about 2-3 times higher than those reported for the neighboring Mediterranean area. This is indicative of the dominance of the mineral dust component in aerosols over the Gulf. Anthropogenic impact was lower in comparison to the more heavily populated areas of the Mediterranean. During the majority of time (69%) the air masses over the Gulf originated from Europe or Mediterranean Sea areas delivering anthropogenic components such as Cu, Cd, Ni, Zn, and P. Airflows derived from North Africa in contrast contained the highest concentrations of Al, Fe, and Sr but generally lower Cu, Cd, Ni, Zn, and P. Relatively high Pb, Ni, and V were found in the local and Arabian airflows suggesting a greater influence of local emission of fuel burning. We used the data and the measured trace metal seawater concentrations to calculate residence times of dissolved trace elements in the upper 50 m surface water of the Gulf (with respect to atmospheric input) and found that the residence times for most elements are in the range of 5-37 years while Cd and V residence times are longer.
Whitney, P.R.
1981-01-01
Manganese oxide coatings on gravels from 255 sites on tributary streams in the Genesee River Watershed were analyzed for Mn, Fe, Zn, Cd, Co, Ni, Pb, and Cu. The results were compared with data on bedrock geology, surficial geology and land use, using factor analysis and stepwise multiple regression. All metals except Pb show strong positive correlation with Mn. This association results from the well-known tendency of Mn oxide precipitates to adsorb and incorporate dissolved trace metals. Pb may be present in a separate phase on the gravel surfaces; alternatively Pb abundance may be so strongly influenced by environmental factors that the effect of varying abundance of the carrier phase becomes relatively unimportant. When the effects of varying Mn abundance are allowed for, Pb and to a lesser extent Zn and Cu abundances are seen to be related to commercial, industrial and residential land use. In addition to this pollution effect, all the trace metals, Cd and Ni most strongly, tend to be more abundant in oxide coatings from streams in the forested uplands in the southern part of the area. This probably reflects increased geochemical mobility of the metals in the more acid soils and groundwater of the southern region. A strong Zn anomaly is present in streams draining areas underlain by the Lockport Formation. Oxide coatings in these streams contain up to 5% Zn, originating from disseminated sphalerite in the Lockport and secondary Zn concentrations in the overlying muck soils. The same group of metals, plus calcium and loss on ignition, were determined in the silt and clay (minus 230 mesh) fraction of stream sediments from 129 of the same sites, using a hot nitric acid leach. The amounts of manganese in the sediments are low (average 1020 ppm) and manganese oxides are, at most, of relatively minor significance in the trace-metal geochemistry of these sediments. The bulk of the trace metals in sediment appears to be associated with iron oxides, clays and organic matter. ?? 1981.
Trace Metal Budgets for a Forested Watershed in the New Jersey Pine Barrens
NASA Astrophysics Data System (ADS)
Swanson, Karen A.; Johnson, Arthur H.
1980-04-01
Deposition of Pb, Cu, Ni, Fe, Mn, and Cd on the McDonalds Branch Basin in bulk precipitation was 25.4, 5.3, 6.6, 64.6, 20.7, and <2 mg m-2 yr-1 for a 1 year period in 1978-1979. Output in streamflow was 1.7, 0.7, 1.9, 148, 12.8, and <1 mg m-2 yr-1, respectively, and loss to deep groundwater was 1.4, 1.9, 2.3, 123, 20.4, and <1 mg m-2 yr-1. Pb, Cu, and Ni accumulated in the basin, while there was a net loss of Fe and Mn from the ecosystem. The major mechanism for movement of Fe and Pb out of the basin was interpreted to be complexation with and transport by mobile organic matter.
Mapping the subcellular localization of Fe3O4@TiO2 nanoparticles by X-ray Fluorescence Microscopy.
Yuan, Y; Chen, S; Gleber, S C; Lai, B; Brister, K; Flachenecker, C; Wanzer, B; Paunesku, T; Vogt, S; Woloschak, G E
The targeted delivery of Fe 3 O 4 @TiO2 nanoparticles to cancer cells is an important step in their development as nanomedicines. We have synthesized nanoparticles that can bind the Epidermal Growth Factor Receptor, a cell surface protein that is overexpressed in many epithelial type cancers. In order to study the subcellular distribution of these nanoparticles, we have utilized the sub-micron resolution of X-ray Fluorescence Microscopy to map the locationof Fe 3 O4@TiO 2 NPs and other trace metal elements within HeLa cervical cancer cells. Here we demonstrate how the higher resolution of the newly installed Bionanoprobe at the Advanced Photon Source at Argonne National Laboratory can greatly improve our ability to distinguish intracellular nanoparticles and their spatial relationship with subcellular compartments.
Determination of Metal Elements in Wine Using Laser-Induced Breakdown Spectroscopy (LIBS).
Bocková, Jana; Tian, Ye; Yin, Hualiang; Delepine-Gilon, Nicole; Chen, Yanping; Veis, Pavel; Yu, Jin
2017-08-01
We developed a method for sensitive elemental analysis of wines using laser-induced breakdown spectroscopy (LIBS). In order to overcome the inefficiency of direct ablation of bulk wine (an organic liquid), a thin layer of wine residue was prepared on a metallic target according to an appropriated heating procedure applied to an amount of liquid wine dropped on the target surface. The obtained ensemble was thus ablated. Such a sample preparation procedure used a very small volume of 2 mL of wine and took only 30 min without reagent or solvent. The results show the detection of tens of metal and non-metal elements including majors (Na, Mg, K, Ca), minors, and traces (Li, B, Si, P, Ti, Mn, Fe, Cu, Zn, Rb, Sr, Ba, and Pb) in wines purchased from local supermarkets and from different production places in France. Commercially available wines were then spiked with certified standard solutions of Ti and Fe. Three series of laboratory reference samples were thus prepared using three different wines (a red wine and a white wine from a same production region and a red wine from another production region) with concentrations of Ti and Fe in the range of 1-40 mg/L. Calibration graphs established with the spiked samples allowed extracting the figures-of-merit parameters of the method for wine analysis such as the coefficient of determination ( R 2 ) and the limits of detection and quantification (LOD and LOQ). The calibration curves built with the three wines were then compared. We studied the residual matrix effect between these wines in the determination of the concentrations of Ti and Fe.
NASA Astrophysics Data System (ADS)
Koo, T. H.; Kim, J. Y.; Kim, J. W.
2016-12-01
The fate and transportation of hazardous trace metal in soil environment can be controlled by various factors including temperature, geological location, properties of bed rock or sediment, human behavior, and biogeochemical reactions. The sorption and desorption process is one of the major process for control the transportation of trace metal in soil-water system. Nonetheless, few studies were focused on the biological controlling parameters, particularly redox reaction of structural metal of clay minerals. Thus, the objective of the present study is to investigate the correlation between the sorption and desorption reaction of Pb and biogeochemical properties of clay minerals. The effects of redox state of structural Fe and layer charge of the minerals on the migration/speciation of Pb at the various geochemical environment will be elucidated. The Fe-rich smectite, nontronite (NAu-1), and bulk soil samples which were collected from abandoned mine areas were reduced by microbial respiration by Shewanella Oneidensis MR-1 and/or Na-dithionite to various oxidation state of structural Fe. Then the Pb-stock solution made with common lead and nitric acid were spiked into the mineral/soil slurry with various Pb concentration to test the sorption and desorption reaction upto 7 days. The reaction was stopped at each time point by freezing the pellet and supernatant separately after centrifugation. Then the concentration and stable isotope ratio of Pb in the supernatant were measured using Inductively Coupled Plasma Mass Spectrometer (ICP-MS) and Multicollector (MC)-ICP-MS. The structural as well as chemical modification on nontronite and bulk soil sample were measured using x-ray diffraction (XRD), scanning electron microscopy (SEM) and wet chemistry analysis. The changes in Pb species in supernatant by sorption and desorption and its consequences on the clay structural/biogeochemical properties will be discussed.
Highly Reducing Partitioning Experiments Relevant to the Planet Mercury
NASA Technical Reports Server (NTRS)
Rowland, Rick, II; Vander Kaaden, Kathleen E.; McCubbin, Francis M.; Danielson, Lisa R.
2017-01-01
With the data returned from the MErcury Surface Space ENvironment GEochemistry and Ranging (MESSENGER) mission, there are now numerous constraints on the physical and chemical properties of Mercury, including its surface composition. The high S and low FeO contents observed from MESSENGER on the planet's surface suggests a low oxygen fugacity of the present planetary materials. Estimates of the oxygen fugacity for Mercurian magmas are approximately 3-7 log units below the Iron-Wüstite (Fe-FeO) oxygen buffer, several orders of magnitude more reducing than other terrestrial bodies we have data from such as the Earth, Moon, or Mars. Most of our understanding of elemental partitioning behavior comes from observations made on terrestrial rocks, but Mercury's oxygen fugacity is far outside the conditions of those samples. With limited oxygen available, lithophile elements may instead exhibit chalcophile, halophile, or siderophile behaviors. Furthermore, very few natural samples of rocks that formed under reducing conditions are available in our collections (e.g., enstatite chondrites, achondrites, aubrites). With this limited amount of material, we must perform experiments to determine the elemental partitioning behavior of typically lithophile elements as a function of decreasing oxygen fugacity. Experiments are being conducted at 4 GPa in an 880-ton multi-anvil press, at temperatures up to 1850degC. The composition of starting materials for the experiments were selected for the final run products to contain metal, silicate melt, and sulfide melt phases. Oxygen fugacity is controlled in the experiments by adding silicon metal to the samples, using the Si-SiO2 oxygen buffer, which is approximately 5 log units more reducing than the Fe-FeO oxygen buffer at our temperatures of interest. The target silicate melt compositional is diopside (CaMgSi2O6) because measured surface compositions indicate partial melting of a pyroxene-rich mantle. Elements detected on Mercury's surface by MESSENGER (K, Na, Fe, Ti, Cl, Al, Cr, Mn, U, Th) and other geochemically relevant elements (P, F, H, N, C, Co, Ni, Mo, Ce, Nd, Sm, Eu, Gd, Dy, Yb) are added to the starting composition at trace abundances (approximately 500 ppm) so that they are close enough to infinite dilution to follow Henry's law of trace elements, and their partitioning behavior can be measured between the metal, silicate, and sulfide phases. The results of these experiments will allow us to assess the thermal and magmatic evolution of the planet Mercury from a geochemical standpoint.
Martin, Rachael; Dowling, Kim; Pearce, Dora C; Florentine, Singarayer; McKnight, Stafford; Stelcer, Eduard; Cohen, David D; Stopic, Attila; Bennett, John W
2017-06-01
Mine wastes and tailings are considered hazardous to human health because of their potential to generate large quantities of highly toxic emissions of particulate matter (PM). Human exposure to As and other trace metals in PM may occur via inhalation of airborne particulates or through ingestion of contaminated dust. This study describes a laboratory-based method for extracting PM 2.5-10 (coarse) and PM 2.5 (fine) particles from As-rich mine waste samples collected from an historical gold mining region in regional, Victoria, Australia. We also report on the trace metal and metalloid content of the coarse and fine fraction, with an emphasis on As as an element of potential concern. Laser diffraction analysis showed that the proportions of coarse and fine particles in the bulk samples ranged between 3.4-26.6 and 0.6-7.6 %, respectively. Arsenic concentrations were greater in the fine fraction (1680-26,100 mg kg -1 ) compared with the coarse fraction (1210-22,000 mg kg -1 ), and Co, Fe, Mn, Ni, Sb and Zn were found to be present in the fine fraction at levels around twice those occurring in the coarse. These results are of particular concern given that fine particles can accumulate in the human respiratory system. Our study demonstrates that mine wastes may be an important source of metal-enriched PM for mining communities.
Elephant Moraine 87521: The first lunar meteorite composed of predominantly mare material
DOE Office of Scientific and Technical Information (OSTI.GOV)
Warren, P.H.; Kallemeyn, G.W.
1989-12-01
The trace-element chemistry and detailed petrography of brecciated Antarctic meteorite EET87521 reveal that it is not, as originally classified, a eucrite. Its Fe/Mn ratio and bulk Co content are fair higher than expected for a eucrite. Only one known type of extraterrestrial material resembles EET87521 in all important respects for which constraints exist: very-low-Ti (VLT) lunar mare basalts. Even compared to VLT basalts, EET87521 is enriched in REE. However, other varieties of high-alumina, low-Ti mare basalt are known that contain REE at even higher concentrations than EET87521. Several clasts in EET87521 preserve clear vestiges of coarse-grained igneous, possibly orthocumulate, textures.more » Mineralogically, these coarse-grained clasts are diverse; e.g., olivine ranges from Fo{sub 15} in one to Fo{sub 67} in another. One clast with an anomalously fine-grained texture is anorthositic and contains exceptionally Mg-rich pyroxene and Na-poor plagioclase, along with the only FeNi-metal in the thin section. Its FeNi-metals have compositions typical of metals incorporated into lunar soils and polymict breccias as debris from metal-rich meteorites. However, the low Ni and Ir contents of our bulk-rock analysis imply that the proportion of impact-projectile matter in our chip sample is probably small. The moderate degree of lithologic diversity among the lithic lasts and the bulk composition in general indicate that EET87521 is dominated by a single rock type: VLT mare basalt.« less
Zaksas, Nataliya; Gluhcheva, Yordanka; Sedykh, Sergey; Madzharova, Maria; Atanassova, Nina; Nevinsky, Georgy
2013-01-01
Cobalt (Co) is a transition metal and an essential trace element, required for vitamin B(12) biosynthesis, enzyme activation and other biological processes, but toxic in high concentrations. There is lack of data for the effect of long-term Co(II) treatment on the concentrations of other trace elements. We estimate the influence of cobalt chloride (CoCl(2)) on the relative content of different metals in mouse plasma using two-jet arc plasmatron atomic emission and on the total protein content. On average, the content of different elements in the plasma of 2-month-old balb/c mice (control group) decreased in the order: Ca>Mg>Si>Fe>Zn>Cu≥Al≥B. The treatment of mice for 60 days with CoCl(2) (daily dose 125 mg/kg) did not appreciably change the relative content of Ca, Cu, and Zn, while a 2.4-fold statistically significant decrease in the content of B and significant increase in the content of Mg (1.4-fold), Al and Fe (2.0-fold) and Si (3.2-fold) was found. A detectable amount of Mo was observed only for two control mice, while the plasma of 9 out of 16 mice of the treated group contained this metal. The administration of Co made its concentration detectable in the plasma of all mice of the treated group, but the relative content varied significantly. The treatment led to a 2.2-fold decrease in the concentration of the total plasma protein. Chronic exposure to CoCl(2) affects homeostasis as well as the concentrations and metabolism of other essential elements, probably due to competition of Co ions for similar binding sites within cells, altered signal transduction and protein biosynthesis. Long-term treatment also leads to significant weight changes and reduces the total protein concentration. The data may be useful for an understanding of Co toxicity, its effect on the concentration of other metal ions and different physiological processes. Copyright © 2012 Elsevier GmbH. All rights reserved.
Apeti, Dennis A; Whitall, David R; Pait, Anthony S; Dieppa, Angel; Zitello, Adam G; Lauenstein, Gunnar G
2012-01-01
As part of an assessment of land-based sources of pollution in Jobos Bay, Puerto Rico, sediment samples were collected at 43 sites to characterize concentrations of a suite of pollutants, including metals. Fifteen major and trace metals (Ag, Al, As, Cd, Cr, Cu, Fe, Hg, Mn Ni, Pb, Sb, Se, Sn, and Zn) were measured along with total organic carbon and grain size in surficial sediments. For most metals, maximum concentrations were seen in the eastern bay; however, values were still within concentration ranges found in other estuarine systems. In contrast, silver was higher in the western region. In general, metal distribution in the bay was positively correlated with grain size. Additionally, correlations between Al and other metals suggest natural sources for metals. The data presented here suggest that, although the Jobos Bay watershed contains both urban centers along with industrial and agricultural developments, anthropogenic inputs of metals may be negligible.
Trace Element Compositions of Pallasite Olivine Grains and Pallasite Origin
NASA Technical Reports Server (NTRS)
Mittlefehldt, David W.; Herrin, J. S.
2010-01-01
Pallasites are mixtures of metal with magnesian olivine. Most have similar metal compositions and olivine oxygen isotopic compositions; these are the main-group pallasites (PMG). The Eagle Station grouplet of pallasites (PES) have distinctive metal and olivine compositions and oxygen isotopic compositions. Pallasites are thought to have formed at the core-mantle boundary of their parent asteroids by mixing molten metal with solid olivine of either cumulatic or restitic origin. We have continued our investigation of pallasite olivines by doing in situ trace element analyses in order to further constrain their origin. We determined Al, P, Ca, Ga and first row transition element contents of olivine grains from suite of PMG and PES by LA-ICP-MS at JSC. Included in the PMG suite are some that have anomalous metal compositions (PMG-am) and atypically ferroan olivines (PMG-as). Our EMPA work has shown that there are unanticipated variations in olivine Fe/Mn, even within those PMG that have uni-form Fe/Mg. Manganese is homologous with Fe2+, and thus can be used the same way to investigate magmatic fractionation processes. It has an advantage for pallasite studies in that it is unaffected by redox exchange with the metal. PMG can be divided into three clusters on the basis of Mn/Mg; low, medium and high that can be thought of as less, typically and more fractionated in an igneous sense. The majority of PMG have medium Mn/Mg ratios. PMG-am occur in all three clusters; there does not seem to be any relationship between putative olivine igneous fractionation and metal composition. The PMG-as and one PMG-am make up the high Mn/Mg cluster; no PMG are in this cluster. The high Mn/Mg cluster ought to be the most fractionated (equivalent to the most Fe-rich in igneous suites), yet they have among the lowest contents of incompatible lithophile elements Al and Ti and the two PMG-as in this cluster also have low Ca and Sc contents. This is inconsistent with simple igneous fractionation on a single, initially homogeneous parent asteroid. For Al and Ti, the low and high Mn/Mg clusters have generally uniform contents, while the medium cluster has wide ranges. This is also true of analyses of duplicate grains from the medium cluster pallasites which can have very different Al and Ti contents. Those from the low and high clusters do not. These observations suggest that pallasite olivines are not cumulates, but rather are restites from high degrees of melting. The moderately siderophile elements P and Ga show wide ranges in the high Mn/Mg cluster, but very uniform compositions in the medium cluster, opposite the case for Al and Ti. There is no correlation of P or Ga and Fe/Mn as might be expected if redox processes controlled the contents of moderately siderophile elements in the olivines. The lack of correlation of P could reflect equilibration with phosphates, although there is no correlation of Ca with P as might be expected
NASA Astrophysics Data System (ADS)
Gelabert, A.; Wang, Y.; Gescher, J.; Ha, J.; Cordova, C. D.; Singer, D. M.; Spormann, A. M.; Trainor, T. P.; Eng, P. J.; Brown, G. E.
2006-12-01
Fe- and Al-(oxyhydr)oxides are among the most reactive mineral surfaces contacted by surface and ground waters, and thus they constitute important sorbents for heavy metal and metalloid ions. As microbial biofilms may be present as coatings on these minerals, they are likely to induce major changes in surface charges and sorption capacities for metal(loid) ions compared to biofilm-free mineral surfaces. In addition, the micro- environments in biofilms can be quite different from those in bulk solutions, which can enhance (or inhibit) metal adsorption on mineral surfaces and produce biominerals that are not predicted by equilibrium thermodynamics based on the bulk solution values. In order to provide a more quantitative understanding of these effects, we have carried out a study of the interaction of Zn(II), Pb(II), and As(V) with Shewanella oneidensis (wild type, EPS-deficient mutant, and ppx- and ppk-deficient mutants) grown on highly polished and oriented single crystal surfaces of α-Al2O3 (1-102) and α-Fe2O3 (0001). This gram-negative bacterium commonly found in soil and sediments can use a wide range of electron donors and terminal electron acceptors including Fe(III) and Mn(IV) oxides under anaerobic conditions. In-situ ATR-FTIR analyses and potentiometric titrations of S. oneidensis biofilm collected from a glass bead-filled column inoculated with S. oneidensis were conducted in order to determine the nature of functional groups present on the bacterial surfaces, to quantify the site densities and protonation constants for these groups, and to determine the electrostatic parameters for S. oneidensis surfaces. GI-XAFS analyses performed on BL 11-2 at SSRL, together with macroscopic metal adsorption experiments as a function of pH (2 to 6.5), metal concentration (10-3 to 10-7 M), and ionic strength (10-1 to 10-3 M), were used to determine ion speciation and local coordination environments in the biofilm and to develop a surface complexation model describing the interactions among biofilm, metal(loid)s, and mineral surfaces. The long-period X-ray Standing Wave- fluorescent yield (XSW-FY) method, performed on BL ID-13-C at the APS, was used to obtain quantitative in situ information on the partitioning of Zn(II), Pb(II), and As(V) at these interfaces as a function of pH and ion concentration. XSW-FY results show that S. oneidensis biofilms do not block reactive sites on the hematite or alumina surfaces under our experimental conditions, which is consistent with the conclusion of our previous studies on trace element distributions at Burkholderia cepacia/mineral/water interfaces. Comparison of the observed trace element partitioning measured by XSW-FY with theoretical predictions of partitioning through thermodynamic models (using binding constants of metal(loid)s with the biofilm determined in this study and published binding constants of metal(loid)s with mineral substrates) allows us to describe biofilm local microenvironments and to understand how the biofilm coatings affect the reactivity of mineral surfaces.
Hydrogen peroxide photocycling in the Gulf of Aqaba, Red Sea.
Shaked, Yeala; Harris, Raviv; Klein-Kedem, Nir
2010-05-01
The dynamics of hydrogen peroxide (H(2)O(2)) was investigated from December 2007 to October 2008 in the Gulf of Aqaba, which in the absence of H(2)O(2) contribution from biological production, rain and runoff, turned out to be a unique natural photochemical laboratory. A distinct seasonal pattern emerged, with highest midday surface H(2)O(2) concentrations in spring-summer (30-90 nM) as compared to winter (10-30 nM). Similarly, irradiation normalized net H(2)O(2) formation rates obtained in concurrent ship-board experiments were faster in spring-summer than in winter. These seasonal patterns were attributed to changes in water characteristics, namely elevated spring-summer chromophoric dissolved organic matter (CDOM). The role of trace elements in H(2)O(2) photoformation was studied by simultaneously measuring superoxide (O(2)(-)), Fe(II), and H(2)O(2) formation and loss in ambient seawater and in the presence of superoxide dismutase, iron and copper. O(2)(-) was found to decay fast in the Gulf water, with a half-life of 15-28 s, primarily due to catalytic reactions with trace metals (predominantly copper). Hence, H(2)O(2) formation in the Gulf involves metal-catalyzed O(2)(-) disproptionation. Added iron moderately lowered net H(2)O(2) photoformation, probably due to its participation in Fe(II) oxidation, a process that may also modify H(2)O(2) formation in situ.
The moon: Composition determined by nebular processes
Morgan, J.W.; Hertogen, J.; Anders, E.
1978-01-01
The bulk composition of the Moon was determined by the conditions in the solar nebula during its formation, and may be quantitatively estimated from the premise that the terrestrial planets were formed by cosmochemical processes similar to those recorded in the chondrites. The calculations are based on the Ganapathy-Anders 7-component model using trace element indicators, but incorportate improved geophysical data and petrological constraints. A model Moon with 40 ppb U, a core 2% by weight (1.8% metal with ???35% Ni and 0.2% FeS) and Mg/(Fe2++Mg)?????0.75 meets the trace element restrictions, and has acceptable density, heat flow and moment of inertia ratio. The high Ni content of the core permits low-Ti mare basalts to equilibrate with metal, yet still retain substantial Ni. The silicate resembles the Taylor-Jakes?? composition (and in some respects the waif Ganapathy-Anders Model 2a), but has lower SiO2. Minor modifications of the model composition (U=30-35 ppb) yield a 50% melt approximating Apollo 15 green glass and a residuum of olivine plus 3 to 4% spinel; the low SiO2, favors spinel formation, and, contrary to expectation, Cr is not depleted in the liquid. There may no longer be any inconsistency between the cosmochemical approach and arguments based on experimental petrology. ?? 1978 D. Reidel Publishing Company.
Composition and source apportionment of dust fall around a natural lake.
