Concentrations and speciation of heavy metals in sludge from nine textile dyeing plants.

PubMed

Liang, Xin; Ning, Xun-an; Chen, Guoxin; Lin, Meiqing; Liu, Jingyong; Wang, Yujie

2013-12-01

The safe disposal of sludge from textile dyeing industry requires research on bioavailability and concentration of heavy metals. In this study, concentrations and chemical speciation of heavy metals (Cd, Cr, Cu, Ni, Zn, Pb) in sludge from nine different textile dyeing plants were examined. Some physiochemical features of sludge from textile dyeing industry were determined, and a sequential extraction procedure recommended by the Community Bureau of Reference (BCR) was used to study the metal speciation. Cluster analysis (CA) and principal component analysis (PCA) were applied to provide additional information regarding differences in sludge composition. The results showed that Zn and Cu contents were the highest, followed by Ni, Cr, Cd and Pb. The concentration of Cd and Ni in some sludge samples exceeded the standard suggested for acidic soils in China (GB18918-2002). In sludge from textile dyeing plants, Pb, Cd and Cr were principally distributed in the oxidizable and residual fraction, Cu in the oxidizable fraction, Ni in all four fractions and Zn in the acid soluble/exchangeable and reducible fractions. The pH and heat-drying method affected the fractionation of heavy metals in sludge. © 2013 Elsevier Inc. All rights reserved.

Comparative characterization of sewage sludge compost and soil: Heavy metal leaching characteristics.

PubMed

Fang, Wen; Wei, Yonghong; Liu, Jianguo

2016-06-05

The leaching and accumulation of heavy metals are major concerns following the land application of sewage sludge compost (SSC). We comparatively characterized SSC, the reference soil, and the SSC amended soil to investigate their similarities and differences regarding heavy metal leaching behavior and then to evaluate the effect of SSC land application on the leaching behavior of soil. Results showed that organic matter, including both of particulate organic matter (POM) and dissolved organic matter (DOM), were critical factors influencing heavy metal leaching from both of SSC and the soil. When SSC was applied to soil at the application rate of 48t/ha, the increase of DOM content slightly enhanced heavy metal leaching from the amended soil over the applicable pH domain (6

Organochlorines in surface soil at electronic-waste wire burning sites and metal contribution evaluated using quantitative X-ray speciation

NASA Astrophysics Data System (ADS)

Fujimori, Takashi; Takigami, Hidetaka; Takaoka, Masaki

2013-04-01

Heavy metals and toxic chlorinated aromatic compounds (aromatic-Cls) such as dioxins and polychlorinated biphenyls (PCBs) are found at high concentrations and persist in surface soil at wire burning sites (WBSs) in developing countries in which various wire cables are recycled to yield pure metals. Chlorine K-edge near-edge X-ray absorption fine structure (NEXAFS) is used to detect the specific chemical form of Cl and estimate its amount using a spectrum jump in the solid phase. Quantitative X-ray speciation of Cl was applied to study the mechanisms of aromatic-Cls formation in surface soil at WBSs in Southeast Asia. Relationships between aromatic-Cls and chlorides of heavy metals were evaluated because heavy metals are promoters of the thermochemical solid-phase formation of aromatic-Cls.

Competitive adsorption of heavy metals in soil underlying an infiltration facility installed in an urban area.

PubMed

Hossain, M A; Furumai, H; Nakajima, F

2009-01-01

Accumulation of heavy metals at elevated concentration and potential of considerable amount of the accumulated heavy metals to reach the soil system was observed from earlier studies in soakaways sediments within an infiltration facility in Tokyo, Japan. In order to understand the competitive adsorption behaviour of heavy metals Zn, Ni and Cu in soil, competitive batch adsorption experiments were carried out using single metal and binary metal combinations on soil samples representative of underlying soil and surface soil at the site. Speciation analysis of the adsorbed metals was carried out through BCR sequential extraction method. Among the metals, Cu was not affected by competition while Zn and Ni were affected by competition of coexisting metals. The parameters of fitted 'Freundlich' and 'Langmuir' isotherms indicated more intense competition in underlying soil compared to surface soil for adsorption of Zn and Ni. The speciation of adsorbed metals revealed less selectivity of Zn and Ni to soil organic matter, while dominance of organic bound fraction was observed for Cu, especially in organic rich surface soil. Compared to underlying soil, the surface soil is expected to provide greater adsorption to heavy metals as well as provide greater stability to adsorbed metals, especially for Cu.