Latif, Mohd Talib; Ngah, Sofia Aida; Dominick, Doreena; Razak, Intan Suraya; Guo, Xinxin; Srithawirat, Thunwadee; Mushrifah, Idris
2015-07-01
The aim of this study was to determine the source apportionment of dust fall around Lake Chini, Malaysia. Samples were collected monthly between December 2012 and March 2013 at seven sampling stations located around Lake Chini. The samples were filtered to separate the dissolved and undissolved solids. The ionic compositions (NO3-, SO4(2-), Cl- and NH4+) were determined using ion chromatography (IC) while major elements (K, Na, Ca and Mg) and trace metals (Zn, Fe, Al, Ni, Mn, Cr, Pb and Cd) were determined using inductively coupled plasma mass spectrometry (ICP-MS). The results showed that the average concentration of total solids around Lake Chini was 93.49±16.16 mg/(m2·day). SO4(2-), Na and Zn dominated the dissolved portion of the dust fall. The enrichment factors (EF) revealed that the source of the trace metals and major elements in the rain water was anthropogenic, except for Fe. Hierarchical agglomerative cluster analysis (HACA) classified the seven monitoring stations and 16 variables into five groups and three groups respectively. A coupled receptor model, principal component analysis multiple linear regression (PCA-MLR), revealed that the sources of dust fall in Lake Chini were dominated by agricultural and biomass burning (42%), followed by the earth's crust (28%), sea spray (16%) and a mixture of soil dust and vehicle emissions (14%). Copyright © 2015. Published by Elsevier B.V.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Marcus, Matthew A.; Edwards, Katrina J.; Gueguen, Bleuenn
Deep-sea ferromanganese nodules accumulate trace elements from seawater and underlying sediment porewaters during the growth of concentric mineral layers over millions of years. These trace elements have the potential to record past ocean geochemical conditions. The goal of this study was to determine whether Fe mineral alteration occurs and how the speciation of trace elements responds to alteration over ~3.7Ma of marine ferromanganese nodule (MFN) formation, a timeline constrained by estimates from 9 Be/ 10 Be concentrations in the nodule material. We determined Fe-bearing phases and Fe isotope composition in a South Pacific Gyre (SPG) nodule. Specifically, the distribution patternsmore » and speciation of trace element uptake by these Fe phases were investigated. The time interval covered by the growth of our sample of the nodule was derived from 9 Be/ 10 Be accelerator mass spectrometry (AMS). The composition and distribution of major and trace elements were mapped at various spatial scales, using micro-X-ray fluorescence (μXRF), electron microprobe analysis (EMPA), and inductively coupled plasma mass spectrometry (ICP-MS). Fe phases were characterized by micro-extended X-ray absorption fine structure (μEXAFS) spectroscopy and micro-X-ray diffraction (μXRD). Speciation of Ti and V, associated with Fe, was measured using micro-X-ray absorption near edge structure (μXANES) spectroscopy. Iron isotope composition (δ 56/54 Fe) in subsamples of 1-3mm increments along the radius of the nodule was determined with multiple-collector ICP-MS (MC-ICP-MS). The SPG nodule formed through primarily hydrogeneous inputs at a rate of 4.0±0.4mm/Ma. The nodule exhibited a high diversity of Fe mineral phases: feroxyhite (δ-FeOOH), goethite (α-FeOOH), lepidocrocite (γ-FeOOH), and poorly ordered ferrihydrite-like phases. These findings provide evidence that Fe oxyhydroxides within the nodule undergo alteration to more stable phases over millions of years. Trace Ti and V were spatially correlated with Fe and found to be adsorbed to Fe-bearing minerals. Ti/Fe and V/Fe ratios, and Ti and V speciation, did not vary along the nodule radius. The δ 56/54 Fe values, when averaged over sample increments representing 0.25-0.75Ma, were homogeneous within uncertainty along the nodule radius, at -0.12±0.07‰ (2sd, n=10). Our results indicate that the Fe isotope composition of the nodule remained constant during nodule growth and that mineral alteration did not affect the primary Fe isotope composition of the nodule. Furthermore, the average δ 56/54 Fe value of -0.12‰ we find is consistent with Fe sourced from continental eolian particles (dust). Despite mineral alteration, the trace element partitioning of Ti and V, and Fe isotope composition, do not appear to change within the sensitivity of our measurements. These findings suggest that Fe oxyhydroxides within hydrogenetic ferromanganese nodules are out of geochemical contact with seawater once they are covered by subsequent concentric mineral layers. Even though Fe-bearing minerals are altered, trace element ratios, speciation and Fe isotope composition are preserved within the nodule.« less
Marcus, Matthew A.; Edwards, Katrina J.; Gueguen, Bleuenn; ...
2015-09-05
Deep-sea ferromanganese nodules accumulate trace elements from seawater and underlying sediment porewaters during the growth of concentric mineral layers over millions of years. These trace elements have the potential to record past ocean geochemical conditions. The goal of this study was to determine whether Fe mineral alteration occurs and how the speciation of trace elements responds to alteration over ~3.7Ma of marine ferromanganese nodule (MFN) formation, a timeline constrained by estimates from 9 Be/ 10 Be concentrations in the nodule material. We determined Fe-bearing phases and Fe isotope composition in a South Pacific Gyre (SPG) nodule. Specifically, the distribution patternsmore » and speciation of trace element uptake by these Fe phases were investigated. The time interval covered by the growth of our sample of the nodule was derived from 9 Be/ 10 Be accelerator mass spectrometry (AMS). The composition and distribution of major and trace elements were mapped at various spatial scales, using micro-X-ray fluorescence (μXRF), electron microprobe analysis (EMPA), and inductively coupled plasma mass spectrometry (ICP-MS). Fe phases were characterized by micro-extended X-ray absorption fine structure (μEXAFS) spectroscopy and micro-X-ray diffraction (μXRD). Speciation of Ti and V, associated with Fe, was measured using micro-X-ray absorption near edge structure (μXANES) spectroscopy. Iron isotope composition (δ 56/54 Fe) in subsamples of 1-3mm increments along the radius of the nodule was determined with multiple-collector ICP-MS (MC-ICP-MS). The SPG nodule formed through primarily hydrogeneous inputs at a rate of 4.0±0.4mm/Ma. The nodule exhibited a high diversity of Fe mineral phases: feroxyhite (δ-FeOOH), goethite (α-FeOOH), lepidocrocite (γ-FeOOH), and poorly ordered ferrihydrite-like phases. These findings provide evidence that Fe oxyhydroxides within the nodule undergo alteration to more stable phases over millions of years. Trace Ti and V were spatially correlated with Fe and found to be adsorbed to Fe-bearing minerals. Ti/Fe and V/Fe ratios, and Ti and V speciation, did not vary along the nodule radius. The δ 56/54 Fe values, when averaged over sample increments representing 0.25-0.75Ma, were homogeneous within uncertainty along the nodule radius, at -0.12±0.07‰ (2sd, n=10). Our results indicate that the Fe isotope composition of the nodule remained constant during nodule growth and that mineral alteration did not affect the primary Fe isotope composition of the nodule. Furthermore, the average δ 56/54 Fe value of -0.12‰ we find is consistent with Fe sourced from continental eolian particles (dust). Despite mineral alteration, the trace element partitioning of Ti and V, and Fe isotope composition, do not appear to change within the sensitivity of our measurements. These findings suggest that Fe oxyhydroxides within hydrogenetic ferromanganese nodules are out of geochemical contact with seawater once they are covered by subsequent concentric mineral layers. Even though Fe-bearing minerals are altered, trace element ratios, speciation and Fe isotope composition are preserved within the nodule.« less
Wang, Joanna Shaofen; Chiu, Kong-Hwa
2006-03-01
The objective of this work is to track the amount of metal complexes distributed in the extraction cell, collection vial, and tubing used in supercritical fluid extraction (SFE) systems after progressive removal of metal ions in supercritical carbon dioxide (SC-CO2). Sodium diethyldithiocarbamate (NaDDC) and dibutylammonium dibutyldithiocarbamate (DBDC) ligands were used to form complexes with Cd, Cu, Pb, and Zn and CO(2)/5% methanol as a supercritical fluid. The mass balance of metal complexes were obtained before and after extraction, and metals in different locations in the system were flushed out using an organic solvent and nitric acid (HNO3). These results infer that the stability constant (beta) of the metal-ligand complex has a strong correlation with SFE. Because of the composition of the stainless-steel cell, Fe, Cr, and Ni or other trace elements in the cell might interfere with the mass balance of metal complexes in SFE due to an exchange mechanism taking place between the cell and the sample.
NASA Astrophysics Data System (ADS)
Moreda-Piñeiro, Jorge; Alonso-Rodríguez, Elia; Moscoso-Pérez, Carmen; Blanco-Heras, Gustavo; Turnes-Carou, Isabel; López-Mahía, Purificación; Muniategui-Lorenzo, Soledad; Prada-Rodríguez, Darío
2014-05-01
In the present research, the rainwater chemistry of soluble (SF) and non-soluble (NSF) fractions is studied over a one a half year period (from March 2011 to August 2012) at a suburban site (Oleiros, A Coruña, Spain). The monthly rainfall in this region during the studied period ranged from 10 to 137 mm, while the NSF ranged from 0.9 to 54 mg L-1. More rainfall occurs within October-January. Eighteen samples, which provide information pertaining to the monthly variation in chemistry, were analyzed. Trace metals (Al, As, Ba, Co, Cu, Cr, Fe, Mn, Ni, Pb, Sr, V, Zn) were enclosed in the study of both fractions of the rainwater. Major inorganic ions (Cl-, NO3-, SO42-, Na+, K+, Ca2+, Mg2+ and NH4+) were also enclosed in the study of the SF of the rainwater. After partition coefficients analysis, univariate and principal components analysis (PCA) and air mass back trajectories analysis, three sources were found for the ionic and metal composition of the SF of rainwater; terrestrial (Ca2+, non sea salt SO42-, Al and Fe), marine (Mg2+, Na+, Cl-) and anthropogenic (K+, NH4+, NO3-, Fe, Mn, Pb, Sr, V and Zn). Results also suggest ubiquitous sources for Ba, Co, Cu, Cr and Ni. One source (terrestrial) was found for NSF of rainwater.
NASA Astrophysics Data System (ADS)
Hassnain Jaffari, G.; Aftab, M.; Anjum, D. H.; Cha, Dongkyu; Poirier, Gerald; Ismat Shah, S.
2015-12-01
Composition gradient and phase separation at the nanoscale have been investigated for arc-melted and solidified with equiatomic Fe-Cu. Diffraction studies revealed that Fe and Cu exhibited phase separation with no trace of any mixing. Microscopy studies revealed that immiscible Fe-Cu form dense bulk nanocomposite. The spatial distribution of Fe and Cu showed existence of two distinct regions, i.e., Fe-rich and Cu-rich regions. Fe-rich regions have Cu precipitates of various sizes and different shapes, with Fe forming meshes or channels greater than 100 nm in size. On the other hand, the matrix of Cu-rich regions formed strips with fine strands of nanosized Fe. Macromagnetic response of the system showed ferromagnetic behavior with a magnetic moment being equal to about 2.13 μB/ Fe atom and a bulk like negligible value of coercivity over the temperature range of 5-300 K. Anisotropy constant has been calculated from various laws of approach to saturation, and its value is extracted to be equal to 1350 J/m3. Inhomogeneous strain within the Cu and Fe crystallites has been calculated for the (unannealed) sample solidified after arc-melting. Annealed sample also exhibited local inhomogeneity with removal of inhomogeneous strain and no appreciable change in magnetic character. However, for the annealed sample phase separated Fe exhibited homogenous strain.
NASA Astrophysics Data System (ADS)
Sapkota, Birendra
Understanding the interactions and effects of biotic and abiotic factors on magnetic parameter measurements used to assess levels of pollutants requires experimental analysis of potential individual parameters. Using magnetic and chemical measurements, three separate experimental studies were conducted in order to evaluate the separate and combined effects of soil composition, atmospheric exposure, and contaminant levels on soil magnetic susceptibility (MS) measurements, plant growth and metal uptake by plants. Experiment 1 examined the effects of incorporating an artificial Fe-rich contaminant into a synthetic soil on surficial soil magnetic properties and plant growth inside a greenhouse. Periodic measurements of surficial soil MS showed significant decreases in MS values in the three treatments (two levels of Fe-contamination and controls), with the greatest reduction in soils with the most contamination, and the least in controls. Three potential causes were suggested: Fe uptake by plants, magnetic minerals transformation, and downward migration of Fe-particles. Some arguments for the first two causes were discussed; however, the third possibility was separately evaluated in the second and third experiments. In the follow-up study (Experiment 2) conducted to examine the effects of ambient atmospheric pollution on magnetic and chemical properties of soils and plant biomass, the overall surficial soil MS was found to be significantly higher in synthetic soils exposed to a natural atmosphere in comparison to controls placed in a greenhouse. Root biomass samples taken from the exposed soils had much higher trace/heavy metal concentrations. Such increases in soil MS and bioavailability of metals in the exposed soils indicate that atmospheric pollution affected the soil and plants grown in there. Microscopic observations of Fe-rich particles from the post-harvest exposed soil revealed morphologies similar to Fe-containing particulates from power plants and transportation and related sources. Experiment 3 examined the vertical migration behavior of Fe-particles in natural soils, and contaminated soil cores showed magnetic enhancement at depths of 2 to 9 cm, with the Fe-rich particles at that depth having very similar morphologies to the contaminant (magnetite powder) used, suggesting that the contaminant migrated vertically downward in soil at a observable rate, most likely due to infiltration of rainwater.
Gas-deposit-alloy corrosion interactions in simulated combustion environments
NASA Astrophysics Data System (ADS)
Luer, Kevin Raymond
High temperature corrosion in aggressive coal combustion environments involves simultaneous corrosion reactions between combustion gases, ash deposits, and alloys. This research investigated the behavior of a ferritic steel (SA387-Gr11) and three weld claddings (309L SS, Alloy 72, and Alloy 622) in five combustion environments beneath solid deposits at 500°C for up to 1000 hours. The synthetic gases consisted of N2-CO-CO-H2-H2O-H 2S-SO2 mixtures that simulated a range of fuel-rich or fuel-lean combustion environments with a constant sulfur content. The synthetic deposits contained FeS2, FeS, Fe3O4 and/or carbon. Reaction kinetics was studied in individual gas-metal, gas deposit, and deposit-alloy systems. A test method was developed to investigate simultaneous gas-deposit-metal corrosion reactions. The results showed reaction kinetics varied widely, depending on the gas-alloy system and followed linear, parabolic, and logarithmic rate laws. Under reducing conditions, the alloys exhibited a range of corrosion mechanisms including carburization-sulfidation, sulfidation, and sulfidation-oxidation. Most alloys were not resistant to the highly reducing gases but offered moderate resistance to mixed oxidation-sulfidation by demonstrating parabolic or logarithmic behavior. Under oxidizing conditions, all of the alloys were resistant. Under oxidizing-sulfating conditions, alloys with high Fe or Cr contents sulfated whereas an alloy containing Mo and W was resistant. In the gas-deposit-metal tests, FeS2-bearing deposits were extremely corrosive to low alloy steel under both reducing and oxidizing conditions but they had little influence on the weld claddings. Accelerated corrosion was attributed to rapid decomposition or oxidation of FeS2 particles that generated sulfur-rich gases above the alloy surface. In contrast, FeS-type deposits had no influence under reducing conditions but they were aggressive to low alloy steel under oxidizing conditions. The extent of damage correlated with the initial sulfur content in the deposit. Fe3O4 in the deposit was beneficial because it acted as a sulfur getter or oxygen source. Carbon had a mixed effect. The reaction behavior was modeled using computational thermochemistry based on Gibbs free energy minimization. A calculation method was introduced to predict equilibrium corrosion microstructures and trace reaction paths in complex gas-deposit-metal environments. Kinetic factors were identified where equilibrium reaction products were not experimentally observed.
Assessment of potable water quality including organic, inorganic, and trace metal concentrations.
Nahar, Mst Shamsun; Zhang, Jing
2012-02-01
The quality of drinking water (tap, ground, and spring) in Toyama Prefecture, Japan was assessed by studying quality indicators including major ions, total carbon, and trace metal levels. The physicochemical properties of the water tested were different depending on the water source. Major ion concentrations (Ca(2+), K(+), Si(4+), Mg(2+), Na(+), SO(4)(2-), HCO(3)(-), NO(3)(-), and Cl(-)) were determined by ion chromatography, and the results were used to generate Stiff diagrams in order to visually identify different water masses. Major ion concentrations were higher in ground water than in spring and tap water. The relationship between alkaline metals (Na(+) and K(+)), alkaline-earth metals (Ca(2+) and Mg(2+)), and HCO(3)(-) showed little difference between deep and shallow ground water. Toyama ground, spring, and tap water were all the same type of water mass, called Ca-HCO(3). The calculated total dissolved solid values were below 300 mg/L for all water sources and met World Health Organization (WHO) water quality guidelines. Trace levels of As, Cd, Cr, Co, Cu, Fe, Pb, Mn, Mo, Ni, V, Zn, Sr, and Hg were detected in ground, spring, and tap water sources using inductively coupled plasma atomic emission spectrometry, and their levels were below WHO and Japanese water quality standard limits. Volatile organic carbon compounds were quantified by headspace gas chromatography-mass spectrometry, and the measured concentrations met WHO and Japanese water quality guidelines. Total trihalomethanes (THMs) were the major contaminant detected in all natural drinking water sources, but the concentration was highest in tap water (37.27 ± 0.05 μg/L). Notably, THMs concentrations reached up to 1.1 ± 0.05 μg/L in deep ground water. The proposed model gives an accurate description of the organic, inorganic, and trace heavy metal indicators studied here and may be used in natural clean water quality management. © Springer Science+Business Media B.V. 2011
NASA Astrophysics Data System (ADS)
Hu, Ningjing; Liu, Jihua; Shi, Xuefa
2015-04-01
Source and distribution of sedimentary thallium in the Bohai Sea: Implications for hydrodynamic forces and anthropogenic impact Hu Ningjing, Liu Jihua, Shi Xuefa First Institute of Oceanography, State Oceanic Administration, Qingdao 266061, China Thallium (Tl), a non-essential and highly toxic trace metal, is listed as priority toxic pollutant by the United States Environmental Protection Agency (USEPA) (Keith and Telliard, 1979). However, its geochemical cycling in aquatic environment has received far less attention than that of many other trace metals. This has been attributed to relatively little commercial interest in Tl and, until recently, problems inherent in its detection at environmental concentrations (Meeravali and Jiang, 2008). In this study, we investigated the sources, distribution and fate of Tl in surface sediments of the Bohai Sea (BS), China, based on the datasets of total Tl and chemical speciation of Tl of 408 surface sediment samples in the total entire BS. The enrichment factors and chemical speciation of Tl indicated that Tl in BS was dominated by natural Tl, although anthropogenic Tl contamination was observed in the Liuguhe River mouth; the mud deposits are the sinks of Tl and the regional currents and tide systems play a key role on the accumulation of Tl in BS. The distribution of Tl consistent with that of MnO and Fe2O3 as well as the level of Fe-Mn fraction is relatively high, indicating MnO and Fe2O3 influence the geochemical behaviors of Tl in the BS. Although the positive correlation between Tl and TOC is observed for the samples in the BS, however, level of Tl in oxidizable faction could be neglected, suggesting TOC might not be a major factor affecting the concentration of Tl in BS. The low proportion of Tl in the non-residual fraction dominated by the Fe-Mn oxides suggested that the labile Tl was controlled by the Fe-Mn oxides and Tl has a low bioavailability and a minor potential threat to biota in BS. Acknowledgements: this work was jointly supported by National Natural Science Foundation of China (Grant Nos.41076032, 41276052 and 41376073) and the State Oceanic Administration, China (Grant No. 201105003). References Keith, L.H., Telliard, W.A., 1979. Priority pollutants-A perspective view. Environmental Science and Technology 13, 416-423. Meeravali, N.M., Jiang, S.-J., 2008. Ultra-trace speciation analysis of thallium in environmental water samples by inductively coupled plasma mass spectrometry after a novel sequential mixed-micelle cloud point extraction. Journal of Analytical Atomic Spectrometry 23, 555-560.
NASA Technical Reports Server (NTRS)
Ahrens, T. J.; Tsay, F.-D.; Live, D. H.
1976-01-01
Electron spin resonance (ESR) studies have been carried out on three single grains of terrestrial olivine (Fo90) shock loaded along the 010 line to peak pressures of 280, 330, and 440 kbar. The results indicate that neither metallic Fe similar to that observed in returned lunar soils nor paramagnetic Fe(3+) caused by oxidation of Fe(2+) has been produced in these shock experiments. Trace amounts of Mn (2+) have been detected in both shocked and unshocked olivine. The ESR signals of Mn(2+) show spectral features which are found to correlate with the degree of shock-induced recrystallization observed petrographically. The increasing mass fraction of recrystallized olivine correlates with increasing shock pressures. This phenomenon is modelled assuming it results from the progressive effect of the shock-induced transformation of the olivine to a yet unknown high-pressure phase and its subsequent reversion to the low-pressure olivine phase. The mass fraction of recrystallized material is predicted to be nearly linear with shock pressure.
Dos Santos, Laíse Milena Ribeiro; Gloaguen, Thomas Vincent; Fadigas, Francisco de Souza; Chaves, Joselisa Maria; Martins, Tamires Moraes Oliveira
2017-12-01
Many countries and some Brazilian regions have defined the guideline values for metals in soils. However, the local geological features may be so heterogeneous that global or even regional guideline values cannot be applied. The Greenstone Belts are worldwide geological formations of vast extension, containing mineralization of various metals (e.g., Au, Cr, Ni, and Ag). Natural concentrations of soils must be known to correctly assess the impact of mining. We studied the soils of the Rio Itapicuru Greenstone Belt (RIGB), of Paleoproterozoic age, sampling at 24 sites (0-0.20m) in the areas not or minimally human impacted, equally distributed in the three units of the RIGB: Volcanic Mafic Unit (VMU), Volcanic Felsic Unit (VFU), and Volcano-clastic Sedimentary Unit (SU). The natural pseudo-total concentrations of Cr, Ni, Cu, Zn, Pb, Fe, and Mn were obtained by acid digestion (EPA3050b) both in the soil and the particle-size fractions (sand and clay+silt). The concentrations of metals in RIGB soils, especially Cr and Ni, are generally higher than those reported for other regions of Brazil or other countries. Even the sedimentary soils have relatively high metal values, naturally contaminated by the VMU of the RIGB; a potential impact on Mesozoic and Cenozoic sedimentary rocks located near the study region is highly expected. Metals are concentrated (80%) in the fine particle-size fraction, implying an easy availability through surface transport (wind and runoff). We introduced a new index, called the Fe-independent accumulation factor - AF -Fe , which reveals that 90-98% of the dynamics of the trace metals is associated with the iron geochemical cycle. We primarily conclude that determining the guideline values for different soil classes in variable geological/geochemical environment and under semiarid climate is meaningless: the concentration of metals in soils is clearly more related to the source material than to the pedogenesis processes. Copyright © 2017 Elsevier B.V. All rights reserved.
NASA Astrophysics Data System (ADS)
Breier, J. A.; Toner, B. M.; Fakra, S. C.; Marcus, M. A.; White, S. N.; Thurnherr, A. M.; German, C. R.
2012-07-01
Deep-sea hydrothermal plume particles are known to sequester seawater trace elements and influence ocean-scale biogeochemical budgets. The relative importance of biotic versus abiotic oxidation-reduction and other particle-forming reaction, however, and the mechanisms of seawater trace element sequestration remain unknown. Suspended particulate material was collected from a non-buoyant hydrothermal plume by in situ filtration at 9°50‧N East Pacific Rise during a 3-day, 24 sample, time-series. Twenty-three samples were digested for total elemental analysis. One representative sample was selected for particle-by-particle geochemical analyses including elemental composition by X-ray fluorescence, speciation of Fe, S, and C by 1s X-ray absorption near edge structure spectroscopy, and X-ray diffraction. Consistent with past studies, positive linear correlations were observed for P, V, As, and Cr with Fe in the bulk chemistry. Arsenic was associated with both Fe oxyhydroxides and sulfides but not uniformly distributed among either mineral type. Particle aggregation was common. Aggregates were composed of minerals embedded in an organic matrix; the minerals ranged from <20 nm to >10 μm in diameter. The speciation of major mineral forming elements (Fe, Mn, S) was complex. Over 20 different minerals were observed, nine of which were either unpredicted by thermodynamic modeling or had no close match in the thermodynamic database. Sulfur-bearing phases consisted of polysulfides (S6, S8), and metal sulfides (Fe, Cu, Zn, Mn). Four dominant species, Fe oxyhydroxide, Fe monosulfide, pyrrhotite, and pyrite, accounted for >80% of the Fe present. Particulate Mn was prevalent in both oxidized and reduced minerals. The organic matrix was: (1) always associated with minerals, (2) composed of biomolecules, and (3) rich in S. Possible sources of this S-rich organic matter include entrained near vent biomass and in situ production by S-oxidizing microorganisms. These results indicate that particle aggregation with organic material is prevalent in dispersing hydrothermal plume fluxes, as well as in sinking particulate matter at this site. Particle aggregation and organic coatings can influence the reactivity, transport, and residence time of hydrothermal particles in the water column. Thus a biogeochemical approach is critical to understanding the net effect of hydrothermal fluxes on ocean and sedimentary trace element budgets.
Abraham, Mwesigye R; Susan, Tumwebaze B
2017-02-01
The mining and processing of copper in Kilembe, Western Uganda, from 1956 to 1982 left over 15 Mt of cupriferous and cobaltiferous pyrite dumped within a mountain river valley, in addition to mine water which is pumped to the land surface. This study was conducted to assess the sources and concentrations of heavy metals and trace elements in Kilembe mine catchment water. Multi-element analysis of trace elements from point sources and sinks was conducted which included mine tailings, mine water, mine leachate, Nyamwamba River water, public water sources and domestic water samples using ICP-MS. The study found that mean concentrations (mg kg -1 ) of Co (112), Cu (3320), Ni (131), As (8.6) in mine tailings were significantly higher than world average crust and were being eroded and discharged into water bodies within the catchment. Underground mine water and leachate contained higher mean concentrations (μg L -1 ) of Cu (9470), Co (3430) and Ni (590) compared with background concentrations (μg L -1 ) in un contaminated water of 1.9, 0.21 and 0.67 for Cu, Co and Ni respectively. Over 25% of household water samples exceeded UK drinking water thresholds for Al of 200 μg L -1 , Co exceeded Winsconsin (USA drinking) water thresholds of 40 μg L -1 in 40% of samples while Fe in 42% of samples exceeded UK thresholds of 200 μg L -1 . The study however found that besides mining activities, natural processes of geological weathering also contributed to Al, Fe, and Mn water contamination in a number of public water sources. Copyright © 2016 Elsevier Ltd. All rights reserved.
NASA Astrophysics Data System (ADS)
Brown, A. L.; Martin, J. B.; Screaton, E.; Spellman, P.; Gulley, J.