Metal speciation in landfill leachates with a focus on the influence of organic matter

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

Claret, Francis, E-mail: f.claret@brgm.fr; Tournassat, Christophe; Crouzet, Catherine

Highlights: > This study characterises the heavy-metal content in leachates collected from eight landfills in France. > Most of the metals are concentrated in the <30 kDa fraction, while Pb, Cu and Cd are associated with larger particles. > Metal complexation with OM is not sufficient to explain apparent supersaturation of metals with sulphide minerals. - Abstract: This study characterises the heavy-metal content in leachates collected from eight landfills in France. In order to identify heavy metal occurrence in the different size fractions of leachates, a cascade filtration protocol was applied directly in the field, under a nitrogen gas atmospheremore » to avoid metal oxidation. The results of analyses performed on the leachates suggest that most of the metals are concentrated in the <30 kDa fraction, while lead, copper and cadmium show an association with larger particles. Initial speciation calculations, without considering metal association with organic matter, suggest that leachate concentrations in lead, copper, nickel and zinc are super-saturated with respect to sulphur phases. Speciation calculations that account for metal complexation with organic matter, considered as fulvic acids based on C1(s) NEXAFS spectroscopy, show that this mechanism is not sufficient to explain such deviation from equilibrium conditions. It is therefore hypothesized that the deviation results also from the influence of biological activity on the kinetics of mineral phase precipitation and dissolution, thus providing a dynamic system. The results of chemical analyses of sampled fluids are compared with speciation calculations and some implications for the assessment of metal mobility and natural attenuation in a context of landfill risk assessment are discussed.« less

Metal Speciation in Landfill Leachates with a Focus on the Influence of Organic Matter

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

F Claret; C Tournassat; C Crouzet

This study characterizes the heavy-metal content in leachates collected from eight landfills in France. In order to identify heavy metal occurrence in the different size fractions of leachates, a cascade filtration protocol was applied directly in the field, under a nitrogen gas atmosphere to avoid metal oxidation. The results of analyses performed on the leachates suggest that most of the metals are concentrated in the <30 kDa fraction, while lead, copper and cadmium show an association with larger particles. Initial speciation calculations, without considering metal association with organic matter, suggest that leachate concentrations in lead, copper, nickel and zinc aremore » super-saturated with respect to sulphur phases. Speciation calculations that account for metal complexation with organic matter, considered as fulvic acids based on C1(s) NEXAFS spectroscopy, show that this mechanism is not sufficient to explain such deviation from equilibrium conditions. It is therefore hypothesized that the deviation results also from the influence of biological activity on the kinetics of mineral phase precipitation and dissolution, thus providing a dynamic system. The results of chemical analyses of sampled fluids are compared with speciation calculations and some implications for the assessment of metal mobility and natural attenuation in a context of landfill risk assessment are discussed.« less

Uranium speciation in biofilms studied by laser fluorescence techniques.

PubMed

Arnold, Thuro; Grossmann, Kay; Baumann, Nils

2010-03-01

Biofilms may immobilize toxic heavy metals in the environment and thereby influence their migration behaviour. The mechanisms of these processes are currently not understood, because the complexity of such biofilms creates many discrete geochemical microenvironments which may differ from the surrounding bulk solution in their bacterial diversity, their prevailing geochemical properties, e.g. pH and dissolved oxygen concentration, the presence of organic molecules, e.g. metabolites, and many more, all of which may affect metal speciation. To obtain such information, which is necessary for performance assessment studies or the development of new cost-effective strategies for cleaning waste waters, it is very important to develop new non-invasive methods applicable to study the interactions of metals within biofilm systems. Laser fluorescence techniques have some superior features, above all very high sensitivity for fluorescent heavy metals. An approach combining confocal laser scanning microscopy and laser-induced fluorescence spectroscopy for study of the interactions of biofilms with uranium is presented. It was found that coupling these techniques furnishes a promising tool for in-situ non-invasive study of fluorescent heavy metals within biofilm systems. Information on uranium speciation and uranium redox states can be obtained.