2011-12-01
Springs located adjacent to rivers can serve as recharge points for aquifers when allogenic runoff increases river stage above the hydraulic head of the spring, forcing river water into the spring vent. Depending on relative compositions of the recharged water and groundwater, the recharged river water could be a source of dissolved trace metals to the aquifer, could mobilize solid phases such as metal oxide coatings, or both. Whether metals are mobilized or precipitated should depend on changes in redox and pH conditions as dissolved oxygen and organic carbon react following intrusion of the river water. To assess how river intrusion events affect metal cycling in springs, we monitored a small recharge event in April 2011 into Madison Blue Spring, which discharges to the Withlacoochee River in north-central Florida. Madison Blue Spring is the entrance to a phreatic cave system that includes over 7.8 km of surveyed conduits. During the event, river stage increased over base flow conditions for approximately 25 days by a maximum of 8%. Intrusion of the river water was monitored with conductivity, temperature and depth sensors that were installed within the cave system and adjacent wells. Decreased specific conductivity within the cave system occurred for approximately 20 days, reflecting the length of time that river water was present in the cave system. During this time, grab samples were collected seven times over a period of 34 days for measurements of major ion and trace metal concentrations at the spring vent and at Martz sink, a karst window connected to the conduit system approximately 150 meters from the spring vent. Relative fractions of surface water and groundwater were estimated based on Cl concentrations of the samples, assuming conservative two end-member mixing during the event. This mixing model indicates that maximum river water contribution to the groundwater system was approximately 20%. River water had concentrations of iron, manganese, and other trace metals that were elevated by several orders of magnitude above the concentrations of groundwater at base flow. Maximum iron concentrations in the grab samples coincide with the peak of river water inflow into the cave system, but preliminary results suggest the maximum concentration is about 13% lower than expected based on mixing alone. This depletion below expected concentrations indicates that some of the iron intruded with the river water has been removed, presumably through precipitation of Fe-oxides. In contrast, peak manganese concentrations in the aquifer occur 14 days after the peak of the reversal when the spring is again discharging, suggesting that manganese within the cave system was mobilized. These data suggest that dissolution and precipitation reactions of Fe and Mn are decoupled in the system. This decoupling could result from changing redox conditions as river water intrudes the caves, driving oxidation of dissolved organic matter introduced with the river water.
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.
The Trace Element Composition of Plankton and Dust in the Qatari EEZ
NASA Astrophysics Data System (ADS)
Turner, J.; Murray, J. W.; Yigiterhan, O.; Al-Ansari, I. S.; Al-Ansi, M.; Abdel-Moati, M.; Paul, B.; Nelson, A.
2015-12-01
We present data on elemental concentrations of plankton net tow samples from the Exclusive Economic Zone (EEZ) of Qatar in the Arabian Gulf as part of a broader study of biogenic and lithogenic influences on particulate trace metal concentrations in the surface ocean. There are relatively few analyses of planktonic trace metals and their associated role in the biogeochemical system. We had the opportunity to investigate the composition of plankton in a region heavily affected by dust, a significant factor for phytoplankton growth. Our samples were collected from 2012 to 2015 using trace metal clean net tows with mesh sizes of 50 and 200 microns for measurements of phytoplankton and zooplankton, respectively. Samples were totally digested and analyzed by inductively coupled plasma-mass spectroscopy (ICP-MS). The biogenic portion was determined by subtracting the lithogenic portion from the total concentration. The lithogenic fraction was defined as the concentration of aluminum in the sample multiplied by a [Me]/Al ratio. Using average Qatari dust for these ratios generated a significant amount of overcorrection, so ratios were established using average upper continental crust (UCC). This method still caused some overcorrection for the lithogenic portion resulting in negative excess values for barium, molybdenum, and lead. These same elements showed the least consistency between measurements. For the other elements, a relative stoichiometry for plankton was determined as Fe > Cu ≈ Zn > As ≈ Cr ≈ Mn ≈ Ni ≈ V > Cd ≈ Co. We also found a significant near shore enrichment for 9 out of 13 elements analyzed, indicative of a possible influence of coastal processes.
Geochemical study of the organic matter from Querecual formation, Anzoategui State, Venezuela
DOE Office of Scientific and Technical Information (OSTI.GOV)
Garban, G.; Lopez, L.; Lo Monaco, S.
1996-08-01
Kerogen and bitumen fractions extracted from twenty-one limestone samples from kind section of Querecual formation (Querecual River, Anzoategui State, Venezuela) were analyzed for their content of Co, Cr, Fe, Mn, Mo, Ni, S, Sr, V and Zn. S and trace-metals content from the kerogen fraction were used to obtain information about paleoenvironmental sedimentation conditions of the Querecual formation. Based on these data, and especially on the V and S content variations plus V/Ni, VIV+Ni and Mo/Mo+Cr ratios, we confirm an ancient-reducer condition on this region according with a sulfur-reducer environment. Trace-metals content variations from the bitumen fraction along the studymore » section were used as possible primary migration indicators. V and Ni were the only elements showing a clear tendency to be used as primary migration indicators. The observed tendency allows us to postulate a vertical migration of the bitumen, from center to the extremes of the section.« less
Qiang, Hong; Lang, Dong-Li; Li, Yu-You
2012-01-01
The effect of trace metals on the mesophilic methane fermentation of high-solid food waste was investigated using both batch and continuous experiments. The continuous experiment was conducted by using a CSTR-type reactor with three run. During the first run, the HRT of the reactor was stepwise decreased from 100 days to 30 days. From operation day 50, the reactor efficiency deteriorated due to the lack of trace metals. The batch experiment showed that iron, cobalt, and nickel combinations had a significant effect on food waste. According to the results of the batch experiment, a combination of iron, cobalt, and nickel was added into the CSTR reactor by two different methods at run II, and III. Based on experimental results and theoretical calculations, the most suitable values of Fe/COD, Co/COD, and Ni/COD in the substrate were identified as 200, 6.0, and 5.7 mg/kg COD, respectively. Copyright © 2011 Elsevier Ltd. All rights reserved.
Fe atom exchange between aqueous Fe2+ and magnetite.
Gorski, Christopher A; Handler, Robert M; Beard, Brian L; Pasakarnis, Timothy; Johnson, Clark M; Scherer, Michelle M
2012-11-20
The reaction between magnetite and aqueous Fe(2+) has been extensively studied due to its role in contaminant reduction, trace-metal sequestration, and microbial respiration. Previous work has demonstrated that the reaction of Fe(2+) with magnetite (Fe(3)O(4)) results in the structural incorporation of Fe(2+) and an increase in the bulk Fe(2+) content of magnetite. It is unclear, however, whether significant Fe atom exchange occurs between magnetite and aqueous Fe(2+), as has been observed for other Fe oxides. Here, we measured the extent of Fe atom exchange between aqueous Fe(2+) and magnetite by reacting isotopically "normal" magnetite with (57)Fe-enriched aqueous Fe(2+). The extent of Fe atom exchange between magnetite and aqueous Fe(2+) was significant (54-71%), and went well beyond the amount of Fe atoms found at the near surface. Mössbauer spectroscopy of magnetite reacted with (56)Fe(2+) indicate that no preferential exchange of octahedral or tetrahedral sites occurred. Exchange experiments conducted with Co-ferrite (Co(2+)Fe(2)(3+)O(4)) showed little impact of Co substitution on the rate or extent of atom exchange. Bulk electron conduction, as previously invoked to explain Fe atom exchange in goethite, is a possible mechanism, but if it is occurring, conduction does not appear to be the rate-limiting step. The lack of significant impact of Co substitution on the kinetics of Fe atom exchange, and the relatively high diffusion coefficients reported for magnetite suggest that for magnetite, unlike goethite, Fe atom diffusion is a plausible mechanism to explain the rapid rates of Fe atom exchange in magnetite.
NASA Technical Reports Server (NTRS)
King, W. E.; Ethridge, E. C.
1985-01-01
The role of trace additions of reactive elements like Y, Ce, Th, or Hf to Cr bearing alloys was studied by applying a new developed technique of transverse section analytical electron microscopy. This reactive-element effect improves the high temperature oxidation resistance of alloys by strongly reducing the high temperature oxidation rate and enhancing the adhesion of the oxide scale, however, the mechanisms for this important effect remain largely unknown. It is indicated that the presence of yttrium affects the oxidation of Fe-Cr-Y alloys in at least two ways. The reactive element alters the growth mechanism of the oxide scale as evidenced by the marked influence of the reactive element on the oxide scale microstructure. The present results also suggest that reactive-element intermetallic compounds, which internally oxidize in the metal during oxidation, act as sinks for excess vacancies thus inhibiting vacancy condensation at the scale-metal interface and possibly enhancing scale adhesion.
Evaluation of elemental enrichments in surface sediments off southwestern Taiwan
NASA Astrophysics Data System (ADS)
Chen, Chen-Tung; Kandasamy, Selvaraj
2008-05-01
Surface slices of 20 sediment cores, off southwestern Taiwan, and bed sediment of River Kaoping were measured for major and trace elements (Al, As, Ca, Cd, Cl, Cr, Cu, Fe, K, Mg, Mn, Na, Ni, P, Pb, S, Si, Ti, V, and Zn) to evaluate the geochemical processes responsible for their distribution, including elemental contamination. Major element/Al ratio and mean grain size indicate quartz-dominated, coarse grained sediments that likely derived from sedimentary rocks of Taiwan and upper crust of Yangtze Craton. Bi-plot of SiO2 versus Fe2O{3/T} suggests the possible iron enrichment in sediments of slag dumping sites. Highest concentrations of Cr, Mn, P, S, and Zn found in sediments of dumping sites support this. Correlation analysis shows dual associations, detrital and organic carbon, for Cr, P, S, and V with the latter association typical for sediments in dumping sites. Normalization of trace elements to Al indicates high enrichment factors (>2) for As, Cd, Pb, and Zn, revealing contamination. Factor analysis extracted four geochemical associations with the principal factor accounted for 25.1% of the total variance and identifies the combined effects of dumped iron and steel slag-induced C-S-Fe relationship owing to authigenic precipitation of Fe-Mn oxyhydroxides and/or metal sulfides, and organic matter complexation of Fe, Mn, Ca, Cr, P, and V. Factors 2, 3, and 4 reveal detrital association (Ti, Al, Ni, Pb, Cu, and V), effect of sea salt (Cl, Mg, Na, and K) and anthropogenic component (As and Zn)-carbonate link, respectively, in the investigated sediments.
Hu, Yunjie; Lin, Jun; Zhang, Suanqin; Kong, Lingdong; Fu, Hongbo; Chen, Jianmin
2015-04-01
For a better understanding of metal particle morphology and behaviors in China, atmospheric aerosols were sampled in the summer of 2012 in Beijing. The single-particle analysis shows various metal-bearing speciations, dominated by oxides, sulfates and nitrates. A large fraction of particles is soluble. Sources of Fe-bearing particles are mainly steel industries and oil fuel combustion, whereas Zn- and Pb-bearing particles are primarily contributed by waste incineration, besides industrial combustion. Other trace metal particles play a minor rule, and may come from diverse origins. Mineral dust and anthropogenic source like vehicles and construction activities are of less importance to metal-rich particles. Statistics of 1173 analyzed particles show that Fe-rich particles (48.5%) dominate the metal particles, followed by Zn-rich particles (34.9%) and Pb-rich particles (15.6%). Compared with the abundances among clear, haze and fog conditions, a severe metal pollution is identified in haze and fog episodes. Particle composition and elemental correlation suggest that the haze episodes are affected by the biomass burning in the southern regions, and the fog episodes by the local emission with manifold particle speciation. Our results show the heterogeneous reaction accelerated in the fog and haze episodes indicated by more zinc nitrate or zinc sulfate instead of zinc oxide or carbonate. Such information is useful in improving our knowledge of fine airborne metal particles on their morphology, speciation, and solubility, all of which will help the government introduce certain control to alleviate metal pollution. Copyright © 2014 Elsevier B.V. All rights reserved.
Geochemistry of Pallasite Olivines and the Origin of Main-Group Pallasites
NASA Technical Reports Server (NTRS)
Mittlefehldt, D. W.; Rumble, D., III
2006-01-01
Main-group pallasites (PMG) are mixtures of iron-nickel metal and magnesian olivine thought to have been formed at the core-mantle boundary of an asteroid [1]. Some have anomalous metal compositions (PMG-am) and a few have atypically ferroan olivines (PMG-as) [2]. PMG metal is consistent with an origin as a late fractionate of the IIIAB iron core [2]. Most PMG olivines have very similar Fe/Mg ratios, likely due to subsolidus redox reaction with the metal [3]. In contrast, minor and trace elements show substantial variation, which may be explained by either: (i) PMG were formed at a range of depths in the parent asteroid; the element variations reflect variations in igneous evolution with depth, (ii) the pallasite parent asteroid was chemically heterogeneous; the heterogeneity partially survived igneous processing, or (iii) PMG represent the core-mantle boundaries of several distinct parent asteroids [4, 5]. We have continued doing major, minor and trace elements by EMPA and INAA on a wider suite of PMG olivines, and have begun doing precise oxygen isotope analyses to test these hypotheses. Manganese is homologous with Fe(2+), and can be used to distinguish between magmatic and redox processes as causes for Fe/Mg variations. PMG olivines have a range in molar 1000*Mn/Mg of 2.3-4.6 indicating substantial igneous fractionation in olivines with very similar Fe/Mg (0.138-0.148). The Mg-Mn-Fe distributions can be explained by a fractional crystallization-reduction model; higher Mn/Mg ratios reflect more evolved olivines while Fe/Mg is buffered by redox reactions with the metal. There is a positive association between Mn/Mg and Sc content that is consistent with igneous fractionation. However, most PMG olivines fall within a narrow Mn/Mg range (3.0-3.6), but these show a substantial range in Sc (1.00-2.29 micro-g/g). Assuming fractional crystallization, this Sc range could have resulted from approx.65% crystallization of an ultramafic magma. This is inconsistent with formation at the core-mantle boundary of a single asteroid [4]. One alternative is that the PMG are fragments of several asteroids, and these could have had different initial Sc contents, Mn/Mg and differences in igneous history. Our preliminary O isotope data and those of [6, 7] do not support this, although the coverage of PMG olivines is incomplete. The PMG-as Springwater is not easily fit in any scenario. Its olivine has among the highest Mn/Mg suggesting it is one of the most evolved, but the lowest Sc content suggesting it is the least evolved. The O isotopic composition of Springwater olivine is the same as that of other PMG. Thus there is no indication that it represents a distinct parent asteroid. Our preliminary O isotopic data favor a single PMG parent asteroid. In this case, the olivines are more likely melt-residues, and that the parent asteroid was initially heterogeneous in chemical, but not isotopic, composition.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Schmidt, R.L.
1982-04-01
This report describes laboratory experiments in which neutron-activated 347 stainless steel specimens were exposed to clayey silt from Sequim Bay, Washington. The properties and trace metal geochemistry of the sediment and the amounts of corrosion products that were released under oxic and reduced conditions and their distribution among different chemical fractions of the sediment are discussed. The distributions of Cr, Mn, Fe, Ni and Cu among different chemical forms in the Sequim Bay sediment show that DTPA removed <10% of extractable Cr, Fe and Mn, approx. 20% of extractable Ni and approx. 30% of extractable Cu. The inorganic fraction (materialmore » soluble in 2.5% acetic acid) accounted for approx. 30% of total extractable Mn and approx. 10% or less of Cr, Fe, Ni and Cu. Major portions of Cr and Cu, and a large amount of Fe were in the organic fraction. Extractable Mn, Fe and Ni were associated with hydrous oxides likely as coatings on the mineral substrate of the sediment. No Co was detectable in any of the extracts. (PSB)« less
Tran, Ashley; Williams, Geoffrey; Younus, Shagufta; Ali, Nujhat N; Blair, Sandra L; Nizkorodov, Sergey A; Al-Abadleh, Hind A
2017-09-05
The role of transition metals in the formation and aging of secondary organic aerosol (SOA) from aliphatic and aromatic precursors in heterogeneous/multiphase reactions is not well understood. The reactivity of soluble Fe(III) toward known benzene photooxidation products that include fumaric (trans-butenedioic) and muconic (trans,trans-2,4-hexadienedioic) acids was investigated. Efficient formation of brightly colored nanoparticles was observed that are mostly rod- or irregular-shaped depending on the structure of the organic precursor. The particles were characterized for their optical properties, growth rate, elemental composition, iron content, and oxidation state. Results indicate that these particles have mass absorption coefficients on the same order as black carbon and larger than that of biomass burning aerosols. The particles are also amorphous in nature and consist of polymeric chains of Fe centers complexed to carboxylate groups. The oxidation state of Fe was found to be in between Fe(III) and Fe(II) in standard compounds. The organic reactant to iron molar ratio and pH were found to affect the particle growth rate. Control experiments using maleic acid (cis-butenedioic acid) and succinic acid (butanedioic acid) produced no particles. The formation of particles reported herein could account for new pathways that lead to SOA and brown carbon formation mediated by transition metals. In addition, the multiple chemically active components in these particles (iron, organics, and acidic groups) may have an effect on their chemical reactivity (enhanced uptake of trace gases, catalysis, and production of reactive oxygen species) and their likely poor cloud/ice nucleation properties.
Regimes of association of arsenic and selenium during pulverized coal combustion
DOE Office of Scientific and Technical Information (OSTI.GOV)
Wayne S. Seames; Jost O.L. Wendt
2007-07-01
A suite of six coals, of widely differing As, Se, Ca, Fe, and sulfur contents, was burned under self-sustaining conditions in a 17 kW downflow laboratory combustor. Size segregated ash-laden aerosol samples were isokinetically withdrawn and collected on a Berner low pressure impactor. Correlations between trace element concentration (As or Se) and that of major elements (as functions of particle size) were then used to infer chemical associations between trace metals and Ca and/or Fe, and how these depended on sulfur. These baseline data led to formation of the following hypotheses, namely: (1) dominant As and Se partitioning mechanisms dependmore » on the availability of Ca and/or Fe active sites for surface reaction; (2) increasing combustion temperature increases the availability of active cation sites, and increases partitioning of As and Se to fly ash by surface reaction; (3) sulfur competes with these surface reactions, decreasing As and Se partitioning to fly ash surfaces. These hypotheses were tested by manipulating the As, Se, Ca, Fe, and S contents for various coals by doping. Temperature was adjusted in order to achieve comparisons of different coals and different coal constituents at similar thermal conditions, through O{sub 2} and CO{sub 2} addition, as required. These results confirmed the hypotheses above, and allowed an association regime map to be constructed. This map shows that both As and Se associate with Fe and Ca, provided active sites are available. Se reacts preferentially with Fe over Ca when both are available while As reactions with both Fe and Ca are comparable. Sulfur can prevent association of both As and Se, by preferentially reacting with active sites, especially those on Fe. When sufficient sites are not available, the release of vapor-phase As and Se species is promoted. 23 refs., 4 figs., 4 tabs.« less
Duran, Ali; Tuzen, Mustafa; Soylak, Mustafa
2014-07-01
Regular consumption of fish has been widely recommended by health authorities. However, it is known that some species accumulate high levels of contaminants including heavy metals (e.g., Hg, Cd, Pb, and As). In this study, Cu, Pb, Co, Ni, Cr, Mn, Cd, and Fe were determined in the muscle tissue of 11 commercially available fish species (Sparus auratus, Dicentrarchus labrax, Mullus barbatus, Belone belone, Psetta maxima, Epinephelus aeneus, Salmothymus, Soleidae, Pomatomus saltatrix, Engraulis encrasicolus, and Sarda sarda) supplied from retailers in Kayseri, Turkey. Determinations were carried out by flame atomic absorption spectrometry after the wet digestion method. The average metal concentrations of the 11 species were determined in the range of 0.54-1.79, 0.82-1.40, 2.38-4.54, 1.23-3.67, 5.01-5.97, 0.77-3.59, 0.48-1.06, and 5.05-122.8 μg/g wet weight for Cu, Pb, Co, Ni, Cr, Mn, Cd, and Fe, respectively. The permissible tolerable daily intake (PTDI) and calculated daily intake (CDI) values were compared, and the calculated daily intake values of the samples were found to be below the established values. Correlations between the metal contents in samples were investigated by performing correlation tests with SPSS 13.0 for windows.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Phelps, Tommy Joe; Moon, Ji Won; Roh, Yul
The behavior of metal ions leaching and precipitated mineral phases of metal-rich fly ash (FA) was examined in order to evaluate microbial impacts on carbon sequestration and metal immobilization. The leaching solutions consisted of aerobic deionized water (DW) and artificial eutrophic water (AEW) that was anaerobic, organic- and mineral-rich, and higher salinity as is typical of bottom water in eutrophic algae ponds. The Fe- and Ca-rich FAs were predominantly composed of quartz, mullite, portlandite, calcite, hannebachite, maghemite, and hematite. After 86 days, only Fe and Ca contents exhibited a decrease in leaching solutions while other major and trace elements showedmore » increasing or steady trends in preference to the type of FA and leaching solution. Ca-rich FA showed strong carbon sequestration efficiency ranging up to 32.3 g CO(2)/kg FA after 86 days, corresponding to almost 65% of biotic carbon sequestration potential under some conditions. Variations in the properties of FAs such as chemical compositions, mineral constituents as well as the type of leaching solution impacted CO(2) capture. Even though the relative amount of calcite increased sixfold in the AEW and the relative amount of mineral phase reached 37.3 wt% using Ca-rich FA for 86 days, chemical sequestration did not accomplish simultaneous precipitation and sequestration of several heavy metals.« less
NASA Astrophysics Data System (ADS)
Williams, H. M.; Prytulak, J.; Woodhead, J. D.; Kelley, K. A.; Brounce, M.; Plank, T.
2018-04-01
Subduction zone systems are central to a multitude of processes from the evolution of the continental crust to the concentration of metals into economically viable deposits. The interplay between oxygen fugacity, sulfur saturation, fluid exsolution and fractionating mineral assemblages that gives rise to typical arc magma chemical signatures is, however, still poorly understood and novel geochemical approaches are required to make further progress. Here we examine a well-characterized suite of arc lavas from the Marianas (W. Pacific) for their stable Fe isotope composition. In agreement with previous work and mass balance considerations, contributions from sediments and/or fluids are shown to have negligible effect on Fe isotopes. Instead, we focus on disentangling processes occurring during basalt through dacite differentiation using a sample suite from the island of Anatahan. Anatahan whole rock Fe isotope compositions (δ57Fe) range from -0.05 ± 0.05 to 0.17 ± 0.03 (2 S.D.)‰. A fractionation model is constructed, where three distinct stages of differentiation are required to satisfy the combined major and trace element and isotopic observations. In particular, the sequestration of isotopically heavy Fe into magnetite and isotopically light Fe into sulfide melts yields important constraints. The data require that lavas are first undersaturated with respect to crystalline or molten sulfide, followed by the crystallisation of magnetite, which then triggers late sulfide saturation. The model demonstrates that the final stage of removal of liquid or crystalline sulfide can effectively sequester Cu (and presumably other chalcophiles) and that late stage exsolution of magmatic fluids or brines may not be required to do this, although these processes are not mutually exclusive. Finally, the new Fe isotope data are combined with previous Tl-Mo-V stable isotope determinations on the same samples. Importantly, the multi-valent transition metal stable isotope systems of Fe and V are decoupled by sulfide saturation, thus providing a potential tool to constrain its somewhat intractable timing. The observed decoupling of notionally redox-sensitive tracers underlines the caution required in the application of transition metal isotopes as direct redox proxies.
NASA Astrophysics Data System (ADS)
Maters, E. C.; Flament, P.; de Jong, J.; Mattielli, N. D. C.; Deboudt, K.
2017-12-01
Iron (Fe) is a key element in ocean biogeochemistry and hence the carbon cycle. Its low concentration in seawater limits primary production in >30% of the surface ocean, and thus strong interest lies in constraining Fe inputs to the ocean on different spatial and temporal scales. During Earth's past, large fluctuations in atmospheric deposition fluxes of continental particles including mineral dust and volcanic ash to the ocean may have played a role in climate change events. At present, anthropogenic particles from metal working, biomass burning, and fossil fuel combustion are increasingly recognised to deliver Fe to the ocean as well. To assess the relative importance of these particulate Fe sources, knowledge of their deposition flux (overall dominated by natural dusts) and their Fe solubility (a proxy for Fe bioavailability, and typically higher in anthropogenic materials) is needed, although large uncertainties remain in these parameters. A potential tool for tracing atmospheric inputs to the ocean is the Fe isotope composition (δ56Fe), previously reported to be distinct for natural versus anthropogenic particles. However, it remains unknown if and how the δ56Fe is influenced by various physicochemical processes (e.g. acidification, photochemistry) shown to enhance Fe solubility in airborne particles. Iron isotopic fractionation has been observed during ligand-controlled and photo-reductive dissolution of goethite at low pH,[1] and similar effects may apply to more complex materials during atmospheric transport. Specifically, isotopic enrichment in partially dissolved particles may result from initial preferential release of 54Fe over 56Fe from the solid surface. To test these hypotheses, we subjected natural and anthropogenic specimens, including mineral dust from the Sahara desert and industrial ash from an Fe-Mn alloy factory, to simulated atmospheric processing in pH 2 solution in the presence/absence of oxalic acid and solar radiation. The Fe solubility and δ56Fe/IRMM-014 values of the solid samples were measured to determine the extents of fractionation relative to unprocessed particles. The results of these experiments and the implications for tracing atmospheric Fe inputs to the ocean will be presented. [1] Wiederhold, J. G. et. al. (2006) Environ. Sci. Technol., 40, 3787-3793.
Iqubal, Md. Asif; Sharma, Rachana; Jheeta, Sohan; Kamaluddin
2017-01-01
The amino acid condensation reaction on a heterogeneous mineral surface has been regarded as one of the important pathways for peptide bond formation. Keeping this in view, we have studied the oligomerization of the simple amino acids, glycine and alanine, on nickel ferrite (NiFe2O4), cobalt ferrite (CoFe2O4), copper ferrite (CuFe2O4), zinc ferrite (ZnFe2O4), and manganese ferrite (MnFe2O4) nanoparticles surfaces, in the temperature range from 50–120 °C for 1–35 days, without applying any wetting/drying cycles. Among the metal ferrites tested for their catalytic activity, NiFe2O4 produced the highest yield of products by oligomerizing glycine to the trimer level and alanine to the dimer level, whereas MnFe2O4 was the least efficient catalyst, producing the lowest yield of products, as well as shorter oligomers of amino acids under the same set of experimental conditions. It produced primarily diketopiperazine (Ala) with a trace amount of alanine dimer from alanine condensation, while glycine was oligomerized to the dimer level. The trend in product formation is in accordance with the surface area of the minerals used. A temperature as low as 50 °C can even favor peptide bond formation in the present study, which is important in the sense that the condensation process is highly feasible without any sort of localized heat that may originate from volcanoes or hydrothermal vents. However, at a high temperature of 120 °C, anhydrides of glycine and alanine formation are favored, while the optimum temperature for the highest yield of product formation was found to be 90 °C. PMID:28346388
Early Diagenesis of Trace Elements in Modern Fjord Sediments of the High Arctic
NASA Astrophysics Data System (ADS)
Herbert, L.; Riedinger, N.; Aller, R. C.; Jørgensen, B. B.; Wehrmann, L.
2017-12-01
Marine sediments are critical repositories for elements that are only available at trace concentrations in seawater, such as Fe, Mn, Co, Ni, As, Mo, and U. The behavior of these trace elements in the sediment is governed by a dynamic interplay of diagenetic reactions involving organic carbon, Fe and Mn oxides, and sulfur phases. In the Arctic fjords of Svalbard, glacial meltwater delivers large amounts of reactive Fe and Mn oxides to the sediment, while organic carbon is deposited episodically and diluted by lithogenic material. These conditions result in pronounced Fe and Mn cycling, which in turn drives other diagenetic processes such as rapid sulfide oxidation. These conditions make the Svalbard fjords ideal sites for investigating trace element diagenesis because they allow resolution of the interconnections between Fe and Mn dynamics and trace element cycling. In August 2016, we collected sediment cores from three Svalbard fjords and analyzed trace elements in the pore water and solid sediment over the top meter. Initial results reveal the dynamic nature of these fjords, which are dominated by non-steady state processes and episodic events such as meltwater pulses and phytoplankton blooms. Within this system, the distribution of As appears to be strongly linked to the Fe cycle, while Co and Ni follow Mn; thus, these three elements may be released from the sediment through diffusion and bioturbation along with Fe and Mn. The pore water profiles of U and Mo indicate removal processes that are independent from Fe or Mn, and which are rather unexpected given the apparent diagenetic conditions. Our results will help elucidate the processes controlling trace element cycling in a dynamic, glacially impacted environment and will ultimately contribute to our understanding of the role of fjords in the biogeochemical cycling of trace elements in a rapidly changing Arctic Ocean.
Chemical characterization of seven Large Area Collector particles by SXRF. [cosmic dust composition
NASA Technical Reports Server (NTRS)
Flynn, G. J.; Sutton, S. R.
1991-01-01
Optical microscopy and synchrotron X-ray fluorescence (SXRF) are used to analyze the chemical composition of seven dark-appearing cosmic-dust particles obtained in the stratosphere during NASA Johnson Large Area Collector flights. The experimental setup and procedures are outlined, and the results are presented in extensive tables. Three of the particles had abundances similar to those of chondrites (except for low Ca values in one particle); two had a metallic appearance and spectra dominated by Fe and Zn; one contained Cu and Cr plus small amounts of Fe and Zn; and one had igneous-type abundances of minor and trace elements while containing all of the elements seen in chondritic particles, suggesting it may be of extraterrestrial origin.
NASA Astrophysics Data System (ADS)
Gopon, Phillip; Spicuzza, Michael J.; Kelly, Thomas F.; Reinhard, David; Prosa, Ty J.; Fournelle, John
2017-09-01
The lunar regolith contains a variety of chemically reduced phases of interest to planetary scientists and the most common, metallic iron, is generally ascribed to space weathering processes (Lucey et al. ). Reports of silicon metal and iron silicides, phases indicative of extremely reducing conditions, in lunar samples are rare (Anand et al. ; Spicuzza et al. ). Additional examples of Fe-silicides have been identified in a survey of particles from Apollo 16 sample 61501,22. Herein is demonstrated the utility of low keV electron probe microanalysis (EPMA), using the Fe Ll X-ray line, to analyze these submicron phases, and the necessity of accounting for carbon contamination. We document four Fe-Si and Si0 minerals in lunar regolith return material. The new Fe-Si samples have a composition close to (Fe,Ni)3Si, whereas those associated with Si0 are close to FeSi2 and Fe3Si7. Atom probe tomography of (Fe,Ni)3Si shows trace levels of C (60 ppma and nanodomains enriched in C, Ni, P, Cr, and Sr). These reduced minerals require orders of magnitude lower oxygen fugacity and more reducing conditions than required to form Fe0. Documenting the similarities and differences in these samples is important to constrain their formation processes. These phases potentially formed at high temperatures resulting from a meteorite impact. Whether carbon played a role in achieving the lower oxygen fugacities—and there is evidence of nearby carbonaceous chondritic material—it remains to be proven that carbon was the necessary component for the unique existence of these Si0 and iron silicide minerals.
NASA Astrophysics Data System (ADS)
Abd El Naby, Ahmed; Al Menoufy, Safia; Gad, Ahmed
2018-03-01
Qarun Lake, in the Fayoum Depression of the Western Desert of Egypt, lies within the deepest area in the River Nile flood plain. The drainage water in the Qarun Lake is derived from the discharge of the natural and artificial drainage systems in the Fayoum. Mixed domestic and agricultural pollutants, including heavy metals, nitrates, phosphates, sulfates and pesticides, are discharged into Qarun Lake. Forty-six samples, collected from the undisturbed layer of sediments were used for benthic foraminiferal analysis. Concentrations of some selected trace metal elements (Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, Sr, V, and Zn) were also determined. Statistical analysis of the abiotic variables (Texture distribution of sediments, Physico-chemical parameters, and metals concentrations) and of the biotic variables (distribution of benthic foraminiferal species) were also performed. The Q-mode cluster analysis of benthic foraminiferal distribution has provided evidence that the Qarun Lake can be subdivided into two cluster groups (A and B), reflecting environmental changes in the lake ecosystem. Cluster B can also be subdivided into two sub-clusters (B1 and B2). The presence of only pollution tolerant taxa with higher faunal density and lower diversity and the absence of the other foraminiferal assemblages in cluster A were attributed to the high concentration of trace metal elements and the strong environmental stress at the eastern and central parts of the Qarun Lake.
Trace elements in ALS patients and their relationships with clinical severity.
Oggiano, Riccardo; Solinas, Giuliana; Forte, Giovanni; Bocca, Beatrice; Farace, Cristiano; Pisano, Andrea; Sotgiu, Maria Alessandra; Clemente, Simonetta; Malaguarnera, Michele; Fois, Alessandro Giuseppe; Pirina, Pietro; Montella, Andrea; Madeddu, Roberto
2018-04-01
An exploratory study of trace elements in ALS and their relationships with clinical severity was detected. Amyotrophic lateral sclerosis (ALS) is a neurodegenerative disorder that causes irreversible damage in humans, with the consequent loss of function of motoneurons (MNs), with a prognosis up to 5 years after diagnosis. Except to genetic rare cases it is not known the etiology of the disorder. Aim of our research is to investigate the possible role of heavy metals in the severity of the disease. In this study, by the use of plasma mass (ICP-MS), we have analyzed the content of essential and heavy metals such: Pb, Cd, Al, Hg, Mn, Fe, Cu, Zn, Se, Mg, and Ca, in blood, urine and hair of ALS patients and controls; moreover we divided the patients in two groups for disease severity and analyzed the difference among the groups, in order to study a possible involvement of metals in the severity of the damage. Our results suggest a protective role of Selenium, involved in protective antioxidant mechanisms, and a risk factor in the case of presence of Lead in blood. The levels of the other metals are not easy to interpret, because these may be due to life style and for essential metals a consequence of the disease condition, not a cause. Copyright © 2018 Elsevier Ltd. All rights reserved.
Abu Bakar, Nur Faizah; Fudholi, Ahmad; Ruslan, Mohd Hafidz; Saroeun, Im
2015-01-01
The content of 12 elements in Cambodian dried striped snakehead fish was determined using inductively coupled plasma mass spectrometry. The present study compares the level of the trace toxic metals and nutritional trace elements in the fish processed using solar drying system (SDS) and open sun drying (OSD). The skin of SDS fish has lower level of As, Pb, and Cd compared to the OSD sample. As such, the flesh of the fish accumulated higher amount of toxic metals during OSD compared to SDS. However, arsenic was detected in both samples within the safe limit. The nutritional elements (Fe, Mn, Mg, Se, Mo, Cu, Ni, and Cr) were higher in the skin sample SDS fish compared to OSD fish. These beneficial metals were not accumulated in the flesh sample SDS fish demonstrating lower level compared to drying under conventional system. The reddish coloration of the SDS fish was due to the presence of high Cu content in both the skin and flesh samples which possibly account for no mold formation 5 days after packaging. As conclusion, drying of Cambodian C. striata using solar-assisted system has proven higher content of the nutritious elements compared to using the conventional system despite only slight difference in the toxic metals level between the two systems. PMID:25688274
NASA Astrophysics Data System (ADS)
Salomone, Vanesa N.; Riera, Marina; Cerchietti, Luciana; Custo, Graciela; Muniain, Claudia
2017-05-01
Seaweed have a great capacity to accumulate heavy metals in their tissues. The chemical characterization of seaweed is important due to their use in environmental monitoring and human or animal food. The aim of the present study was to evaluate the multi-elemental composition of seaweed from San Jorge Gulf (Patagonia, Argentina) by Total Reflection X-ray Fluorescence (TXRF). The elements As, Br, Cu, Cr, Fe, Mn, Ni, Pb, Rb, Sr, V and Zn were seasonally analyzed and quantified in blades of Macrocystis pyrifera. TXRF showed to be a suitable technique for simultaneous multi-element analysis in this kind of samples. The results revealed seasonal variations in the chemical content for some elements; arsenic content was maximum in summer and autumn, iron concentration increased to the winter and zinc concentration was maximum in autumn. The sum of principal micronutrients (Fe + Zn + Mn + Cu) varied between 114 and 171 mg k- 1 g dw. The total As concentration ranged between 36 and 66 mg kg- 1. Lead, nickel and copper were not detected.
NASA Astrophysics Data System (ADS)
Knipping, Jaayke L.; Bilenker, Laura D.; Simon, Adam C.; Reich, Martin; Barra, Fernando; Deditius, Artur P.; Wälle, Markus; Heinrich, Christoph A.; Holtz, François; Munizaga, Rodrigo
2015-12-01
Iron oxide-apatite (IOA) deposits are an important source of iron and other elements (e.g., REE, P, U, Ag and Co) vital to modern society. However, their formation, including the namesake Kiruna-type IOA deposit (Sweden), remains controversial. Working hypotheses include a purely magmatic origin involving separation of an Fe-, P-rich, volatile-rich oxide melt from a Si-rich silicate melt, and precipitation of magnetite from an aqueous ore fluid, which is either of magmatic-hydrothermal or non-magmatic surface or metamorphic origin. In this study, we focus on the geochemistry of magnetite from the Cretaceous Kiruna-type Los Colorados IOA deposit (∼350 Mt Fe) located in the northern Chilean Iron Belt. Los Colorados has experienced minimal hydrothermal alteration that commonly obscures primary features in IOA deposits. Laser ablation-inductively coupled plasma-mass spectroscopy (LA-ICP-MS) transects and electron probe micro-analyzer (EPMA) wavelength-dispersive X-ray (WDX) spectrometry mapping demonstrate distinct chemical zoning in magnetite grains, wherein cores are enriched in Ti, Al, Mn and Mg. The concentrations of these trace elements in magnetite cores are consistent with igneous magnetite crystallized from a silicate melt, whereas magnetite rims show a pronounced depletion in these elements, consistent with magnetite grown from an Fe-rich magmatic-hydrothermal aqueous fluid. Further, magnetite grains contain polycrystalline inclusions that re-homogenize at magmatic temperatures (>850 °C). Smaller inclusions (<5 μm) contain halite crystals indicating a saline environment during magnetite growth. The combination of these observations are consistent with a formation model for IOA deposits in northern Chile that involves crystallization of magnetite microlites from a silicate melt, nucleation of aqueous fluid bubbles on magnetite surfaces, and formation and ascent of buoyant fluid bubble-magnetite aggregates. Decompression of the fluid-magnetite aggregate during ascent along regional-scale transcurrent faults promotes continued growth of the magmatic magnetite microlites from the Fe-rich magmatic-hydrothermal fluid, which manifests in magnetite rims that have trace element abundances consistent with growth from a magmatic-hydrothermal fluid. Mass balance calculations indicate that this process can leach and transport sufficient Fe from a magmatic source to form large IOA deposits such as Los Colorados. Furthermore, published experimental data demonstrate that a saline magmatic-hydrothermal ore fluid will scavenge significant quantities of metals such as Cu and Au from a silicate melt, and when combined with solubility data for Fe, Cu and Au, it is plausible that the magmatic-hydrothermal ore fluid that continues to ascend from the IOA depositional environment can retain sufficient concentrations of these metals to form iron oxide copper-gold (IOCG) deposits at lateral and/or stratigraphically higher levels in the crust. Notably, this study provides a new discrimination diagram to identify magnetite from Kiruna-type deposits and to distinguish them from IOCG, porphyry and Fe-Ti-V/P deposits, based on low Cr (<100 ppm) and high V (>500 ppm) concentrations.
Hg and Pt-metals in meteorite carbon-rich residues - Suggestions for possible host phase for Hg
NASA Technical Reports Server (NTRS)
Jovanovic, S.; Reed, G. W., Jr.
1980-01-01
Carbon-rich and oxide residual phases have been isolated from Allende and Murchison by acid demineralization for the determination of their Hg, Pt-metal, Cr, Sc, Co, and Fe contents. Experimental procedures used eliminated the possibility of exogenous and endogenous contaminant trace elements from coprecipitating with the residues. Large enrichments of Hg and Pt-metals were found in Allende but not in Murchison residues. Hg-release profiles from stepwise heating experiments suggest a sulfide as the host for Hg. Diffusion calculations for Hg based on these experiments indicate an activation energy of 7-8 kcal/mol, the same as that for Hg in troilite from an iron meteorite. This is further support for a sulfide host phase for Hg. Equilibration of Hg with this phase at approximately 900 K is indicated. Reasons for the presence of Pt-metals in noncosmic relative abundances are explored.
Use of induced fluorescence measurements to assess aluminum-organic interactions in acidified lakes
NASA Technical Reports Server (NTRS)
Vodacek, A.; Philpot, W. D.
1985-01-01
The application of laser fluorosensing to the tracing of metals in acid lakes is proposed. The effects of the metals on the dissolving organic carbon (DOC) fluorescence is studied using laboratory mixed water samples and natural water samples from Hamilton and Big Moose Lakes in New York. The operation of the laser fluorosensing system employed in the experiment is described. The DOC fluorescence was quenched by Al, Cu, and Fe, and the relation between pH and the quenching rate is examined. The humic substances fluorescence spectra are analyzed to estimate the concentrations of DOC in water and the relative concentration of Al. The interference problems caused by chemical competition between metal ions and ligands, and changes in the background DOC fluorescence are discussed. It is noted that an airborne laser fluorescence is useful for detecting elevated concentrations of metals.
Establishing the environmental risk of metal contaminated river bank sediments
NASA Astrophysics Data System (ADS)
Lynch, Sarah; Batty, Lesley; Byrne, Patrick
2016-04-01
Climate change predictions indicate an increase in the frequency and duration of flood events along with longer dry antecedent conditions, which could alter patterns of trace metal release from contaminated river bank sediments. This study took a laboratory mesocosm approach. Chemical analysis of water and sediment samples allowed the patterns of Pb and Zn release and key mechanisms controlling Pb and Zn mobility to be determined. Trace metal contaminants Pb and Zn were released throughout flooded periods. The highest concentrations of dissolved Pb were observed at the end of the longest flood period and high concentrations of dissolved Zn were released at the start of a flood. These concentrations were found to exceed environmental quality standards. Key mechanisms controlling mobility were (i) evaporation, precipitation and dissolution of Zn sulphate salts, (ii) anglesite solubility control of dissolved Pb, (iii) oxidation of galena and sphalerite, (iv) reductive dissolution of Mn/Fe hydroxides and co-precipitation/adsorption with Zn. In light of climate change predictions these results indicate future scenarios may include larger or more frequent transient 'pulses' of dissolved Pb and Zn released to river systems. These short lived pollution episodes could act as a significant barrier to achieving the EU Water Framework Directive objectives.
Dissolved trace elements in a nitrogen-polluted river near to the Liaodong Bay in Northeast China.
Bu, Hongmei; Song, Xianfang; Guo, Fen
2017-01-15
Dissolved trace element concentrations (Ba, Fe, Mn, Si, Sr, and Zn) were investigated in the Haicheng River near to the Liaodong Bay in Northeast China during 2010. Dissolved Ba, Fe, Mn, and Sr showed significant spatial variation, whereas dissolved Fe, Mn, and Zn displayed seasonal variations. Conditions such as water temperature, pH, and dissolved oxygen were found to have an important impact on redox reactions involving dissolved Ba, Fe, and Zn. Dissolved Fe and Mn concentrations were regulated by adsorption or desorption of Fe/Mn oxyhydroxides and the effects of organic carbon complexation on dissolved Ba and Sr were found to be significant. The sources of dissolved trace elements were found to be mainly from domestic sewage, industrial waste, agricultural surface runoff, and natural origin, with estimated seasonal and annual river fluxes established as important inputs of dissolved trace elements from the Haicheng River into the Liaodong Bay or Bohai Sea. Copyright © 2016 Elsevier Ltd. All rights reserved.
Comparison of digestion methods for determination of trace and minor metals in plant samples.
Lavilla, I; Filgueiras, A V; Bendicho, C
1999-12-01
In this paper, three dissolution methods using pressure digestion vessels (low-, medium-, and high-pressure vessels) for the determination of metals in plant samples are described. The Plackett-Burman saturated factorial design was used to identify the significant factors influencing wet ashing and to select optimized dissolution conditions. The three methods were statistically compared (on-way ANOVA) on the same sample; no significant differences were obtained. In all cases the relative standard deviation values were <3%. The digestion method based on the use of low-pressure vessels and a microwave oven was validated against CRM GBW07605 tea leaves. This method was applied to the determination of Cu, Zn, Mn, Fe, Mg, and Ca in 22 different medicinal, aromatic, and seasoning plants by flame-atomic absorption spectrometry. The concentration intervals of metal in the plants analyzed were the following: Cu, 4 (Allium sativum)-35 (Thea sinensis) microg g(-1); Zn, 7 (Piper nigrum)-90 (Betula alba) microg g(-1); Mn, 9 (Allium sativum)-939 (Caryophylus aromaticus) microg g(-1); Fe, 33 (Allium sativum)-2486 (Anethum graveolens) microg g(-1); Mg, 495 (Allium sativum)-7458 (Ocimum basilicum) microg g(-1); Ca, 386 (Allium sativum)-21500 (Ocimum basilicum) microg g(-1).
Al-Rousan, Saber A; Al-Shloul, Rashid N; Al-Horani, Fuad A; Abu-Hilal, Ahmad H
2007-12-01
In order to assess pollutants and impact of environmental changes in the coastal region of the Jordanian Gulf of Aqaba, concentrations of six metals were traced through variations in 5 years growth bands sections of recent Porties coral skeleton. X-radiography showed annual growth band patterns extending back to the year 1925. Baseline metal concentrations in Porites corals were established using 35 years-long metal record from late Holocene coral (deposited in pristine environment) and coral from reef that is least exposed to pollution in the marine reserve in the Gulf of Aqaba. The skeleton samples of the collected corals were acid digested and analyzed for their Cd, Cu, Fe, Mn, Pb and Zn content using Flame Atomic Absorption Spectrophotometer (FAAS). All metal profiles (except Fe and Zn) recorded the same metal signature from recent coral (1925-2005) in which low steady baseline levels were displayed in growth bands older than 1965, similar to those obtained from fossil and unpolluted corals. Most metals showed dramatic increase (ranging from 17% to 300%) in growth band sections younger than 1965 suggesting an extensive contamination of the coastal area since the mid sixties. This date represents the beginning of a period that witnessed increasing coastal activities, constructions and urbanization. This has produced a significant reduction in coral skeletal extension rates. Results from this study strongly suggest that Porites corals have a high tendency to accumulate heavy metals in their skeletons and therefore can serve as proxy tools to monitor and record environmental pollution (bioindicators) in the Gulf of Aqaba.
Redox systematics of a magma ocean with variable pressure-temperature gradients and composition
Righter, K.; Ghiorso, M. S.
2012-01-01
Oxygen fugacity in metal-bearing systems controls some fundamental aspects of the geochemistry of the early Earth, such as the FeO and siderophile trace element content of the mantle, volatile species that influence atmospheric composition, and conditions for organic compounds synthesis. Redox and metal-silicate equilibria in the early Earth are sensitive to oxygen fugacity (fO2), yet are poorly constrained in modeling and experimentation. High pressure and temperature experimentation and modeling in metal-silicate systems usually employs an approximation approach for estimating fO2 that is based on the ratio of Fe and FeO [called “ΔIW (ratio)” hereafter]. We present a new approach that utilizes free energy and activity modeling of the equilibrium: Fe + SiO2 + O2 = Fe2SiO4 to calculate absolute fO2 and relative to the iron-wüstite (IW) buffer at pressure and temperature [ΔIW (P,T)]. This equilibrium is considered across a wide range of pressures and temperatures, including up to the liquidus temperature of peridotite (4,000 K at 50 GPa). Application of ΔIW (ratio) to metal-silicate experiments can be three or four orders of magnitude different from ΔIW (P,T) values calculated using free energy and activity modeling. We will also use this approach to consider the variation in oxygen fugacity in a magma ocean scenario for various thermal structures for the early Earth: hot liquidus gradient, 100 °C below the liquidus, hot and cool adiabatic gradients, and a cool subsolidus adiabat. The results are used to assess the effect of increasing P and T, changing silicate composition during accretion, and related to current models for accretion and core formation in the Earth. The fO2 in a deep magma ocean scenario may become lower relative to the IW buffer at hotter and deeper conditions, which could include metal entrainment scenarios. Therefore, fO2 may evolve from high to low fO2 during Earth (and other differentiated bodies) accretion. Any modeling of core formation and metal-silicate equilibrium should take these effects into account. PMID:22778438
The effects of pressure, temperature and composition on olivine-liquid exchange coefficients
NASA Astrophysics Data System (ADS)
Matzen, A. K.; Wood, B. J.
2017-12-01
It has recently been observed that there is a correlation between trace element (Ni and Mn) concentrations in olivine (ol) phenocrysts and thickness of the lithosphere on which they were erupted [1]. There are a number of potential explanations for this observation: the mantle may have interacted with the Ni-rich core; the trace element concentrations reflect presence of recycled crust in the mantle; or it arises from melting of peridotite at different temperatures (T) and pressures (P). Discriminating between these hypotheses requires accurate models of olivine-silicate liquid (liq) partitioning. The three variables that control the observed variations in experimentally-derived ol-liq partition coefficients are T, P, and the composition of the silicate liquid (and to a lesser extent the olivine composition). However, experiments cannot unambiguously disentangle the effects of these variables. For olivine-saturated liquids at constant P, any change in T results in the crystallization or dissolution of olivine and thus a change in liquid composition, resulting in a correlation between T and silicate liquid composition (note that changing the bulk composition such that olivine saturation occurs at a different T also results in a correlation with composition and T). Alternatively, P and T can be varied in concert such that liquid and olivine compositions remain approximately constant [e.g., 2], resulting in a correlation between T and P. In an attempt to resolve the conflation of T, P and compositional effects we turned to metal (met)-liq partitioning studies. Experiments show that, unlike most other elements, P has a strong effect on the partitioning of Ni between Fe-rich metal and silicate melt. Assuming that the pressure dependence of K_{D, Ni-Fe}^{met-liq} (0-25 GPa) [3] is driven primarily by the changing activities in the silicate melt, we can approximate the effect that pressure will have on K_{D, Ni-Fe}^{ol-liq} as measured by [2], using Kress and Carmichael [4] to calculate Fe3+/Fe2+. We find that the pressure effect should be a significant contributor to the observed systematics of K_{D, Ni-Fe}^{ol-liq} between 1 atm and 3 GPa [2]. [1] Sobolev et al (2007) Science, 316, 412-417, [2] Matzen et al (2017) CMP 172:3, [3] Kegler et al (2008) EPSL 268, 28-40, [4] Kress & Carmichael (1991) CMP 108, 82-92.