Fate of heavy metals during municipal solid waste incineration.

PubMed

Abanades, S; Flamant, G; Gagnepain, B; Gauthier, D

2002-02-01

A thermodynamic analysis was performed to determine whether it is suitable to predict the heavy metal (HM) speciation during the Municipal Solid Waste Incineration process. The fate of several selected metals (Cd, Pb, Zn, Cr, Hg, As, Cu, Co, Ni) during incineration was theoretically investigated. The equilibrium analysis predicted the metal partitioning during incineration and determined the impact of operating conditions (temperature and gas composition) on their speciation. The study of the gas composition influence was based on the effects of the contents of oxygen (reducing or oxidising conditions) and chlorine on the HM partitioning. The theoretical HM speciation which was calculated in a complex system representing a burning sample of Municipal Solid Waste can explain the real partitioning (obtained from literature results) of all metals among the various ashes except for Pb. Then, the results of the thermodynamic study were compared with those of characterisation of real incinerator residues, using complementary techniques (chemical extraction series and X-ray micro-analyses). These analysis were performed to determine experimentally the speciation of the three representative metals Cr, Pb, and Zn. The agreement is good for Cr and Zn but not for Pb again, which mainly shows unleachable chemical speciations in the residues. Pb tends to remain in the bottom ash whereas thermodynamics often predicts its complete volatilisation under chlorides, and thus its presence exclusively in fly ash.

Performance of Raphidocelis subcapitata exposed to heavy metal mixtures.

PubMed

Expósito, Nora; Kumar, Vikas; Sierra, Jordi; Schuhmacher, Marta; Giménez Papiol, Gemma

2017-12-01

Microalgae growth inhibition assays are candidates for referent ecotoxicological assays, and are a fundamental part in the strategy to reduce the use of fish and other animal models in aquatic toxicology. In the present work, the performance of Raphidocelis subcapitata exposed to heavy metals following standardized growth inhibition assays has been assessed in three different scenarios: 1) dilutions of single heavy metals, 2) artificial mixture of heavy metals at similar levels than those found in natural rivers and, 3) natural samples containing known mixtures of contaminants (heavy metals). Chemical speciation of heavy metals has been estimated with Eh-pH diagram and Visual MINTEQ software; heavy metal and free heavy metal ion concentrations were used as input data, together with microalgae growth inhibition, for Dr. Fit software. The final goal was to assess the suitability of the ecotoxicological test based on the growth inhibition of microalgae cultures, and the mathematic models based on these results, for regulatory and decision-making purposes. The toxicity of a given heavy metal is not only determined by its chemical speciation; other chemical and biological interaction play an important role in the final toxicity. Raphidocelis subcapitata 48h-h-EC50 for tested heavy metals (especially Cu and Zn) were in agreement with previous studies, when ion metal bioavailability was assumed to be 100%. Nevertheless, the calculated growth inhibition was not in agreement with the obtained inhibition when exposed to the artificial mixture of heavy metals or the natural sample. Interactions between heavy metal ions and the compounds of the culture media and/or the natural sample determine heavy metal bioavailability, and eventually their toxicity. More research is needed for facing the challenge posed by pollutant mixtures as they are present in natural environments, and make microalgae-based assays suitable for pollution management and regulatory purposes. Copyright © 2017 Elsevier B.V. All rights reserved.

Factors affecting fixation of heavy metals in solidified/stabilized matrix: a review.

PubMed

Malviya, Rachana; Chaudhary, Rubina

2010-07-01

In this paper, an effort has been made to understand the factors, which affect fixation of heavy metals in solidified/stabilized matrix. Various aspects related to the solidification/stabilization of different heavy metals (Ar, Ba, Cu, Cr, Pb, Zn, Hg) are reviewed. A comparative study of different binders for the fixation of each metal has also been carried out to suggest the most suitable binder, pretreatment required for the metal. Valence, speciation, pH and other factors are also considered while reviewing metal retention capacity of different matrix.