Geochemical study of stream waters affected by mining activities in the SE Spain
NASA Astrophysics Data System (ADS)
Garcia-Lorenzo, Maria Luz; Perez-Sirvent, Carmen; Martinez-Sanchez, Maria Jose; Bech, Jaime
2015-04-01
Water pollution by dissolved metals in mining areas has mainly been associated with the oxidation of sulphide-bearing minerals exposed to weathering conditions, resulting in low quality effluents of acidic pH and containing a high level of dissolved metals. According to transport process, three types of pollution could be established: a) Primary contamination, formed by residues placed close to the contamination sources; b) Secondary contamination, produced as a result of transport out of its production areas; c) Tertiary contamination. The aim of this work was to study trace element in water samples affected by mining activities and to apply the MINTEQ model for calculating aqueous geochemical equilibria. The studied area constituted an important mining centre for more than 2500 years, ceasing activity in 1991. The ore deposits of this zone have iron, lead and zinc as the main metal components. As a result, a lot of contaminations sources, formed by mining steriles, waste piles and foundry residues are present. For this study, 36 surficial water samples were collected after a rain episode in 4 different areas. In these samples, the trace element content was determined by by flame atomic absorption spectrometry (Fe and Zn), electrothermal atomization atomic absorption spectrometry (Pb and Cd), atomic fluorescence spectrometry (As) and ICP-MS for Al. MINTEQA2 is a geochemical equilibrium speciation model capable of computing equilibria among the dissolved, adsorbed, solid, and gas phases in an environmental setting and was applied to collected waters. Zone A: A5 is strongly influenced by tailing dumps and showed high trace element content. In addition, is influenced by the sea water and then showed high bromide, chloride, sodium and magnesium content, together with a basic pH. The MINTEQ model application suggested that Zn and Cd could precipitate as carbonate (hidrocincite, smithsonite and otavite). A9 also showed acid pH and high trace element content; is influenced by tailing dumps and also by waters from gully watercourses, transporting materials from Sierra Minera. The MINTEQ simulation showed that Pb and Ca could precipitate as sulphates (anglesite and gypsum). Waters affected by secondary contamination have been mixed with carbonate materials, present in the zone increasing the pH. Some elements have precipitated, such as Cu and Pb, while Cd, Zn and As are soluble. The MINTEQ model results showed that in A10 and A14, Al could precipitate as diaspore but also carbonates could be formed, particularly dolomite. These model in A12 sample showed that soluble Zn could precipitate as carbonate and Al as oxyhydroxide, similarly than in A13. A2 and A6 waters are affected by tertiary contamination and showed basic pH, soluble carbonates and lower trace element content. Only Zn, Cd and Al are present. The speciation model showed that in A2, Cd and Zn could precipitate as carbonates while Al as oxihydroxide. In A6, the model suggested that soluble Pb could precipitate as carbonate (hidrocerusite and cerusite) or as hydroxide; Al as diaspore, Ca as calcite and Fe as hematite. Zone B: All waters are strongly affected by mining activities and showed acid pH, high trace element content and high content of soluble sulphates. The MINTEQ results showed that in B8, Fe could precipitate as hydroxychloride and in B12 could form alunite. In B9, B10, B13 y B14, the model estimates the precipitation of anglesite, gypsum and Fe hydroxichloride (B9 and B10), diaspore in B13 and B14, and gypsum and Fe hydroxychloride in B13. All the sampling points collected in Zone C are affected by primary contamination, because there are a lot of tailing dumps. C1 showed high trace element content because is a reception point of a lot of tailing dumps. Water samples from C3 to C8 also had acid pH and high trace element content, particularly As, Zn and Cd. In addition, they showed high soluble sulphates. C2 water showed neutral pH, soluble carbonate and low trace element content because is influenced by a stabilised tailing dump. In all samples, except C2, the MINTEQ model showed that a lot of efflorescences could be formed, mainly sulphates. Zone D: All waters collected in this zone showed acid pH and high trace element content, mainly Zn, Cd and As. MINTEQ model results showed that elements could precipitate as jarosite but also anglesite in D8 and gypsum in D9, D11 and D12. D1 is affected by secondary contamination, which showed higher pH (still acid) and lower content in soluble salts and trace elements. The MINTEQ model suggested that Al could precipitate as diaspore, gibbsite and alunite. The applied model is an appropriate tool for the analysis of waters affected by mining activities. The obtained simulations confirm natural attenuation processes.
Gholampour, Akbar; Nabizadeh, Ramin; Hassanvand, Mohammad Sadegh; Taghipour, Hasan; Rafee, Mohammad; Alizadeh, Zahra; Faridi, Sasan; Mahvi, Amir Hossein
2016-01-01
Concentration of particulate matter (PM10 and total suspended particulate (TSP)) and their elemental constituents were measured to identify the major sources of elements in urban and industrial suburban sites in Tabriz, Iran, from September 2012 to June 2013. TSP and PM10 samples were collected using high-volume samplers. Concentrations of 31 elements in aerosols and crustal soil were determined by ICPMS. The most abundant detected metals in the urban sampling sites were Al (217.5-4019.9 ng m(-3)), Fe (272.5-7658.0 ng m(-3)), Pt (4.7-1994.4 ng m(-3)), and P (13.6-2054.8 ng m(-3) (for TSP and Al (217.6-3687.3 ng m(-3)), Fe (197.1-3724.9 ng m(-3)), Pt (65.9-2054.5 ng m(-3)), and P (11.0-756.6 ng m(-3)( for PM10. In the suburban sampling site, the most abundant detected metals were Al (2083.0-9664.0 ng m(-3)), Fe (360.0-7221.5 ng m(-3)), P (229.4-870.5 ng m(-3)), and Ti (137.3-849.7 ng m(-3)) for TSP and Al (218.5-4179.6 ng m(-3)), Fe (106.3-2005.1 ng m(-3)), P (251.9-908.4 ng m(-3)), and Ba (10.6-584.9 ng m(-3)) for PM10. For the crustal soil, the most abundant detected elements included Al (60,088-60,694 ppm), Fe (19,886-20,474 ppm), Ti (894-3481 ppm), and Si (365-4246 ppm). Key emission sources were identified, and the concentrations contributed from individual sources were estimated. Enrichment factor (EF) explaining a preponderance of the variance in the data was applied to the datasets. EF calculations revealed that non-crustal trace elements were more enriched in the urban than suburban sampling sites. Results of the factor analysis on the elements showed that emissions from road traffic (involving oil and fuel combustions by vehicles, platinum group elements from vehicle exhaust, and resuspension of particulate matter from polluted soil) and construction dust from nearby construction sites and electricity generation plant were the major contributors of anthropogenic metals at ambient atmosphere in Tabriz. Results of this study elucidated the need for developing pollution control strategy, especially vehicle exhaust control, and creating green spaces around the city.
Crocetta, Valentina; Consalvo, Ada; Zappacosta, Roberta; Di Ilio, Carmine; Di Bonaventura, Giovanni
2014-01-01
Metal ions are necessary for the proper functioning of the immune system, and, therefore, they might have a significant influence on the interaction between bacteria and host. Ionic dyshomeostasis has been recently observed also in cystic fibrosis (CF) patients, whose respiratory tract is frequently colonized by Stenotrophomonas maltophilia. For the first time, here we used an inductively mass spectrometry method to perform a spatial and temporal analysis of the pattern of changes in a broad range of major trace elements in response to pulmonary infection by S. maltophilia. To this, DBA/2 mouse lungs were comparatively infected by a CF strain and by an environmental one. Our results showed that pulmonary ionomic profile was significantly affected during infection. Infected mice showed increased lung levels of Mg, P, S, K, Zn, Se, and Rb. To the contrary, Mn, Fe, Co, and Cu levels resulted significantly decreased. Changes of element concentrations were correlated with pulmonary bacterial load and markers of inflammation, and occurred mostly on day 3 post-exposure, when severity of infection culminated. Interestingly, CF strain – significantly more virulent than the environmental one in our murine model - provoked a more significant impact in perturbing pulmonary metal homeostasis. Particularly, exposure to CF strain exclusively increased P and K levels, while decreased Fe and Mn ones. Overall, our data clearly indicate that S. maltophilia modulates pulmonary metal balance in a concerted and virulence-dependent manner highlighting the potential role of the element dyshomeostasis during the progression of S. maltophilia infection, probably exacerbating the harmful effects of the loss of CF transmembrane conductance regulator function. Further investigations are required to understand the biological significance of these alterations and to confirm they are specifically caused by S. maltophilia. PMID:24586389
Shirmohammadi, Farimah; Hasheminassab, Sina; Wang, Dongbin; Saffari, Arian; Schauer, James J.; Shafer, Martin M.; Delfino, Ralph J.; Sioutas, Constantinos
2015-01-01
In this study, potential sources of water-soluble (WS) and water-insoluble (WI) fractions of metals and trace elements in coarse particulate matter (CPM) (PM10–2.5, 2.5
Barst, Benjamin D; Rosabal, Maikel; Campbell, Peter G C; Muir, Derek G C; Wang, Xioawa; Köck, Günter; Drevnick, Paul E
2016-05-01
We sampled landlocked Arctic char (Salvelinus alpinus) from four lakes (Small, 9-Mile, North, Amituk) in the Canadian High Arctic that span a gradient of mercury contamination. Metals (Hg, Se, Tl, and Fe) were measured in char tissues to determine their relationships with health indices (relative condition factor and hepatosomatic index), stable nitrogen isotope ratios, and liver histology. A subcellular partitioning procedure was employed to determine how metals were distributed between potentially sensitive and detoxified compartments of Arctic char livers from a low- and high-mercury lake (Small Lake and Amituk Lake, respectively). Differences in health indices and metal concentrations among char populations were likely related to differences in feeding ecology. Concentrations of Hg, Se, and Tl were highest in the livers of Amituk char, whereas concentrations of Fe were highest in Small and 9-Mile char. At the subcellular level we found that although Amituk char had higher concentrations of Tl in whole liver than Small Lake char, they maintained a greater proportion of this metal in detoxified fractions, suggesting an attempt at detoxification. Mercury was found mainly in potentially sensitive fractions of both Small and Amituk Lake char, indicating that Arctic char are not effectively detoxifying this metal. Histological changes in char livers, mainly in the form of melano-macrophage aggregates and hepatic fibrosis, could be linked to the concentrations and subcellular distributions of essential or non-essential metals. Copyright © 2016 Elsevier Ltd. All rights reserved.
NASA Astrophysics Data System (ADS)
Lin, Y.-C.; Tsai, C.-J.; Wu, Y.-C.; Zhang, R.; Chi, K.-H.; Huang, Y.-T.; Lin, S.-H.; Hsu, S.-C.
2014-05-01
Traffic emissions are a significant source of airborne particulate matter (PM) in ambient environments. These emissions contain high abundance of toxic metals and thus pose adverse effects on human health. Size-fractionated aerosol samples were collected from May to September 2013 by using micro-orifice uniform deposited impactor (MOUDI). Sample collection was conducted simultaneously at the inlet and outlet sites of Hsuehshan Tunnel in northern Taiwan, which is the second longest freeway tunnel (12.9 km) in Asia. Such endeavor aims to characterize the chemical constituents, size distributions, and fingerprinting ratios, as well as the emission factors of particulate metals emitted by vehicle fleets. A total of 36 metals in size-resolved aerosols were determined through inductively coupled plasma mass spectrometry. Three major groups, namely, tailpipe emissions (Zn, Pb, and V), wear debris (Cu, Cd, Fe, Ga, Mn, Mo, Sb, and Sn), and resuspended dust (Ca, Mg, K, and Rb), of airborne PM metals were categorized on the basis of the results of enrichment factor, correlation matrix, and principal component analysis. Size distributions of wear-originated metals resembled the pattern of crustal elements, which were predominated by super-micron particulates (PM1-10). By contrast, tailpipe exhaust elements such as Zn, Pb, and V were distributed mainly in submicron particles. By employing Cu as a tracer of wear abrasion, several inter-metal ratios, including Fe/Cu (14), Ba/Cu (1.05), Sb/Cu (0.16), Sn/Cu (0.10), and Ga/Cu (0.03), served as fingerprints for wear debris. Emission factor of PM10 mass was estimated to be 7.7 mg vkm-1. The metal emissions were mostly predominated in super-micron particles (PM1-10). Finally, factors that possibly affect particulate metal emissions inside Hsuehshan Tunnel are discussed.
Trace metals in Antarctica related to climate change and increasing human impact.
Bargagli, R
2000-01-01
Metals are natural constituents of the abiotic and biotic components of all ecosystems, and under natural conditions they are cycled within and between the geochemical spheres--the atmosphere, lithosphere, hydrosphere, and biosphere--at quite steady fluxes. In the second half of the twentieth century, the huge increase in energy and mineral consumption determined anthropogenic emissions of several metals exceeding those from natural sources, e.g., volcanoes and windborne soil particles. In the Northern Hemisphere, the biogeochemical cycles of Pb, Cd, Zn, Cu, and other metals were significantly altered, even in Arctic regions. On the contrary, available data on trace metal concentrations in abiotic matrices from continental Antarctica, summarized in this review, suggest that the biogeochemical cycle of Pb is probably the only one that has been significantly altered by anthropogenic emissions in Antarctica and elsewhere in the Southern Hemisphere, especially in the period 1950-1975. Environmental contamination by other metals from anthropogenic sources in Antarctica itself can generally only be detected in snow samples taken within a range of a few kilometers or several hundred meters from scientific stations. Local metal pollution from human activities in Antarctica may compromise studies aimed at assessing the biogeochemical cycle of trace elements and the effects of global climate change. Thus, this review focuses on concentrations of metals in atmospheric particulate, snow, surface soils, and freshwater from the Antarctic continent and surface sediments and seawater from the Southern Ocean, which can plausibly be regarded as global background values of trace elements. These baselines are also necessary in view of the construction of new stations, the expansion of existing facilities to support research, and the growth of tourism and fisheries. Despite difficulties in making comparisons with data from other remote areas of the world, concentrations of trace metals in most samples of atmospheric particulates, snow, ice, soils, and marine sediments from Antarctica can be taken as global background levels. Comparison between the results of trace element surveys in marine waters of the Southern Ocean and in other seas is practically impossible. The upwelling or subduction of water masses, the seasonality in ice cover and in phytoplankton biomass, the low fallout of atmospheric dust, and many other peculiar characteristics of the Southern Ocean make concentrations of trace metals in surface waters quite variable in space and time. The depletion of nutrients in surface waters, which is a regular feature of many marine environments, rarely occurs in the Southern Ocean. Waters in some regions are characterized by very low concentrations of Fe and Mn, whereas in others the content of Cd is relatively high at the beginning of summer and may decrease about one order of magnitude during the phytoplankton bloom. Although in most Antarctic coastal ecosystems the input of metals from geochemical and anthropogenic sources and from long-range transport is negligible, concentrations of Cd in the waters and biota may be higher than in waters and related species of organisms from polluted coastal areas. Like the Southern Ocean, Antarctic lakes have many peculiar characteristics. They are often perennially ice covered and without outlet, and their water, which is gained only from short-term melting of snow and glaciers in summer, is lost mainly by sublimation of surface ice. Several lakes are distinctly stratified: the water under the ice may be cool, rich in oxygen, and among the cleanest and clearest of natural waters, whereas water near the bottom becomes anoxic, tepid, and richer in major and trace elements. Considering the specificity of Antarctic environments, to evaluate the extent and consequences of global changes and increasing human activities in Antarctica itself, research on the biogeochemistry of trace metals and monitoring programs
NASA Astrophysics Data System (ADS)
Helgoe, J. M.; Townsend, E.; John, S.
2014-12-01
A new method has been developed for the rapid analysis of metal concentrations and stable isotope ratios using a prepFAST automated sample processing robot. Although concentrations and isotopes are processed separately, similar methods are used for both. Initially all seawater is acidified to pH 2. Then Nobias resin with EDTA/IDA functional groups is added to either 10mL of sample for concentrations or ~1L samples for isotopes. Fe binds to the resin at low pH, and the pH is subsequently raised to allow Zn and Cd to bind. For concentration analyses, all subsequent chemistry is automated on the prepFAST including removal of seawater, rinsing of resin, and elution of resin into acid. For isotope samples these extraction techniques are performed manually, but the subsequent purification of Fe, Zn, and Cd by anion exchange chromatography is automated using the prepFAST. With these new methods, samples from the US GEOTRACES cruise GP16, in the eastern tropical South Pacific, are being analyzed. High concentrations of dissolved Fe are observed near the continental shelf and near submarine hydrothermal vents. Interestingly, isotope data show that dissolved Fe near the continental shelf generally has a δ56Fe close to 0 ‰. This δ56 Fe signature is suggestive of a non-reductive dissolution source for Fe, as Fe(II) released by reductive dissolution is typically closer to -2 ‰. Preliminary data show nutrient-type profiles for Zn and Cd, with Zn matching Si and Cd having a similar distribution to P. An increase in dissolved Zn near hydrothermal vents suggests a possible hydrothermal zinc source to the deep ocean. Continuing analysis of isotope data will reveal more about the source and biogeochemical cycling of these three chemically and biologically important trace metals throughout the eastern tropical Pacific Ocean.
High salinity volatile phases in magmatic Ni-Cu-platinum group element deposits
NASA Astrophysics Data System (ADS)
Hanley, J. J.; Mungall, J. E.
2004-12-01
The role of "deuteric" fluids (exsolved magmatic volatile phases) in the development of Ni-Cu-PGE (platinum group element) deposits in mafic-ultramafic igneous systems is poorly understood. Although considerable field evidence demonstrates unambiguously that fluids modified most large primary Ni-Cu-PGE concentrations, models which hypothesize that fluids alone were largely responsible for the economic concentration of the base and precious metals are not widely accepted. Determination of the trace element composition of magmatic volatile phases in such ore-forming systems can offer considerable insight into the origin of potentially mineralizing fluids in such igneous environments. Laser ablation ICP-MS microanalysis allows researchers to confirm the original metal budget of magmatic volatile phases and quantify the behavior of trace ore metals in the fluid phase in the absence of well-constrained theoretical or experimental predictions of ore metal solubility. In this study, we present new evidence from major deposits (Sudbury, Ontario, Canada; Stillwater Complex, Montana, U.S.A.) that compositionally distinct magmatic brines and halide melt phases were exsolved from crystallizing residual silicate melt and trapped within high-T fluid conduits now comprised of evolved rock compositions (albite-quartz graphic granite, orthoclase-quartz granophyre). Petrographic evidence demonstrates that brines and halide melts coexisted with immiscible carbonic phases at the time of entrapment (light aliphatic hydrocarbons, CO2). Brine and halide melt inclusions are rich in Na, Fe, Mn, K, Pb, Zn, Ba, Sr, Al and Cl, and homogenize by either halite dissolution at high T ( ˜450-700° C) or by melting of the salt phase (700-800° C). LA-ICPMS analyses of single inclusions demonstrate that high salinity volatile phases contained abundant base metals (Cu, Fe, Sn, Bi) and precious metals (Pt, Pd, Au, Ag) at the time of entrapment. Notably, precious metal concentrations in the inclusions are comparable to and often exceed the economic concentrations of the metals within the ores themselves. As a consequence of these results, current genetic models must be revised to consider the role played by hydrous saline melts and magmatic brines in deposit development, and the potential for interaction and competition between sulfide liquids (or PGE-bearing sulfide minerals) and hydrosaline volatiles for available PGE and Au in a crystallizing mafic igneous system must be critically evaluated.
Euhedral metallic-Fe-Ni grains in extraterrestrial samples
NASA Technical Reports Server (NTRS)
Rubin, Alan E.
1993-01-01
Metallic Fe-Ni is rare in terrestrial rocks, being largely restricted to serpentinized peridotites and volcanic rocks that assimilated carbonaceous material. In contrast, metallic Fe-Ni is nearly ubiquitous among extraterrestrial samples (i.e., meteorites, lunar rocks, and interplanetary dust particles). Anhedral grains are common. For example, in eucrites and lunar basalts, most of the metallic Fe-Ni occurs interstitially between silicate grains and thus tends to have irregular morphologies. In many porphyritic chondrules, metallic Fe-Ni and troilite form rounded blebs in the mesostasis because their precursors were immiscible droplets. In metamorphosed ordinary chondrites, metallic Fe-Ni and troilite form coarse anhedral grains. Some of the metallic Fe-Ni and troilite grains has also been mobilized and injected into fractures in adjacent silicate grains where local shock-reheating temperatures reached the Fe-FeS eutectic (988 C). In interplanetary dust particles metallic Fe-Ni most commonly occurs along with sulfide as spheroids and fragments. Euhedral metallic Fe-Ni grains are extremely rare. Several conditions must be met before such grains can form: (1) grain growth must occur at free surfaces, restricting euhedral metallic Fe-Ni grains to systems that are igneous or undergoing vapor-deposition; (2) the metal (+/-) sulfide assemblage must have an appropriate bulk composition so that taenite is the liquidus phase in igneous systems or the stable condensate phase in vapor-deposition systems; and (3) metallic Fe-Ni grains must remain underformed during subsequent compaction, thermal metamorphism, and shock. Because of these restrictions, the occurrence of euhedral metallic Fe-Ni grains in an object can potentially provide important petrogenetic information. Despite its rarity, euhedral metallic Fe-Ni occurs in a wide variety of extraterrestrial materials. Some of these materials formed in the solar nebula; others formed on parent body surfaces by meteoroid impacts.
NASA Technical Reports Server (NTRS)
Holzheid, Astrid; Grove, Timothy L.
2005-01-01
Metal-olivine Fe-Ni exchange distribution coefficients were determined at 1500 C over the pressure range of 1 to 9 GPa for solid and liquid alloy compositions. The metal alloy composition was varied with respect to the Fe/Ni ratio and the amount of dissolved carbon and sulfur. The Fe/Ni ratio of the metal phase exercises an important control on the abundance of Ni in the olivine. The Ni abundance in the olivine decreases as the Fe/Ni ratio of the coexisting metal increases. The presence of carbon (up to approx. 3.5 wt.%) and sulfur (up to approx. 7.5 wt.%) in solution in the liquid Fe-Ni-metal phase has a minor effect on the partitioning of Fe and Ni between metal and olivine phases. No pressure dependence of the Fe-Ni-metal-olivine exchange behavior in carbon- and sulfur-free and carbon- and sulfur-containing systems was found within the investigated pressure range. To match the Ni abundance in terrestrial mantle olivine, assuming an equilibrium metal-olivine distribution, a sub-chondritic Fe/Ni-metal ratio that is a factor of 17 to 27 lower than the Fe/Ni ratios in estimated Earth core compositions would be required, implying higher Fe concentrations in the core forming metal phase. A simple metal-olivine equilibrium distribution does not seem to be feasible to explain the Ni abundances in the Earth's mantle. An equilibrium between metal and olivine does not exercise a control on the problem of Ni overabundance in the Earth's mantle. The experimental results do not contradict the presence of a magma ocean at the time of terrestrial core formation, if olivine was present in only minor amounts at the time of metal segregation.
Evaluation of aquifer environment under Hazaribagh leather processing zone of Dhaka city
NASA Astrophysics Data System (ADS)
Zahid, Anwar; Balke, K.-D.; Hassan, M. Qumrul; Flegr, Matthias
2006-07-01
Hazaribagh is a densely populated area of Dhaka city where about 185 leather processing industries have been operating and discharging solid and liquid wastes directly to the low-lying areas, river and natural canals without proper treatment. The area is covered by alluvial deposits of Holocene age and is underlain by Pleistocene Madhupur clay. The Dupi Tila Formation of Mio-Pliocene age underlain by this yellowish gray to brick red clay bed serves as the main water-bearing aquifer of Dhaka city. To assess the environmental degradation as well as the groundwater environment, major anions, cations and heavy metals of water samples, heavy metals and organic carbon content of sediment samples were analyzed in this study. Analyses of tannery effluent detect high concentration of Na+, Mg2+, Cl- and SO{4/2-} followed by Ca2+, NH{4/+} and K+ with remarkable contents of some trace elements, mainly Cr, Fe, Mn, S, Ni and Pb. Higher accumulations of Cr, Al and Fe are observed in topsoil samples with significant amounts of Mn, Zn, Ni and Cu. Concentrations of ions and all the investigated trace elements of sampled groundwater were within the maximum allowable limit for drinking water of the Department of Environment, Bangladesh (DoE), and World Health Organization (WHO). However, excessive concentrations of Cr, Pb, etc., have already been reported in the shallow groundwater (10-20 m) of the area. Due to excessive withdrawal the vulnerability of groundwater contamination in deeper parts cannot be avoided for the future.
Wang, Guiqin; Wu, Yangsiqian; Lin, Yangting
2016-02-28
Nearly 99% of the total content of extraterrestrial metals is composed of Fe and Ni, but with greatly variable trace element contents. The accuracy obtained in the inductively coupled plasma mass spectrometry (ICP-MS) analysis of solutions of these samples can be significantly influenced by matrix contents, polyatomic ion interference, and the concentrations of external standard solutions. An ICP-MS instrument (X Series 2) was used to determine 30 standard solutions with different concentrations of trace elements, and different matrix contents. Based on these measurements, the matrix effects were determined. Three iron meteorites were dissolved separately in aqua regia and HNO3. Deviations due to variation of matrix contents in the external standard solutions were evaluated and the analysis results of the two digestion methods for iron meteorites were assessed. Our results show obvious deviations due to unmatched matrix contents in the external standard solutions. Furthermore, discrepancy in the measurement of some elements was found between the sample solutions prepared with aqua regia and HNO3, due to loss of chloride during sample preparation and/or incomplete digestion of highly siderophile elements in iron meteorites. An accurate ICP-MS analysis method for extraterrestrial metal samples has been established using external standard solutions with matched matrix contents and digesting the samples with HNO3 and aqua regia. Using the data from this work, the Mundrabilla iron meteorite previously classified as IAB-ung is reclassified as IAB-MG. Copyright © 2016 John Wiley & Sons, Ltd.
Effects of metal ions on the reactivity and corrosion electrochemistry of Fe/FeS nanoparticles.
Kim, Eun-Ju; Kim, Jae-Hwan; Chang, Yoon-Seok; Turcio-Ortega, David; Tratnyek, Paul G
2014-04-01
Nano-zerovalent iron (nZVI) formed under sulfidic conditions results in a biphasic material (Fe/FeS) that reduces trichloroethene (TCE) more rapidly than nZVI associated only with iron oxides (Fe/FeO). Exposing Fe/FeS to dissolved metals (Pd(2+), Cu(2+), Ni(2+), Co(2+), and Mn(2+)) results in their sequestration by coprecipitation as dopants into FeS and FeO and/or by electroless precipitation as zerovalent metals that are hydrogenation catalysts. Using TCE reduction rates to probe the effect of metal amendments on the reactivity of Fe/FeS, it was found that Mn(2+) and Cu(2+) decreased TCE reduction rates, while Pd(2+), Co(2+), and Ni(2+) increased them. Electrochemical characterization of metal-amended Fe/FeS showed that aging caused passivation by growth of FeO and FeS phases and poisoning of catalytic metal deposits by sulfide. Correlation of rate constants for TCE reduction (kobs) with electrochemical parameters (corrosion potentials and currents, Tafel slopes, and polarization resistance) and descriptors of hydrogen activation by metals (exchange current density for hydrogen reduction and enthalpy of solution into metals) showed the controlling process changed with aging. For fresh Fe/FeS, kobs was best described by the exchange current density for activation of hydrogen, whereas kobs for aged Fe/FeS correlated with electrochemical descriptors of electron transfer.
Moskovchenko, D V; Kurchatova, A N; Fefilov, N N; Yurtaev, A A
2017-05-01
The concentrations of several trace elements and iron were determined in 26 soil samples from Belyi Island in the Kara Sea (West Siberian sector of Russian Arctic). The major types of soils predominating in the soil cover were sampled. The concentrations of trace elements (mg kg -1 ) varied within the following ranges: 119-561 for Mn, 9.5-126 for Zn, 0.082-2.5 for Cd, <0.5-19.2 for Cu, <0.5-132 for Pb, 0.011-0.081 for Hg, <0.5-10.3 for Co, and 7.6-108 for Cr; the concentration of Fe varied from 3943 to 37,899 mg kg -1 . The impact of particular soil properties (pH, carbon and nitrogen contents, particle-size distribution) on metal concentrations was analyzed by the methods of correlation, cluster, and factor analyses. The correlation analysis showed that metal concentrations are negatively correlated with the sand content and positively correlated with the contents of silt and clay fractions. The cluster analysis allowed separation of the soils into three clusters. Cluster I included the soils with the high organic matter content formed under conditions of poor drainage; cluster II, the low-humus sandy soils of the divides and slopes; and cluster III, saline soils of coastal marshes. It was concluded that the geomorphic position largely controls the soil properties. The obtained data were compared with data on metal concentrations in other regions of the Russian Arctic. In general, the concentrations of trace elements in the studied soils were within the ranges typical of the background Arctic territories. However, some soils of Belyi Island contained elevated concentrations of Pb and Cd.
NASA Astrophysics Data System (ADS)
Rivaro, Paola; Luisa Abelmoschi, Maria; Grotti, Marco; Ianni, Carmela; Magi, Emanuele; Margiotta, Francesca; Massolo, Serena; Saggiomo, Vincenzo
2012-04-01
Surface water (<100 m) samples were collected from the Terra Nova Bay polynya region of the Ross Sea (Antarctica) in January 2006, with the aim of evaluating the individual and combined effects of hydrographic structure, iron and copper concentration and availability on the phytoplankton growth. The measurements were conducted within the framework of the Climatic Long Term Interaction for the Mass-balance in Antarctica (CLIMA) Project of the Programma Nazionale di Ricerca in Antartide activities. Dissolved oxygen, nutrients, phytoplankton pigments and concentration and complexation of dissolved trace metals were determined. Experimental data were elaborated by Principal Component Analysis (PCA). As a result of solar heating and freshwater inputs from melting sea-ice, the water column was strongly stratified with an Upper Mixed Layer 4-16 m deep. The integrated Chl a in the layer 0-100 m ranged from 60 mg m-2 to 235 mg m-2, with a mean value of 138 mg m-2. The pigment analysis showed that diatoms dominated the phytoplankton assemblage. Major nutrients were generally high, with the lowest concentration at the surface and they were never fully depleted. The Si:N drawdown ratio was close to the expected value of 1 for Fe-replete diatoms. We evaluated both the total and the labile dissolved fraction of Fe and Cu. The labile fraction was operationally defined by employing the chelating resin Chelex-100, which retains free and loosely bound trace metal species. The total dissolved Fe ranged from 0.48 to 3.02 nM, while the total dissolved Cu from 3.68 to 6.84 nM. The dissolved labile Fe ranged from below the detection limit (0.15 nM) to 1.22 nM, and the dissolved labile Cu from 0.31 to 1.59 nM, respectively. The labile fractions measured at 20 m were significantly lower than values in 40-100 m samples. As two stations were re-sampled 5 days later, we evaluated the short-term variability of the physical and biogeochemical properties. In particular, in a re-sampled station at 20 m, the total dissolved Fe increased and the total dissolved Cu decreased, while their labile fraction was relatively steady. As a result of the increase in total Fe, the percentage of the labile Fe decreased. An increase of the Si:N, Si:P and Si:FUCO ratios was measured also in the re-sampled station. On this basis, we speculated that a switch from a Fe-replete to a Fe-deplete condition was occurring.
Three-Dimensional Mathematical Model of Oxygen Transport Behavior in Electroslag Remelting Process
NASA Astrophysics Data System (ADS)
Huang, Xuechi; Li, Baokuan; Liu, Zhongqiu
2018-04-01
A transient three-dimensional model has been proposed to investigate the oxygen transport behavior in electroslag remelting process. The electromagnetism, heat transfer, multiphase flow, and species transport were calculated simultaneously by finite volume method. The volume of fluid approach was adopted to trace the metal-slag-air three-phase flow. Based on the necessary thermodynamics of oxygen transport behavior, a kinetic model was established to predict the mass source terms in species transport equation. The kinetic correction factor was proposed to account for the effect of the oxide scale formed on the electrode on the FeO content in slag. Finally, the effect of applied current on the oxygen transfer was studied. The predicted result agrees well with the measured data when the kinetic correction factor is set to be 0.5. The temperature distribution that affects the thermodynamics differs at the interfaces. The oxygen in air is absorbed into slag due to the oxidation at the slag/air interface. The Fe2O3 in slag and the oxide scale contribute to the increase of FeO content in slag, and the latter one plays the leading role. The oxygen transfer from slag to metal mainly occurs during the formation of the droplet at the slag/metal droplet interface. With the current increasing from 1200 to 1800 A, the oxygen content increases from 76.4 to 89.8 ppm, and then slightly declines to 89.2 ppm when the current increases to 2100 A.
Association of metals with plastic production pellets in the marine environment.
Ashton, Karen; Holmes, Luke; Turner, Andrew
2010-11-01
Plastic production pellets sampled from four beaches along a stretch of coastline (south Devon, SW England) and accompanying, loosely adhered and entrapped material removed ultrasonically have been analysed for major metals (Al, Fe, Mn) and trace metals (Cu, Zn, Pb, Ag, Cd, Co, Cr, Mo, Sb, Sn, U) following acid digestion. In most cases, metal concentrations in composite pellet samples from each site were less than but within an order of magnitude of corresponding concentrations in the pooled extraneous materials. However, normalisation of data with respect to Al revealed enrichment of Cd and Pb in plastic pellets at two sites. These observations are not wholly due to the association of pellets with fine material that is resistant to ultrasonication since new polyethylene pellets suspended in a harbour for 8 weeks accumulated metals from sea water through adsorption and precipitation. The environmental implications and potential applications of these findings are discussed. Copyright © 2010 Elsevier Ltd. All rights reserved.
NASA Astrophysics Data System (ADS)
Abdullah, M. I.; Elbaz-Poulichet, Francoise
Coastal lagoons are important marine environments for fisheries resources, wild life sanctuaries as well as many other economic activities. The Thau lagoon (at Sette, south coast of france) a major shell fisheries development in the region, receives inputs from a variety of sources namely seasonal run-off, river discharge, manmade waterways, karstic and thermal underground waters. A wide variety of material is thus added to the lagoon particularly trace metals such as Cu, Zn, Pb, Fe, Mn etc. . Metals added through karstic and thermal waters are particularly significant. Althought the lagoon covers some 75 km2, it is shallow with a maximum depth of only 9 m and with exchange with the Mediterranean being restricted along the narrow canal de Sette. Consequently, metal level can build up to quite high concentration upto x30 of that for normal seawater par- ticularly for metals such as Pb and Cu. While water exchange is severely limited, ma- jor water replacement do occur particularly during prolonged turbulent weather con- ditions with sustained onshore/offshore winds. Such episode occurred during March 2000 when it was observed that a significant proportion of the Thau lagoon was re- place by Mediterranean water. This water was characterized by it lower metal content and REE distribution. Such episodes are known to occur several times annually caus- ing significant amounts of metal-rich Thau water to discharge into the Gulf of Lion. It is concluded that such episodic exchanges constitute an important source of metals to the coastal zone and the Gulf of Lion which has been previously reported to have elevated metal levels.
Partitioning of metals in a degraded acid sulfate soil landscape: influence of tidal re-inundation.
Claff, Salirian R; Sullivan, Leigh A; Burton, Edward D; Bush, Richard T; Johnston, Scott G
2011-11-01
The oxidation and acidification of sulfidic soil materials results in the re-partitioning of metals, generally to more mobile forms. In this study, we examine the partitioning of Fe, Cr, Cu, Mn, Ni and Zn in the acidified surface soil (0-0.1 m) and the unoxidised sub-soil materials (1.3-1.5 m) of an acid sulfate soil landscape. Metal partitioning at this acidic site was then compared to an adjacent site that was previously acidified, but has since been remediated by tidal re-inundation. Differences in metal partitioning were determined using an optimised six-step sequential extraction procedure which targets the "labile", "acid-soluble", "organic", "crystalline oxide", "pyritic" and "residual" fractions. The surficial soil materials of the acidic site had experienced considerable losses of Cr, Cu, Mn and Ni compared to the underlying parent material due to oxidation and acidification, yet only minor losses of Fe and Zn. In general, the metals most depleted from the acidified surface soil materials exhibited the greatest sequestration in the surface soil materials of the tidally remediated site. An exception to this was iron, which accumulated to highly elevated concentrations in the surficial soil materials of the tidally remediated site. The "acid-soluble", "organic" and "pyritic" fractions displayed the greatest increase in metals following tidal remediation. This study demonstrates that prolonged tidal re-inundation of severely acidified acid sulfate soil landscapes leads to the immobilisation of trace metals through the surficial accumulation of iron oxides, organic material and pyrite. Copyright © 2011 Elsevier Ltd. All rights reserved.
Albers, P.H.; Camardese, M.B.
1993-01-01
The pH of lake water is often inversely correlated with concentrations of trace metals in the water column. Concentrations of Al, Cd, Ca, Cu, Fe, Hg, Pb, Mg, Mn, Ni, P, and Zn were compared in water, plants, and aquatic insects from three acidified (pH 5.0) and three nonacidified (pH 6.5) constructed wetlands. Concentrations of Zn in water and bur-reed (Sparganium americanum) were higher in acidified wetlands than in nonacidified wetlands. Floating nonrooted plants contained mean concentrations of Fe, Mg, and Mn that were higher than recommended maximum levels for poultry feed. The mean concentrations of all metals in insects were below recommended maximum levels for poultry feed and below levels that cause toxic effects in wild birds. Smaller than expected increases of metal concentrations in the water of acidified wetlands were probably due to limited mobilization of metals from the sediments and insignificant changes in sedimentation of aqueous metals. Calcium was lower in acidified than in nonacidified wetland water, but the Ca content of insects and bur-reed was not lower. Low concentrations of Ca in aquatic insects from both groups of wetlands indicate that calcium-rich crustaceans and mollusks are probably important to female waterfowl and their young during the spring, when invertebrates make up the majority of the diet. Although toxic effects from metal ingestion seem to be unlikely consequences of wetland acidification, the adverse effect of low pH on the occurrence of crustaceans and mollusks could threaten egg production and development of young.
The Influence of Oxygen and Sulfur on Uranium Partitioning Into the Core
NASA Astrophysics Data System (ADS)
Moore, R. D., Jr.; Van Orman, J. A.; Hauck, S. A., II
2017-12-01
Uranium, along with K and Th, may provide substantial long-term heating in planetary cores, depending on the magnitude of their partitioning into the metal during differentiation. In general, non-metallic light elements are known to have a large influence on the partitioning of trace elements, and the presence of sulfur is known to enhance the partitioning of uranium into the metal. Data from the steelmaking literature indicate that oxygen also enhances the solubility of oxygen in liquid iron alloys. Here we present experimental data on the partitioning of U between immiscible liquids in the Fe-S-O system, and use these data along with published metal-silicate partitioning data to calibrate a quantitative activity model for U in the metal. We also determined partition coefficients for Th, K, Nb, Nd, Sm, and Yb, but were unable to fully constrain activity models for these elements with available data. A Monte Carlo fitting routine was used to calculate U-S, U-O, and U-S-O interaction coefficients, and their associated uncertainties. We find that the combined interaction of uranium with sulfur and oxygen is predominant, with S and O together enhancing the solubility of uranium to a far greater degree than either element in isolation. This suggests that uranium complexes with sulfite or sulfate species in the metal. For a model Mars core composition containing 14 at% S and 5 at% O, the metal/silicate partition coefficient for U is predicted to be an order of magnitude larger than for a pure Fe-Ni core.
Analysis of biological materials using a nuclear microprobe
NASA Astrophysics Data System (ADS)
Mulware, Stephen Juma
The use of nuclear microprobe techniques including: Particle induced x-ray emission (PIXE) and Rutherford backscattering spectrometry (RBS) for elemental analysis and quantitative elemental imaging of biological samples is especially useful in biological and biomedical research because of its high sensitivity for physiologically important trace elements or toxic heavy metals. The nuclear microprobe of the Ion Beam Modification and Analysis Laboratory (IBMAL) has been used to study the enhancement in metal uptake of two different plants. The roots of corn (Zea mays) have been analyzed to study the enhancement of iron uptake by adding Fe (II) or Fe(III) of different concentrations to the germinating medium of the seeds. The Fe uptake enhancement effect produced by lacing the germinating medium with carbon nanotubes has also been investigated. The aim of this investigation is to ensure not only high crop yield but also Fe-rich food products especially from calcareous soil which covers 30% of world's agricultural land. The result will help reduce iron deficiency anemia, which has been identified as the leading nutritional disorder especially in developing countries by the World Health Organization. For the second plant, Mexican marigold (Tagetes erecta ), the effect of an arbuscular mycorrhizal fungi (Glomus intraradices ) for the improvement of lead phytoremediation of lead contaminated soil has been investigated. Phytoremediation provides an environmentally safe technique of removing toxic heavy metals (like lead), which can find their way into human food, from lands contaminated by human activities like mining or by natural disasters like earthquakes. The roots of Mexican marigold have been analyzed to study the role of arbuscular mycorrhizal fungi in enhancement of lead uptake from the contaminated rhizosphere.
Bhasmas: unique ayurvedic metallic-herbal preparations, chemical characterization.
Kumar, A; Nair, A G C; Reddy, A V R; Garg, A N
2006-03-01
Bhasmas are unique Ayurvedic metallic preparations with herbal juices/fruits, known in the Indian subcontinent since the seventh century BC and widely recommended for treatment of a variety of chronic ailments. Twenty bhasmas based on calcium, iron, zinc, mercury, silver, potassium, arsenic, copper, tin, and gemstones were analyzed for up to 18 elements by instrumental neutron activation analysis, including their C, H, N, and S contents. In addition to the major constituent element found at % level, several other essential elements such as Na, K, Ca, Mg, V, Mn, Fe, Cu, and Zn have also been found in microg/g amounts and ultratrace (ng/g) amounts of Au and Co. These seem to remain chelated with organic ligands derived from medicinal herbs. The bhasmas are biologically produced nanoparticles and are taken along with milk, butter, honey, or ghee (a preparation from milk); thus, this makes these elements easily assimilable, eliminating their harmful effects and enhancing their biocompatibility. Siddha Makaradhwaja, a mercury preparation is found to be stoichiometrically HgS without any traces of any other element. Similarly, Swet Parpati is stoichiometrically KNO3 but is found to have Mn, Cu, Zn, Na, P, and Cl as well. An attempt has been made to correlate the metallic contents with their medicinal importance. Na and K, the two electrolytic elements, seem to be well correlated, although K/Na varies in a wide range from 0.06 to 95, with specifically low values for Ca-, Fe-, and Zn-based bhasmas. K/P also varies in a wide range from 0.23 to 12, although for most bhasmas (n = 12), it is 2.3 +/- 1.2. Further, Fe/Mn is linearly correlated (r = 0.96) with Fe in nine noniron bhasmas.
NASA Astrophysics Data System (ADS)
Cheriyan, Eldhose; Sreekanth, Athira; Mrudulrag, S. K.; Sujatha, C. H.
2015-10-01
The present study investigated the distribution of environmentally relevant metals and organic matter in the shelf sediments of the southeastern Arabian Sea using biogeochemical proxies for the assessment of environmental quality and trophic status. The distribution of metals in the study site followed the order: Fe>Mg>Pb>Ni>Mn>Co>Cu>Zn>Cd. High biological productivity associated with upwelling leads to significant accumulation of Cd higher than crustal abundance in the shelf region. The enrichment factor (EF) of metals demonstrate enrichment of Pb and Co which suggests the anthropogenic influence and not redox conditions. The sediment quality guidelines (SQG) in comparison with metal concentration revealed adverse effects, possibly occurring in marine benthic species. The spatial trend of metal enrichment along transects is appreciably controlled by the adsorption to fine grained sediments. The multivariate statistical analyses, such as correlations and principal component analysis (PCA) clearly indicated the control of texture, association of clay minerals in the degree of trace metal (Cd, Pb, Ni and Co) contamination from anthropogenic as well as natural sources. Low levels of Zn, preferably display scavenging by Fe/Mn metal oxides. Biochemical descriptors in sediments indicated meso-oligotrophic conditions prevailing in the summer monsoon. The ratios among various biogeochemical parameters such as total organic carbon/total nitrogen (TOC/TN<10), protein/carbohydrate (PRT/CHO<1) displayed that the organic matter deposited of marine origin which is relatively old with potentially low nutritional value. The close relationship between biochemical components and phytopigments suggest a major contribution of autochthonous phytodetritus derived organic matter. The study provides important information about sediment biogeochemistry and metal contamination from a potential fishery zone of Indian exclusive economic zone.
Multivariate analysis of selected metals in tannery effluents and related soil.
Tariq, Saadia R; Shah, Munir H; Shaheen, N; Khalique, A; Manzoor, S; Jaffar, M
2005-06-30
Effluent and relevant soil samples from 38 tanning units housed in Kasur, Pakistan, were obtained for metal analysis by flame atomic absorption spectrophotometric method. The levels of 12 metals, Na, Ca, K, Mg, Fe, Mn, Cr, Co, Cd, Ni, Pb and Zn were determined in the two media. The data were evaluated towards metal distribution and metal-to-metal correlations. The study evidenced enhanced levels of Cr (391, 16.7 mg/L) and Na (25,519, 9369 mg/L) in tannery effluents and relevant soil samples, respectively. The effluent versus soil trace metal content relationship confirmed that the effluent Cr was strongly correlated with soil Cr. For metal source identification the techniques of principal component analysis, and cluster analysis were applied. The principal component analysis yielded two factors for effluents: factor 1 (49.6% variance) showed significant loading for Ca, Fe, Mn, Cr, Cd, Ni, Pb and Zn, referring to a tanning related source for these metals, and factor 2 (12.6% variance) with higher loadings of Na, K, Mg and Co, was associated with the processes during the skin/hide treatment. Similarly, two factors with a cumulative variance of 34.8% were obtained for soil samples: factor 1 manifested the contribution from Mg, Mn, Co, Cd, Ni and Pb, which though soil-based is basically effluent-derived, while factor 2 was found associated with Na, K, Ca, Cr and Zn which referred to a tannery-based source. The dendograms obtained from cluster analysis, also support the observed results. The study exhibits a gross pollution of soils with Cr at levels far exceeding the stipulated safe limit laid down for tannery effluents.
Heavy - metal biomonitoring by using moss bags in Florence urban area, Italy
NASA Astrophysics Data System (ADS)
Pellizzaro, Grazia; Canu, Annalisa; Arca, Angelo; Duce, Pierpaolo
2013-04-01
In the last century, pollution has become one of the most important risks for environment. In particular, heavy metal presence in air, water and soil induces toxic effects on ecosystems and human health. Monitoring airborne trace element over large areas is a task not easy to reach since the concentrations of pollutants are variable in space and time. Data from automatic devices are site-specific and very limited in number to describe spatial-temporal trends of pollutants. In addition, especially in Italy, trace elements concentrations are not often recorded by most of the automated monitoring stations. In the last decades, development of alternative and complementary methods as bio-monitoring techniques, allowed to map deposition patterns not only near single pollution sources, but also over relatively large areas at municipal or even regional scale. Bio-monitoring includes a wide array of methodologies finalised to study relationships between pollution and living organisms. Mosses and lichens have been widely used as bio-accumulators for assessing the atmospheric deposition of heavy metals in natural ecosystems and urban areas. In this study bio-monitoring of airborne trace metals was made using moss bags technique. The moss Hypnum cupressiforme was used as bio-indicator for estimating atmospheric traces metal deposition in the urban area of Florence. Moss carpets were collected in a forested area of central Sardinia (municipality of Bolotana - Nuoro), which is characterised by absence of air pollution. Moss bags were located in the urban area of Florence close to three monitoring air quality stations managed by ARPAT (Agenzia Regionale Protezione Ambiente Toscana). Two stations were located in high-traffic roads whereas the other one was located in a road with less traffic density. In each site moss bags were exposed during three campaigns of measurement conducted during the periods March-April, May-July, and August-October 2010. Two moss bags, used as control, were not exposed. After exposure periods, moss bags were removed and moss samples were analyzed for As, Cr, Cu, Fe, Ni, Pb, V, and Zn by Inductively Coupled Plasma Atomic Emission Spectrometry. Results show differences between mean concentration of trace metals in moss bags after-exposure and the respective blanks in the three sample sites of Florence during the three campaigns of measurement. The highest concentrations for almost all elements were recorded at high-traffic road sites. Whereas lower values were detected in site located in a road with less traffic density In conclusion, Hypnum cupressiforme, for his high ability to accumulate trace metals, can be efficiently used as bio-indicator to estimate the trend of air pollution in a urban area during a period time.
Oxygen Oases Before and After the GOE: Insights From Metals and Models
NASA Astrophysics Data System (ADS)
Olson, S. L.; Reinhard, C. T.; Planavsky, N. J.; Lyons, T. W.; Roy, M.; Anbar, A. D.
2014-12-01
The evolution of oxygenic photosynthesis fundamentally changed the structure of the marine biosphere and the chemistry of Earth's ocean-atmosphere system. Atmospheric oxygenation, however, was decoupled from the onset of biological O2 production—possibly lagging by as much as half a billion years—and O2 remained low for two billion years following initial O2 accumulation. Although uncertainties remain regarding the fate of biogenic O2 during the Precambrian, it is becoming clear that the consequences of oxygenesis were both spatially and temporally variable. Several lines of evidence support the existence of aerobic ecosystems associated with O2 oases within an otherwise anoxic Archean ocean; however—with notable exceptions—atmospheric O2 remained low enough to severely curtail oxidative weathering processes on long-term average throughout the Archean. During the subsequent Great Oxidation Event (GOE) in the early Paleoproterozoic, atmospheric O2 irreversibly increased above the sensitivity thresholds of several well-established proxies, but the level at which O2 eventually stabilized remains unclear. Consequently, the dynamics of O2 cycling are poorly characterized both before and after the GOE. Nevertheless, recent analytical and numerical results suggest exceptionally low O2 levels that may have favored Archean-style O2 oases in the mid-Proterozoic. We used Fe speciation and trace metal records from Precambrian shales, including data from two new cores that target the 2.7 Ga Roy Hill Shale, to investigate pre- and post- GOE redox heterogeneity in Earth's surface environments. Fe speciation supports the reconstruction of local marine redox conditions, and, in this context, trace metals can allow glimpses of redox conditions beyond the local environment, which may have throttled the supply of key redox-sensitive trace metals to the ocean. Then, using O2 constraints derived from these inorganic proxies, we use an Earth System model to explore C, O, and nutrient cycling in the late Archean and into the mid-Proterozoic. Although our results allow profound perturbation to several biogeochemical cycles and the climate system as a result of the GOE, we find that the GOE may have had only minor significance for the long-term average O2 content of typical surface seawater in the Proterozoic.
Löpez-Alonso, Marta; Miranda, Marta; García-Partida, Paulino; Mendez, Adriana; Castillo, Cristina; Benedito, José Luis
2007-05-01
The aim of this study was to provide data on the main toxic and trace metals in the liver and kidney of domestic dogs in Galicia, NW Spain and to evaluate the influence of diet, sex, age, and pathological lesions on metal accumulation. Samples of the liver and kidney from 77 male and female dogs, aged between 6 mo and 18 yr, were collected during ordinary necropsy. Samples were acid-digested and metal concentrations determined by inductively coupled plasma (ICP)-mass spectrometry and ICP-atomic emission spectrometry. Mean toxic metal concentrations (geometric means for liver and kidney respectively) were 11.5 and 15.8 microg/kg wet weight for As, 56.3 and 166 microg/kg for Cd, 32.7 and 51.9 microg/kg for Hg, and 60.1 and 23.6 microg/kg for Pb. For the trace metals, these concentrations were respectively 16.3 and 21.0 microg/kg for Co, 57.6 and 43.9 microg/kg for Cr, 42.1 and 5.95 mg/kg for Cu, 394 mg/kg and 95.7 mg/kg for Fe, 2.39 and 0.956 mg/kg for Mn, 0.522 and 0.357 mg/kg for Mo, 23.8 and 26.8 microg/kg for Ni, 0.686 and 1.39 mg/kg for Se, and 46.7 and 26.0 mg/kg for Zn. Cd concentrations in the kidney significantly increased with age, and Co concentrations in the liver and kidney significantly decreased with age. Hepatic Pb concentrations were significantly higher in growing (<1 yr) and old (>10 yr) dogs. Animals with pathological lesions showed significantly higher Co and lower Mn and Zn concentrations in liver than animals without macroscopic abnormalities. Dogs that received commercial diets in general showed low variability in hepatic mineral status compared to animals that receive homemade feeds or a mixture of commercial and homemade feeds.
Althaf Hussain, Shaik; Kareem, Mohammed Abdul; Rasool, Shaik Nayab; Al Omar, Suliman Yousef; Saleh, Alwasel; Al-Fwuaires, Manal Abdulrahman; Daddam, Jayasimha Rayalu; Devi, Kodidhela Lakshmi
2018-01-01
The trace elements and minerals in Terminalia pallida fruit ethanolic extract (TpFE) were determined by the instrument inductively coupled plasma-mass spectrometry (ICP-MS), and the cardioprotection of TpFE against isoproterenol (ISO)-administered rats was studied. Rats were pretreated with TpFE (100, 300, and 500 mg/kg bw) for 30 days, with concurrent administration of ISO (85 mg/kg bw) for two consecutive days. The levels of trace elements and minerals in TpFE were below the permitted limits of World Health Organization standards. ISO administration significantly increased the heart weight and cardiac marker enzymes in serum, xanthine oxidase, sodium, and calcium in the heart, whereas significantly decreased body weight, reduced glutathione, glutathione-S-transferase, superoxide dismutase, and potassium in the heart. Oral pretreatment of TpFE significantly prevented the ISO-induced alterations. This is the first report that revealed the determination of trace elements and mineral nutrients of TpFE by ICP-MS which plays a principal role in the herbal drug discovery for the treatment of cardiovascular diseases.
Trace element contaminants in mineral fertilizers used in Iran.
Latifi, Zahra; Jalali, Mohsen
2018-05-25
The application of mineral fertilizers which have contaminants of trace elements may impose concern regarding the entry and toxic accumulation of these elements in agro-ecosystems. In this study, 57 mineral fertilizers (nitrogen, potassium, phosphate, and compound fertilizers) distributed in Iran were analyzed for their contents of Cd, Co, Cr, Cu, Mn, Ni, Pb, Zn, and Fe. The results revealed that the contents of these trace elements varied considerably depending on the type of the element and the fertilizer. Among these elements, Fe displayed the highest average content, whereas Cd showed the lowest. Generally, the trace element contents in P-containing fertilizers were higher than those in nitrogen and potassium fertilizers. The mean values of trace elements (mg kg -1 ) in P-containing fertilizers were 4.0 (Cd), 5.5 (Co), 35.7 (Cr), 24.4 (Cu), 272 (Mn), 14.3 (Ni), 6.0 (Pb), 226 (Zn), and 2532 (Fe). Comparing trace element contents to limit values set by the German Fertilizer Ordinance showed that the mean contents of potentially toxic trace elements, such as Cd and Pb, were lower than their limit values in all groups of fertilizers. On the other hand, while a number of fertilizers contained a high content of some essential trace elements, particularly Fe, they were not labeled as such.
Sources and Chemical Composition of Atmospheric Fine Particles in Rabigh, Saudi Arabia
NASA Astrophysics Data System (ADS)
Nayebare, S. R.; Aburizaiza, O. S.; Siddique, A.; Hussain, M. M.; Zeb, J.; Khwaja, H. A.
2014-12-01
Air pollution research in Saudi Arabia and the whole of Middle East is at its inception, making air pollution in the region a significant problem. This study presents the first detailed data on fine particulate matter (PM2.5) concentrations of Black Carbon (BC), ions, and trace metals at Rabigh, Saudi Arabia, and assesses their sources. Results showed several characteristic aspects of air pollution at Rabigh. Daily levels of PM2.5 and BC showed significant temporal variability ranging from 12.2 - 75.9 µg/m3 and 0.39 - 1.31 µg/m3, respectively. More than 90% of the time, the daily PM2.5 exceeded the 24 h WHO guideline of 20 µg/m3. Sulfate, NO3-, and NH4+ dominated the identifiable components. Trace metals with significantly higher concentrations included Si, S, Ca, Al, Fe, Na, Cl, Mg, K, and Ti, with average concentrations of 3.1, 2.2, 1.6, 1.2, 1.1, 0.7, 0.7, 0.5, 0.4 and 0.1 µg/m3, respectively. Based on the Air Quality Index (AQI), there were 44% days of moderate air quality, 33% days of unhealthy air quality for sensitive groups, and 23% days of unhealthy air quality throughout the study period. Two categories of aerosol trace metal sources were defined: anthropogenic (S, V, Cr, Ni, Cu, Zn, Br, Cd, Sb, and Pb) and naturally derived elements (Si, Al, and Fe). The extent of anthropogenic contribution was estimated by the degree of enrichment of these elements compared to the crustal composition. Soil resuspension and/or mobilization is an important source of "natural" elements, while "anthropogenic" elements originate primarily from fossil fuel combustion and industries. Ni and V correlated strongly pointing to combustion of heavy fuel oil as the likely source. A positive matrix factorization (PMF) was used to obtain information about possible sources. Our study highlights the need for stringent laws on PM2.5 emission control to protect human health and the environment.
NASA Astrophysics Data System (ADS)
Wittmann, H.; von Blanckenburg, F.; Mohtadi, M.; Christl, M.; Bernhardt, A.
2017-12-01
Meteoric 10Be to stable 9Be ratios combine a cosmogenic nuclide produced in the atmosphere at a rate known from reconstructions of magnetic field strength with a stable isotope that records the present and past continental weathering and erosion flux. In seawater, the 10Be/9Be ratio provides important information on metal release from bottom sediments, called boundary exchange, and the oceanic mixing of reactive trace metals due to the inherently different sources of the two isotopes. When measured in the authigenic phase of marine sediments, the 10Be/9Be ratio allows deriving the feedbacks between erosion, weathering, and climate in the geologic past. At an ocean margin site 37°S offshore Chile, we use the 10Be/9Be ratio to trace changes in terrestrial particulate composition due to exchange with seawater. We analyzed the reactive (sequentially extracted) phase of marine surface sediments along a coast-perpendicular transect, and compared to samples from their riverine source. We find evidence for growth of authigenic rims through co-precipitation, not via reversible adsorption, that incorporate an open ocean 10Be/9Be signature from a deep water source only 30 km from the coast, thereby overprinting terrestrial riverine 10Be/9Be signatures. We show that the measured 10Be/9Be ratios in marine sediments comprise a mixture between seawater-derived and riverine-sourced phases. As 10Be/9Be ratios increase due to exchange with seawater, particulate-bound Fe concentrations increase, which we attribute to release of Fe-rich pore waters during boundary exchange in the sediment. The implications for the use of 10Be/9Be in sedimentary records for paleo-denudation flux reconstructions are that in coast-proximal sites that are neither affected by deeper water nor by narrow boundary currents, the authigenic record will be a direct recorder of terrigenous denudation of the adjacent river catchments. Hence archive location and past oceanic circulation have to be accounted for when reconstructing continental erosion and weathering, and only at open ocean sites that are fully reset by seawater global signals can be reconstructed.
NASA Astrophysics Data System (ADS)
Manoli, E.; Chelioti-Chatzidimitriou, A.; Karageorgou, K.; Kouras, A.; Voutsa, D.; Samara, C.; Kampanos, I.
2017-10-01
Harbors are often characterized by high levels of air pollutants that are emitted from ship traffic and other harbor activities. In the present study, the concentrations of Polycyclic Aromatic Hydrocarbons (PAHs) and trace elements (As, Cd, Ni, Pb, Cr, Mn, Zn, and Fe) bounded to the inhalable particulate matter PM10 were studied in the harbor of Volos, central Greece, during a 2-year period (2014-2015). Seasonal and daily variations were investigated. Moreover, total carcinogenic and mutagenic activities of PAHs were calculated. The effect of major wind sectors (sea, city, industrial, harbor) was estimated to assess the potential contribution of ship traffic and harbor activities, such as scrap metal handling operations. Results showed that the harbor sector (calm winds ≤ 0.5 m s-1) was associated with the highest concentrations of PM10. The harbor sector was also associated with relatively increased levels of trace elements (As, Fe, Cr, Mn, Ni), however the effect of this sector was lower than the corresponding effect of the industrial wind sector. The sea sector showed only a slight increase in B[a]Py and Σ12PAHs, whereas the highest increasing effect for PAHs and traffic-related elements, such as Pb and Zn, was evidenced for the city sector.
NASA Astrophysics Data System (ADS)
Wade, Terry L.; Soliman, Yousra; Sweet, Stephen T.; Wolff, Gary A.; Presley, Bobby J.
2008-12-01
The concentrations of polycyclic aromatic hydrocarbons (PAHs) and trace elements were determined for surface (top 2 cm) sediment samples collected during the deep Gulf of Mexico benthos (DGoMB) study .These elements and compounds are known to be toxic to organisms at high concentrations and may affect biological communities. There is no indication of major anthropogenic input of the elements Be, Co, Cr, Fe, Si, Tl, V, K, Mg, Ca, Sr and Zn, based on normalization to Al. The concentrations of these metals in the sediment are a function of the relative amounts of trace-metal-rich Mississippi River-derived silicate material and trace-metal-poor plankton-derived carbonate. This is not true for the elements Ba, Ni, Pb, Cd, As, Cu and Mn, whose concentrations show considerable scatter when normalized to Al and a general enrichment. On a normalized basis, Mn is enriched 5-10 fold, Cu and Ni 2-3 fold and Pb 2 fold over Mississippi River-derived material. These enrichments are likely the result of remobilization of metals from depths in the sediment column where reducing conditions exist. The Ba concentrations at selected sites are higher than those of average clay-rich sediments, but are typical of sediments from near oil well platforms in the northern Gulf of Mexico. In the case of Ba, it seems likely that the enrichments, as high as a factor of 10, are due to disposal of oil well drilling mud. The Ba-enriched samples are from the three shallowest water sites in the Mississippi Trough (sites MT1, 2 and 3) and from site C1 and WC5. All are in an area of intense petroleum exploration and development. PAH concentrations are also elevated at MT1, MT3 and C1. The total PAH concentration ranged from not detected (ND) to 1033 ng/g with a mean of 140 ng/g. Even at the sites most enriched in PAHs and trace elements, the concentrations are not at the levels expected to adversely affect the biota. However, these predicted non-effects are based on research using mostly near-shore estuarine species, not on the indigenous species at the sampling sites.
Mills, Deryck J; Vitt, Stella; Strauss, Mike; Shima, Seigo; Vonck, Janet
2013-01-01
Methanogenic archaea use a [NiFe]-hydrogenase, Frh, for oxidation/reduction of F420, an important hydride carrier in the methanogenesis pathway from H2 and CO2. Frh accounts for about 1% of the cytoplasmic protein and forms a huge complex consisting of FrhABG heterotrimers with each a [NiFe] center, four Fe-S clusters and an FAD. Here, we report the structure determined by near-atomic resolution cryo-EM of Frh with and without bound substrate F420. The polypeptide chains of FrhB, for which there was no homolog, was traced de novo from the EM map. The 1.2-MDa complex contains 12 copies of the heterotrimer, which unexpectedly form a spherical protein shell with a hollow core. The cryo-EM map reveals strong electron density of the chains of metal clusters running parallel to the protein shell, and the F420-binding site is located at the end of the chain near the outside of the spherical structure. DOI: http://dx.doi.org/10.7554/eLife.00218.001 PMID:23483797
Organic matter controls of iron incorporation in growing sea ice
NASA Astrophysics Data System (ADS)
Janssens, Julie; Meiners, Klaus M.; Townsend, Ashley T.; Lannuzel, Delphine
2018-03-01
This study presents the first laboratory-controlled sea-ice growth experiment conducted under trace metal clean conditions. The role played by organic matter, in the incorporation of iron (Fe) into sea ice was investigated by means of laboratory ice-growth experiments using a titanium cold-finger apparatus. Experiments were also conducted to understand the role of extracellular polymeric substances (EPS) in the enrichment of ammonium in sea ice. Sea ice was grown from several seawater solutions containing different quantities and qualities of particulate Fe (PFe), dissolved Fe (DFe) and organic matter. Sea ice and seawater were analyzed for particulate organic carbon and nitrogen, macro-nutrients, extracellular EPS, PFe and DFe, and particulate aluminium. The experiments showed that biogenic PFe is preferentially incorporated into sea ice compared to lithogenic PFe. Furthermore, sea ice grown from ultra-violet (UV) and non-UV treated seawaters exhibits contrasting incorporation rates of organic matter and Fe. Whereas the effects of UV-treatments were not always significant, we do find indications that the type or organic matter controls the enrichment of Fe in forming sea ice.. Specifically, we come to the conclusion that the incorporation of DFe is favored by the presence of organic ligands in the source solution.
Root exudation of phytosiderophores from soil-grown wheat
Oburger, Eva; Gruber, Barbara; Schindlegger, Yvonne; Schenkeveld, Walter D C; Hann, Stephan; Kraemer, Stephan M; Wenzel, Walter W; Puschenreiter, Markus
2014-01-01
For the first time, phytosiderophore (PS) release of wheat (Triticum aestivum cv Tamaro) grown on a calcareous soil was repeatedly and nondestructively sampled using rhizoboxes combined with a recently developed root exudate collecting tool. As in nutrient solution culture, we observed a distinct diurnal release rhythm; however, the measured PS efflux was c. 50 times lower than PS exudation from the same cultivar grown in zero iron (Fe)-hydroponic culture. Phytosiderophore rhizosphere soil solution concentrations and PS release of the Tamaro cultivar were soil-dependent, suggesting complex interactions of soil characteristics (salinity, trace metal availability) and the physiological status of the plant and the related regulation (amount and timing) of PS release. Our results demonstrate that carbon and energy investment into Fe acquisition under natural growth conditions is significantly smaller than previously derived from zero Fe-hydroponic studies. Based on experimental data, we calculated that during the investigated period (21–47 d after germination), PS release initially exceeded Fe plant uptake 10-fold, but significantly declined after c. 5 wk after germination. Phytosiderophore exudation observed under natural growth conditions is a prerequisite for a more accurate and realistic assessment of Fe mobilization processes in the rhizosphere using both experimental and modeling approaches. PMID:24890330
Evaluation of digestion methods for analysis of trace metals in mammalian tissues and NIST 1577c.
Binder, Grace A; Metcalf, Rainer; Atlas, Zachary; Daniel, Kenyon G
2018-02-15
Digestion techniques for ICP analysis have been poorly studied for biological samples. This report describes an optimized method for analysis of trace metals that can be used across a variety of sample types. Digestion methods were tested and optimized with the analysis of trace metals in cancerous as compared to normal tissue as the end goal. Anthropological, forensic, oncological and environmental research groups can employ this method reasonably cheaply and safely whilst still being able to compare between laboratories. We examined combined HNO 3 and H 2 O 2 digestion at 170 °C for human, porcine and bovine samples whether they are frozen, fresh or lyophilized powder. Little discrepancy is found between microwave digestion and PFA Teflon pressure vessels. The elements of interest (Cu, Zn, Fe and Ni) yielded consistently higher and more accurate values on standard reference material than samples heated to 75 °C or samples that utilized HNO 3 alone. Use of H 2 SO 4 does not improve homogeneity of the sample and lowers precision during ICP analysis. High temperature digestions (>165 °C) using a combination of HNO 3 and H 2 O 2 as outlined are proposed as a standard technique for all mammalian tissues, specifically, human tissues and yield greater than 300% higher values than samples digested at 75 °C regardless of the acid or acid combinations used. The proposed standardized technique is designed to accurately quantify potential discrepancies in metal loads between cancerous and healthy tissues and applies to numerous tissue studies requiring quick, effective and safe digestions. Copyright © 2017 Elsevier Inc. All rights reserved.
Tabatadze, T; Zhorzholiani, L; Kherkheulidze, M; Kandelaki, E; Ivanashvili, T
2015-11-01
Our study aims evaluation of level of essential trace elements and heavy metals in the hair samples of children with autistic spectrum disorder (ASD) and identification of changes that are associated with autistic spectrum disorders. Case-control study was conducted at Child Development Center of Iashvili Children's Central Hospital (LD).We studied 60 children aged from 4 to 5 years old. The concentrations of 28 elements among (Ca,Zn, K, Fe, Cu, Se, Mn, Cr, S, Br, Cl, Co, Ag, V, Ni, Rb, Mo, Sr, Ti, Ba, Pb, As, Hg, Cd, Sb, Zr, Sn, Bi) them trace elements and toxic metals) were determined in scalp hair samples of children (n=30) with autistic spectrum disorder (ASD) and from control group of healthy children (n=30) with matched sex and age. Micro-elemental status was detected in the hair, with roentgen-fluorescence spectrometer method (Method MBИ 081/12-4502-000, Apparatus ALVAX- CIP, USA - UKRAIN) .To achieve the similarity of study and control groups, pre and postnatal as well as family and social history were assessed and similar groups were selected. Children with genetic problems, malnourished children, children from families with social problems were excluded from the study. The diagnosis of ASD were performed by pediatrician and psychologist (using M-CHAT and ADOS) according to DSM IV (Diagnostic and Statistical Manual of Mental Disorders from the American Psychiatric association) criteria. The study was statistically analyzed using computer program SPSS 19. Deficiencies of essential trace microelements revealed in both group, but there was significant difference between control and studied groups. The most deficient element was zinc (92% in target and 20% in control), then - manganese (55% and 8%) and selenium (38% and 4%). In case of cooper study revealed excess concentration of this element only in target group in 50% of cases. The contaminations to heavy metals were detected in case of lead (78% and 16), mercury (43% and 10%) and cadmium (38% and 8%). The study statistical results indicated, that deficient concentrations of trace elements such as zinc, manganese, molybdenum and selenium in hair significantly linked with ASD (Kramer's V was 0,740; 0,537; 0,333; 0,417 accordingly). In case of cooper we got excess levels of this element and this data was highly linked with autism spectrum disorder. We got high associations and significant values between of lead, mercury and cadmium concentrations and ASD. Study results indicate that there are significant differences of hair essential trace elements concentrations in children with autism spectrum disorder comparing with healthy children group. The result obtained also showed high contamination to heavy metals such as lead, mercury and cadmium in ASD children compared to healthy ones. So, our study demonstrated alteration in levels of toxic heavy metals and essential trace elements in children with autistic spectrum disorders as compared to healthy children. This suggests a possible pathophysiological role of heavy metals and trace elements in the genesis of symptoms of autism spectrum disorders.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Allouis, C.; Beretta, F.; L'Insalata, A.
2007-04-15
The combustion of heavy fuel oil for power generation is a great source of carbonaceous and inorganic particle emissions, even though the combustion technologies and their efficiency are improving. The information about the size distribution function of the particles originated by trace metals present into the fuels is not adequate. In this paper, we focused our attention the influence of emulsion oil-water on the larger distribution mode of both the carbonaceous and metallic particles. Isokinetic sampling was performed at the exhausts of flames of a low-sulphur content heavy oil and its emulsion with water produced in two large pilot plants.more » The samples were size-segregated by mean of an 8-stages Andersen impactor. Further investigation performed on the samples using electronic microscopy (SEM) coupled with X-ray analysis (EDX) evidenced the presence of solid spherical particles, plerosphere, with typical dimensions ranging between 200 nm and 2-3 {mu}m, whose atomic composition contains a large amount of the trace metals present in the parent oils (Fe, V, Ni, etc.). EDX analyses revealed that the metal concentration increases as the plerosphere dimension decreases. We also observed that the use of emulsion slightly reduce the emission of fine particles (D{sub 50} < 8 {mu}m) in the large scale plant. (author)« less
Barik, Saroja K; Muduli, Pradipta R; Mohanty, Bita; Rath, Prasanta; Samanta, Srikanta
2018-01-01
The article presents first systematic report on the concentration of selected major elements [iron (Fe) and manganese (Mn)] and minor elements [zinc (Zn), copper (Cu), chromium (Cr), lead (Pb), nickel (Ni), and cobalt (Co)] from the core sediment of Chilika Lake, India. The analyzed samples revealed higher content of Pb than the background levels in the entire study area. The extent of contamination from minor and major elements is expressed by assessing (i) the metal enrichments in the sediment through the calculations of anthropogenic factor (AF), pollution load index (PLI), Enrichment factor (EF), and geoaccumulation index (Igeo) and (ii) potential biological risks by the use of sediment quality guidelines like effect range median (ERM) and effect range low (ERL) benchmarks. The estimated indices indicated that sediment is enriched with Pb, Ni, Cr, Cu and Co. The enrichment of these elements seems to be due to the fine granulometric characteristics of the sediment with Fe and Mn oxyhydroxides being the main metal carriers and fishing boats using low grade paints, fuel, and fishing technology using lead beads fixed to fishing nets. Trace element input to the Chilika lake needs to be monitored with due emphasis on Cr and Pb contaminations since the ERM and ERL benchmarks indicated potential biological risk with these metals.
NASA Astrophysics Data System (ADS)
Lin, Y.-C.; Tsai, C.-J.; Wu, Y.-C.; Zhang, R.; Chi, K.-H.; Huang, Y.-T.; Lin, S.-H.; Hsu, S.-C.
2015-04-01
Traffic emissions are a significant source of airborne particulate matter (PM) in ambient environments. These emissions contain an abundance of toxic metals and thus pose adverse effects on human health. Size-fractionated aerosol samples were collected from May to September 2013 by using micro-orifice uniform deposited impactors (MOUDIs). Sample collection was conducted simultaneously at the inlet and outlet sites of Hsuehshan Tunnel in northern Taiwan, which is the second-longest freeway tunnel (12.9 km) in Asia. This endeavor aims to characterize the chemical constituents and size distributions, as well as fingerprinting ratios of particulate metals emitted by vehicle fleets. A total of 36 metals in size-resolved aerosols were determined through inductively coupled plasma mass spectrometry. Three major groups - namely, tailpipe emissions (Zn, Pb, and V in fine mode), wear debris (Cu, Cd, Fe, Ga, Mn, Mo, Sb, and Sn), and resuspended dust (Ca, Mg, K, and Rb) - of airborne PM metals were categorized on the basis of the results of enrichment factor, correlation matrix, and principal component analysis. Size distributions of wear-originated metals resembled the pattern of crustal elements, which were predominated by super-micron particulates (PM1-10). By contrast, tailpipe exhaust elements such as Zn, Pb, and V were distributed mainly in submicron particles. By employing Cu as a tracer of wear abrasion, several inter-metal ratios - including Fe / Cu (14), Ba / Cu (1.05), Sb / Cu (0.16), Sn / Cu (0.10), and Ga / Cu (0.03) - served as fingerprints for wear debris. However, the data set collected in this work is useful for further studies on traffic emission inventory and human health effects of traffic-related PM.
NASA Astrophysics Data System (ADS)
Yigiterhan, O.; Al-Ansari, I. S.; Abdel-Moati, M.; Murray, J. W.; Al-Ansi, M.
2016-02-01
We focus on the trace element geochemistry of particulate matter in the Exclusive Economic Zone (EEZ) of Qatar. A main goal of this research was to analyze a complete suite of trace elements on particulate matter samples from the water column from different oceanographic biogeochemical zones of the EEZ around Qatar. The sample set also includes plankton samples which are the main source of biogenic particles, dust samples which are a source of abiological particles to surface seawater and surface sediments which can be a source of resuspended particles and a sink for settling particles. The 15 metals and 2 non-metals analyzed in this study will be Al, Ti, V, Cd, Co, Cu, Fe, Mn, Ni, Pb, Zn, Mo, Ag, Ba, U and P, N. Many factors control the composition of trace elements in marine particles. Most of these are important in the EEZ of Qatar, including:1. Natural sources: These are rivers, atmospheric dust, sediment resuspension and leaks from oil beds. However, due to very limited rainfall rivers play no major role in Qatar but resuspension of shallow carbonate rich sediments and input of atmospheric dust are important due to strong currents and surrounding deserts.2. Adsorption/desorption: These chemical processes occur everywhere in the ocean and transfer metals between particles and the solution phase.3. Biological uptake: This process is likewise a universal ocean process and results in transport of metals from the solution phase to biological particles.4. Redox conditions: These are important chemical reactions in the oxic, suboxic and anoxic zones. This can be the dominant controlling mechanism in the northeastern hypoxic deeper waters of the Qatar EEZ.5. Anthropogenic sources: The eastern part of the Qatar contains numerous industrial sites, petroleum/gas platforms and refineries. There are numerous industrial sources but the main hot spots are the port of Doha and the industrial cities of Mesaieed, Khor Al-Odaid, and Ras Laffan. We aimed to determine the influence of the different current systems, water masses, and terrestrial inputs on the distribution, fractionation, and fate of trace metal contaminants and elemental pollutants. We have also observed the level of anthropogenic enrichments for some of the elements which have not been previously documented. This research should be viewed as the first stage of a complete study.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Willie, S.
1998-11-01
The report summarizes the results of the Twelfth Round Intercomparison for Trace Metals in Marine Sediments and Biological Tissues under the directive of the NOAA National Status and Trends Program. A total of forty-four participants were included in the exercise, including NOAA, USEPA, state, Austrailian, Canadian, Mexican and Argentinean laboratories. Two samples were sent by NRC to each participant, a marine sediment collected on the east coast of Canada and a freeze-dried mussel tissue. Laboratories were also asked to analyze two certified reference materials (CRMs) MESS-2 and CRM 2976. The elements to be determined were Al, Cr, Fe, Ni, Cu,more » Zn, As, Se, Ag, Cd, Sn, Hg, and Pb for both matrices, plus Be, Si, Mn, Sb, and Tl for the sediments. An accepted mean and confidence interval was calculated for each analyte in the two unknown samples, laboratory biases were identified and an overall rating of superior, good, fair or others were assigned to each laboratory.« less
Obiri-Danso, K; Adonadaga, M G; Hogarh, J N
2011-01-01
The effect of agrochemical use in agricultural activities on the drinking water quality of ground and surface water within Agogo, a prominent tomato growing area in the Ashanti region of Ghana was assessed by monitoring physicochemical parameters, trace metals and microbial quality of two water sources. Levels of contamination were greater in surface water than groundwater. Trace metal levels (mg/L) were 1.40, 0.12, 0.08 and 0.18 in surface water and 0.08, 0.10, 0.05 and 0.08 in groundwater for Fe, Pb, Zn and Cd, respectively. Lead and Cd in surface and groundwater exceeded USEPA maximum acceptable levels (MCLs) for drinking water. Bacterial indicator numbers (geometric means/100 mL) in surface water varied from 9.35 x 10⁵ to 1.57 x 10¹¹ for total coliforms, 4.15 x 10⁴ to 2.10 x 10⁷ for faecal coliforms and 2.80 x 10 to 3.25 x 10² for enterococci, but none was found in groundwater.
Emissions inventory of PM2.5 trace elements across the United States
DOE Office of Scientific and Technical Information (OSTI.GOV)
Adam Reff; Prakash V. Bhave; Heather Simon
2009-08-15
This paper presents the first National Emissions Inventory (NEI) of fine particulate matter (PM2.5) that includes the full suite of PM2.5 trace elements (atomic number >10) measured at ambient monitoring sites across the U.S. PM2.5 emissions in the NEI were organized and aggregated into a set of 84 source categories for which chemical speciation profiles are available (e.g., Unpaved Road Dust, Agricultural Soil, Wildfires). Emission estimates for ten metals classified as Hazardous Air Pollutants (HAP) were refined using data from a recent HAP NEI. All emissions were spatially gridded, and U.S. emissions maps for dozens of trace elements (e.g., Fe,more » Ti) are presented for the first time. Nationally, the trace elements emitted in the highest quantities are silicon (3.8 x 10{sup 5} ton/yr), aluminium (1.4 x 10{sup 5} ton/yr), and calcium (1.3 x 10{sup 5} ton/yr). Our chemical characterization of the PM2.5 inventory shows that most of the previously unspeciated emissions are comprised of crustal elements, potassium, sodium, chlorine, and metal-bound oxygen. Coal combustion is the largest source of S, Se, Sr, Hg and primary sulfates. This work also reveals that the largest PM2.5 sources lacking specific speciation data are off-road diesel-powered mobile equipment, road construction dust, marine vessels, gasoline-powered boats, and railroad locomotives. 28 refs., 4 figs.« less
Hopkins, D.M.
1991-01-01
Trace metals that are commonly associated with mineralization were concentrated and separated from natural water by coprecipitation with ammonium pyrollidine dithiocarbamate (APDC) and cobalt and determined by inductively coupled plasma-atomic emission spectroscopy (ICP-AES). The method is useful in hydrogeochemical surveys because it permits preconcentration near the sample sites, and selected metals are preserved shortly after the samples are collected. The procedure is relatively simple: (1) a liter of water is filtered; (2) the pH is adjusted; (3) Co chloride and APDC are added to coprecipitate the trace metals; and (4) later, the precipitate is filtered, dissolved, and diluted to 10 ml for a 100-fold concentration enrichment of the separated metals. Sb(III), As(III), Cd, Cr, Cu, Fe, Pb, Mo, Ni, Ag, V, and Zn can then be determined simultaneously by ICP-AES. In an experiment designed to measure the coprecipitation efficiency, Sb(III), Cd and Ag were recovered at 70 to 75% of their original concentration. The remaining metals were recovered at 85 to 100% of their original concentrations, however. The range for the lower limits of determination for the metals after preconcentration is 0.1 to 3.0 ??g/l. The precision of the method was evaluated by replicate analyses of a Colorado creek water and two simulated water samples. The accuracy of the method was estimated using a water reference standard (SRM 1643a) certified by the U.S. National Bureau of Standards. In addition, the method was evaluated by analyzing groundwater samples collected near a porphyry copper deposit in Arizona and by analyzing meltwater from glacier-covered areas favorable for mineralization in south-central Alaska. The results for the ICP-AES analyses compared favorably with those obtained using the sequential technique of GFAAS on the acidified but unconcentrated water samples. ICP-AES analysis of trace-metal preconcentrates for hydrogeochemical surveys is more efficient than GFAAS because a large suite of metals is simultaneously determined with acceptable analytical accuracy and precision. The proposed analytical technique can provide direct evidence of mineralization and is useful in the exploration for unknown ore deposits. ?? 1991.
Eppinger, Robert G.; Briggs, Paul H.; Dusel-Bacon, Cynthia; Giles, Stuart A.; Gough, Larry P.; Hammarstrom, Jane M.; Hubbard, Bernard E.
2007-01-01
Water samples with the lowest pH values, highest specific conductances, and highest major- and trace-element concentrations are from springs and streams within the quartz-sericite-pyrite alteration zone. Aluminum, As, Cd, Co, Cu, Fe, Mn, Ni, Pb, Y, and particularly Zn and the REEs are all found in high concentrations, ranging across four orders of magnitude. Waters collected upstream from the alteration zone have near-neutral pH values, lower specific conductances, lower metal concentrations, and measurable alkalinities. Water samples collected downstream of the alteration zone have pH values and metal concentrations intermediate between these two extremes. Stream sediments are anomalous in Zn, Pb, S, Fe, Cu, As, Co, Sb, and Cd relative to local and regional background abundances. Red Mountain Creek and its tributaries do not support, and probably never have supported, significant megascopic faunal aquatic life.
Nagarajan, R; Jonathan, M P; Roy, Priyadarsi D; Wai-Hwa, L; Prasanna, M V; Sarkar, S K; Navarrete-López, M
2013-08-15
Forty-three sediment samples were collected from the beaches of Miri City, Sarawak, Malaysia to identify the enrichment of partially leached trace metals (PLTMs) from six different tourist beaches. The samples were analyzed for PLTMs Fe, Mn, Cr, Co, Cu, Ni, Pb, Sr and Zn. The concentration pattern suggest that the southern side of the study area is enriched with Fe (1821-6097 μg g(-1)), Mn (11.57-90.22 μg g(-1)), Cr (51.50-311 μg g(-1)), Ni (18-51 μg g(-1)), Pb (8.81-84.05 μg g(-1)), Sr (25.95-140.49 μg g(-1)) and Zn (12.46-35.04 μg g(-1)). Compared to the eco-toxicological values, Cr>Effects range low (ERL), Lowest effect level (LEL), Severe effect level (SEL); Cu>Unpolluted sediments, ERL, LEL; Pb>Unpolluted sediments and Ni>ERL and LEL. Comparative results with other regions indicate that Co, Cr, Cu, Ni and Zn are higher, indicating an external input rather than natural process. Copyright © 2013 Elsevier Ltd. All rights reserved.
Transmission electron microscope studies of extraterrestrial materials
NASA Technical Reports Server (NTRS)
Keller, Lindsay P.
1995-01-01
Transmission Electron Microscopy, X-Ray spectrometry and electron-energy-loss spectroscopy are used to analyse carbon in interplanetary dust particles. Optical micrographs are shown depicting cross sections of the dust particles embedded in sulphur. Selected-area electron diffraction patterns are shown. Transmission Electron Microscope specimens of lunar soil were prepared using two methods: ion-milling and ultramicrotomy. A combination of high resolution TEM imaging and electron diffraction is used to characterize the opaque assemblages. The opaque assemblages analyzed in this study are dominated by ilmenite with lesser rutile and spinel exsolutions, and traces of Fe metal.
Chemical fractionation of metals in wetland sediments: Indiana Dunes National Lakeshore.
Dollar, N L; Souch, C J; Filippelli, G M; Mastalerz, M
2001-09-15
Tessier-type (1979) sequential extractions for heavy metals (Cd, Cr, Cu, Fe, Mn, Pb, and Zn) were conducted on sediments from two wetland sites, one inundated and the other drained, within the Indiana Dunes National Lakeshore (IDNL), NW Indiana, with the objective of (i) evaluating extraction techniques on organic-rich sediments, (ii) determining the geochemistry and mobility of potentially biotoxic trace metals in a contaminated environment, and (iii) considering the implications of different restoration strategies on the potential for heavy metal remobilization. Long and repeated extractions were needed to effectively degrade the organic-rich sediments (up to 75% of the sediment by mass). Analysis of sulfur fractionation revealed that it was predominantly sequestered along with the organically bound fraction (renamed oxidizable). Metal recovery was good with the sum of the extractant steps typically within 20% of the total metal concentration determined after total microwave digestion. Results showed metal fractionation to be both metal- and site-specific, The oxidizable fraction is dominant for Cu, Cr, and Fe (>65% of the nonresidual fraction for almost all samples) and overall is most important also for Cd and Pb. The iron/manganese oxide fraction is important for Pb, Mn, and Zn, particularly at the drained site. The carbonate bound fraction is relatively insignificant at both sites, except for Cd and Mn, although it is more important at the drained site. The exchangeable fraction is significant in the uppermost sediments at the drained site, particularly for Cd (3-24%), Pb (3-14%), and Zn (36-45%); whereas, for the inundated site, it ranged only from 0 to 1% Zn, with no detectable Cd or Pb. Chromium, Cu, and Fe exist in forms not likely to be remobilized, whereas Cd, Mn, Pb, and Zn are potentially mobile if drained wetland sites are reflooded (and pH and redox potential altered). Simple mass balance calculations illustrate the potential for the removal of approximately 84,375 kg of exchangeable Zn if currently drained sites across the IDNL are reflooded, with concentrations in water draining into Lake Michigan as high as 5 ppm.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Zhang, Fan; Parker, Jack C.; Brooks, Scott C
This study investigated sorption of uranium and technetium onto aluminum and iron hydroxides during titration of a contaminated groundwater using both Na hydroxide and carbonate as titrants. The contaminated groundwater has a low pH of 3.8 and high concentrations of NO3-, SO42-, Al, Ca, Mg, Mn, trace metals such as Ni and Co, and radionuclides such as U and Tc. During titration, most Al and Fe were precipitated out at pH above ~4.5. U as well as Tc was found to be removed from aqueous phase at pH below ~5.5, but to some extent released at higher pH values. Anmore » earlier geochemical equilibrium reaction path model that considered aqueous complexation and precipitation/dissolution reactions predicted mineral precipitation and adequately described concentration variations of Al, Fe and some other metal cations, but failed to predict sulfate, U and Tc concentrations during titration. Previous studies have shown that Fe- and Al-oxyhydroxides strongly sorb dissolved sulfate, U and Tc species. Therefore, an anion exchange model was developed for the sorption of sulfate, U and Tc onto Al and Fe hydroxides. With the additional consideration of the anion exchange reactions, concentration profiles of sulfate, U and Tc were more accurately predicted. Results of this study indicate that consideration of complex reactions such as sorption/desorption on mixed mineral phases, in addition to hydrolysis and precipitation, could improve the prediction of various contaminants during pre- and post-groundwater treatment practices.« less
Malik, Riffat Naseem; Nadeem, Muhammad
2011-12-01
Rawal Lake Reservoir is renowned for its ecological significance and is the sole source of drinking water of the third largest city of Pakistan. However, fish kill in recent years and anthropogenic impacts from human-related activities in its catchment area have resulted in deterioration of its surface water quality. This study aims to characterize spatial and temporal variations in surface water quality, identify contaminant sources, and compare their levels with quality guidelines. Surface water samples were collected from 10 sites and analyzed for 27 physicochemical parameters for a period of 2 years on a seasonal basis. Concentration of metals in surface water in pre-monsoon were in the order: Fe > Mg > Ca > Mn > Zn > Ni > Cr > Cu > Co > Pb, whereas in post-monsoon, the order of elemental concentrations was: Ca > Mg > Na > Fe > K > Zn > Cr > Li > Pb > Co > Ni > Cu > Mn > Cd. Metals (Ni, Fe, Zn, and Ca), pH, electrical conductivity (EC), dissolved oxygen (DO), chemical oxygen demand (COD), and nutrients (PO (4) (3-) , NO(3)-N, and SO (4) (2-) ) were measured higher in pre-monsoon, whereas concentration of Cu, Mn, Cr, Co, Pb, Cd, K, Na, Mg, Li, Cl(-), and NH(4)-N were recorded higher in post-monsoon. Results highlighted serious metal pollution of surface water. Mean concentration of Zn, Cd, Ni, Cu, Fe, Cr, and Pb in both seasons and Mn in post-monsoon were well above the permissible level of surface water quality criteria. Results stress the dire need to reduce heavy-metal input into the lake basin and suggest that heavy-metal contamination should be considered as an integral part of future planning and management strategies for restoration of water quality of the lake reservoir.
NASA Astrophysics Data System (ADS)
Warren, Paul H.; Rubin, Alan E.; Isa, Junko; Gessler, Nicholas; Ahn, Insu; Choi, Byeon-Gak
2014-09-01
The Northwest Africa 5738 eucrite contains a record of unprecedented geochemical complexity for a sample from the HED asteroid. It originated with a uniquely evolved (Stannern Trend) primary igneous composition, combining ultra-high bulk incompatible element and Na2O concentrations with a relatively low mg. Its bulk oxygen-isotopic composition (Δ‧17O = -0.27‰), as well as its trace element composition (e.g., Ga/Al), confirm other evidence for classification as a eucrite. Pyroxene mg equilibration, exsolution and ;cloudy; inclusions, all reflect a typical eucritic degree of thermal metamorphism. The rock contains an unprecedented array of microscopic fluid-metasomatic vein deposits. Most common are curvy microveins within pyroxene, which consist dominantly of Ca-plagioclase (typically An95, in stark contrast with the rock's An68-78 primary-igneous plagioclase), with Fe-olivine (Fo14) and Cr-spinel as additional major constituents. Likely related to these microveins are small masses of intergrown Ca-plagioclase (again roughly An95) and silica (or high-Si glass). Analyses of the microvein Cr-spinels show stoichiometry implying a significant Fe3+ content (Fe2O3 0.7-2.3 wt.%), and fO2 up to roughly IW+3; clearly elevated in comparison to the normal HED fO2 of about IW-1. The fO2 results show an anticorrelation with equilibration T (and with Mg/Fe), which suggests the parent fluid system became more oxidizing as it cooled. NWA 5738 also contains apparent secondary iron metal. The Fe-metals are very pure, with Ni consistently below an EPMA detection limit of ∼0.01 wt.%. The vein-like shapes of roughly 1/3 of the largest Fe-metals suggest origin by deposition from a fluid. The role of pyroxene exsolution as template for a denticular (sawtooth) Fe-metal edge shape, and the survival of Fo14 olivine in a rock with abundant silica and a far higher bulk mg, suggest that the most intense thermal metamorphism occurred no later than the secondary alteration. Near-complete lack of spatial association suggests that the Fe-metals formed during a distinct time period from the curvy microveins. The immediate cause of Fe-metal deposition was most plausibly (or anyway, least implausibly) an abrupt downshift in the fluid fO2. Considering the extremely evolved bulk composition, the fluid(s) may have been largely deuteric. However, more likely the main source of fluid was a nearby buried mass of volatile-rich impactor matter, such as carbonaceous chondrite, that hit the asteroid at low enough velocity to remain mostly intact. We further speculate that the abrupt drop in fluid fO2 may have been caused by a process of carbon-fueled ;smelting; (cf. ureilites), triggered by an impact-effected shift of the carbonaceous material to a changed environment, with higher T and/or lower P. These and other recent eucrite results point to a need for greater scrutiny regarding the absence of comparable alteration-veining in rocks from the lunar highland crust, a mysterious lack in view of recent evidence for abundant lunar water.
Naz, Gul Jabeen; Dong, Dandan; Geng, Yaoxiang; Wang, Yingmin; Dong, Chuang
2017-08-22
It is known that bulk metallic glasses follow simple composition formulas [cluster](glue atom) 1 or 3 with 24 valence electrons within the framework of the cluster-plus-glue-atom model. Though the relevant nearest-neighbor cluster can be readily identified from a devitrification phase, the glue atoms remains poorly defined. The present work is devoted to understanding the composition rule of Fe-(B,P,C) based multi-component bulk metallic glasses, by introducing a cluster-based eutectic liquid model. This model regards a eutectic liquid to be composed of two stable liquids formulated respectively by cluster formulas for ideal metallic glasses from the two eutectic phases. The dual cluster formulas are first established for binary Fe-(B,C,P) eutectics: [Fe-Fe 14 ]B 2 Fe + [B-B 2 Fe 8 ]Fe ≈ Fe 83.3 B 16.7 for eutectic Fe 83 B 17 , [P-Fe 14 ]P + [P-Fe 9 ]P 2 Fe≈Fe 82.8 P 17.2 for Fe 83 P 17 , and [C-Fe 6 ]Fe 3 + [C-Fe 9 ]C 2 Fe ≈ Fe 82.6 C 17.4 for Fe 82.7 C 17.3 . The second formulas in these dual-cluster formulas, being respectively relevant to devitrification phases Fe 2 B, Fe 3 P, and Fe 3 C, well explain the compositions of existing Fe-based transition metals-metalloid bulk metallic glasses. These formulas also satisfy the 24-electron rule. The proposition of the composition formulas for good glass formers, directly from known eutectic points, constitutes a new route towards understanding and eventual designing metallic glasses of high glass forming abilities.
Significance of floods in metal dynamics and export in a small agricultural catchment
NASA Astrophysics Data System (ADS)
Roussiez, Vincent; Probst, Anne; Probst, Jean-Luc
2013-08-01
High-resolution monitoring of water discharge and water sampling were performed between early October 2006 and late September 2007 in the Montoussé River, a permanent stream draining an experimental agricultural catchment in Gascogne region (SW France). Dissolved and particulate concentrations of major elements and trace metals (i.e. Al, Fe, Mn, As, Cd, Cr, Cu, Ni, Pb, Sc and Zn) were examined. Our results showed that contamination levels were deficient to moderate, as a result of sustainable agricultural practices. Regarding dynamics, metal partitioning between particulate and dissolved phases was altered during flood conditions: the particulate phase was diluted by coarser and less contaminated particles from river bottom and banks, whereas the liquid phase was rapidly enriched owing to desorption mechanisms. Soluble/reactive elements were washed-off from soils at the beginning of the rain episode. The contribution of the flood event of May 2007 (by far the most significant episode over the study period) to the annual metal export was considerable for particulate forms (72-82%) and moderate for dissolved elements (0-20%). The hydrological functioning of the Montoussé stream poses dual threat on ecosystems, the consequences of which differ from both temporal and spatial scales: (i) desorption processes at the beginning of floods induce locally a rapid enrichment (up to 3.4-fold the pre-flood signatures on average for the event of May 2007) of waters in bioavailable metals, and (ii) labile metals - enriched by anthropogenic sources - associated to particles (mainly via carbonates and Fe/Mn oxides), were predominantly transferred during floods into downstream-connected rivers.
Kuhn, M. Keshia; Neubauer, Elisabeth; Hofmann, Thilo; von der Kammer, Frank; Aiken, George R.; Maurice, Patricia A.
2015-01-01
Concentrations and distributions of metals in Suwannee River (SR) raw filtered surface water (RFSW) and dissolved organic matter (DOM) processed by reverse osmosis (RO), XAD-8 resin (for humic and fulvic acids [FA]), and XAD-4 resin (for “transphilic” acids) were analyzed by asymmetrical flow field-flow fractionation (AsFlFFF). SR samples were compared with DOM samples from Nelson's Creek (NLC), a wetland-draining stream in northern Michigan; previous International Humic Substances Society (IHSS) FA and RO samples from the SR; and an XAD-8 sample from Lake Fryxell (LF), Antarctica. Despite application of cation exchange during sample processing, all XAD and RO samples contained substantial metal concentrations. AsFlFFF fractograms allowed metal distributions to be characterized as a function of DOM component molecular weight (MW). In SR RFSW, Fe, Al, and Cu were primarily associated with intermediate to higher than average MW DOM components. SR RO, XAD-8, and XAD-4 samples from May 2012 showed similar MW trends for Fe and Al but Cu tended to associate more with lower MW DOM. LF DOM had abundant Cu and Zn, perhaps due to amine groups that should be present due to its primarily algal origins. None of the fractograms showed obvious evidence for mineral nanoparticles, although some very small mineral nanoparticles might have been present at trace concentrations. This research suggests that AsFlFFF is important for understanding how metals are distributed in different DOM samples (including IHSS samples), which may be key to metal reactivity and bioavailability.
Interaction of Fe-Al-Cr-C with the melt of an alkali metal carbonate
NASA Astrophysics Data System (ADS)
Nikitina, E. V.
2015-08-01
The interaction of an Fe-Al-Cr-C (29.5 wt % Fe, 29.35 wt % Cr, 2.56 wt % C, 38.59 wt % Al) alloy with the melt of a lithium, sodium, or potassium carbonate containing 1-5 wt % addition to a salt phase is studied by gravimetry and measuring the corrosion potential and anode polarization curves in the temperature range 500-600°C. As passivators, the substances that decrease the corrosion losses due to hardening and thickening of an oxide film (lithium, sodium, potassium hydroxides) are used. As corrosion stimulators (activators), sodium chloride, fluoride, and sulfate are used. The coalloying of iron with chromium and aluminum results in high corrosion resistance against both frontal (continuous) and local (pitting, intercrystalline) corrosion as a result of formation of chemically resistant and high-adhesion oxide layers with their participation. X-ray diffraction analysis reveals gamma aluminum oxide, spinel (alumochromite) traces, and lithium aluminate at the surface.
Islam, Aminul; Ahmad, Akil; Laskar, Mohammad Asaduddin
2015-01-01
Amberlite® XAD-16 was functionalized with p-aminobenzene sulfonic acid via an azo spacer in order to prepare a new chelating resin, which was then characterized by water regain value, hydrogen ion capacity, elemental analyses, and IR spectral and thermal studies. The maximum uptake of Cu(II), Ni(II), Zn(II), Co(II), Cr(III), Fe(III), and Pb(II) ions was observed in the pH range 4.0-6.0 with the corresponding half-loading times of 6.5, 7.0, 8.0, 9.0, 11.0, 8.5, and 16.5 min. The sorption data followed Langmuir isotherms and a pseudo-second-order model. Thermodynamic quantities, ΔH and ΔS, based on the variation of the distribution coefficient with temperature were also evaluated. High preconcentration factors of 60-100 up to a low preconcentration limit of 4.0-6.6 μg/L have been achieved for the metal ions. The validity of the method was checked by analyzing standard reference materials and recoveries of trace metals after spiking. The analytical applications of the method were explored by analyzing natural water, mango pulp, mint leaves, and fish.
Begum, Shaheen; Shah, Mohammad Tahir; Muhammad, Said; Khan, Sardar
2015-12-01
This study investigates the drinking water (groundwater and surface water) quality and potential risk assessment along mafic and ultramafic rocks in the Swat district of Khyber Pakhtunkhwa Provence, Pakistan. For this purpose, 82 groundwater and 33 surface water samples were collected and analyzed for physico-chemical parameters. Results showed that the majority of the physico-chemical parameters were found to be within the drinking water guidelines set by the World Health Organization. However, major cationic metals such as magnesium (Mg), and trace metals (TM) including iron (Fe), manganese (Mn), nickel (Ni), chromium (Cr) and cobalt (Co) showed exceeded concentrations in 13%, 4%, 2%, 20%, 20% and 55% of water samples, respectively. Health risk assessment revealed that the non-carcinogenic effects or hazard quotient values through the oral ingestion pathway of water consumption for the TM (viz., Fe, Cr and Mn) were found to be greater than 1, could result in chronic risk to the exposed population. Results of statistical analyses revealed that mafic and ultramafic rocks are the main sources of metal contamination in drinking water, especially Ni and Cr. Both Ni and Cr have toxic health effects and therefore this study suggests that contaminated sites should be avoided or treated for drinking and domestic purposes.
Andrew Fowler
2015-04-01
Analytical results for X-ray fluorescence (XRF) and inductively coupled plasma mass spectrometry (ICP-MS) measurement of major, trace and rare earth elements in drill core from geothermal wells in Reykjanes, Iceland. Total Fe was analyzed as FeO, therefore is not included under the Fe2O3 column.
Andrew Fowler
2015-05-01
Analytical results for x-ray fluorescence (XRF) and Inductively Couple Plasma Mass Spectrometry (ICP-MS) measurement of major, trace and rare earth elements in drill cuttings from geothermal wells in Reykjanes, Iceland. Total Fe was analyzed as FeO, therefore is not included under the Fe2O3 column.
Heavy Metals Induce Iron Deficiency Responses at Different Hierarchic and Regulatory Levels1[OPEN
2017-01-01
In plants, the excess of several heavy metals mimics iron (Fe) deficiency-induced chlorosis, indicating a disturbance in Fe homeostasis. To examine the level at which heavy metals interfere with Fe deficiency responses, we carried out an in-depth characterization of Fe-related physiological, regulatory, and morphological responses in Arabidopsis (Arabidopsis thaliana) exposed to heavy metals. Enhanced zinc (Zn) uptake closely mimicked Fe deficiency by leading to low chlorophyll but high ferric-chelate reductase activity and coumarin release. These responses were not caused by Zn-inhibited Fe uptake via IRON-REGULATED TRANSPORTER (IRT1). Instead, Zn simulated the transcriptional response of typical Fe-regulated genes, indicating that Zn affects Fe homeostasis at the level of Fe sensing. Excess supplies of cobalt and nickel altered root traits in a different way from Fe deficiency, inducing only transient Fe deficiency responses, which were characterized by a lack of induction of the ethylene pathway. Cadmium showed a rather inconsistent influence on Fe deficiency responses at multiple levels. By contrast, manganese evoked weak Fe deficiency responses in wild-type plants but strongly exacerbated chlorosis in irt1 plants, indicating that manganese antagonized Fe mainly at the level of transport. These results show that the investigated heavy metals modulate Fe deficiency responses at different hierarchic and regulatory levels and that the interaction of metals with physiological and morphological Fe deficiency responses is uncoupled. Thus, this study not only emphasizes the importance of assessing heavy metal toxicities at multiple levels but also provides a new perspective on how Fe deficiency contributes to the toxic action of individual heavy metals. PMID:28500270