Speciation evolution of zinc and copper during pyrolysis and hydrothermal carbonization treatments of sewage sludges

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

Huang, Rixiang; Zhang, Bei; Saad, Emily M.

Thermal and hydrothermal treatments are promising techniques for sewage sludge management that can potentially facilitate safe waste disposal, energy recovery, and nutrient recovery/recycling. Content and speciation of heavy metals in the treatment products affect the potential environmental risks upon sludge disposal and/or application of the treatment products. Therefore, it is important to study the speciation transformation of heavy metals and the effects of treatment conditions. By combining synchrotron X-ray spectroscopy/microscopy analysis and sequential chemical extraction, this study systematically characterized the speciation of Zn and Cu in municipal sewage sludges and their chars derived from pyrolysis (a representative thermal treatment technique)more » and hydrothermal carbonization (HTC; a representative hydrothermal treatment technique). Spectroscopy analysis revealed enhanced sulfidation of Zn and Cu by anaerobic digestion and HTC treatments, as compared to desulfidation by pyrolysis. Overall, changes in the chemical speciation and matrix properties led to reduced mobility of Zn and Cu in the treatment products. These results provide insights into the reaction mechanisms during pyrolysis and HTC treatments of sludges and can help evaluate the environmental/health risks associated with the metals in the treatment products.« less

Characterization of typical heavy metals in pyrolysis MSWI fly ash.

PubMed

Xu, Tengtun; Wang, Li'ao; Zeng, Yunmin; Zhao, Xue; Wang, Lei; Zhan, Xinyuan; Li, Tong; Yang, Lu

2018-06-07

Thermal treatment methods are used extensively in the process of municipal solid waste incineration fly ash. However, the characterization of heavy metals during this process should be understood more clearly in order to control secondary pollution. In this paper, the content, speciation and leaching toxicity of mercury (Hg), plumbum (Pb), cadmium (Cd) and zinc (Zn) in fly ash treated under different temperatures and time were firstly analysed as pre-tests. Later, pilot-scale pyrolysis equipment was used to explore the concentration and speciation changes in the heavy metals of fly ash. Finally, the phase constitution and microstructure changes in fly ash were compared before and after pyrolysis using X-ray diffraction (XRD) and scanning electron microscope (SEM), respectively. The results showed that (a) The appropriate processing temperature was between 400°C and 450°C, and the processing time should be 1 h. (b) The stability of heavy metals in fly ash increased after pyrolysis. (c) XRD and SEM results indicated that phase constitution changed a little, but the microstructure varied to a porous structure similar to that of a coral reef after pyrolysis. These results suggest that pyrolysis could be an effective method in controlling heavy metal pollution in fly ash.

Speciation of heavy metals in different grain sizes of Jiaozhou Bay sediments: Bioavailability, ecological risk assessment and source analysis on a centennial timescale.

PubMed

Kang, Xuming; Song, Jinming; Yuan, Huamao; Duan, Liqin; Li, Xuegang; Li, Ning; Liang, Xianmeng; Qu, Baoxiao

2017-09-01

Heavy metal contamination is an essential indicator of environmental health. In this work, one sediment core was used for the analysis of the speciation of heavy metals (Cr, Mn, Ni, Cu, Zn, As, Cd, and Pb) in Jiaozhou Bay sediments with different grain sizes. The bioavailability, sources and ecological risk of heavy metals were also assessed on a centennial timescale. Heavy metals were enriched in grain sizes of < 63µm and were predominantly present in residual phases. Moreover, the mobility sequence based on the sum of the first three phases (for grain sizes of < 63µm) was Mn > Pb > Cd > Zn > Cu >Ni > Cr > As. Enrichment factors (EF) indicated that heavy metals in Jiaozhou Bay presented from no enrichment to minor enrichment. The potential ecological risk index (RI) indicated that Jiaozhou Bay had been suffering from a low ecological risk and presented an increasing trend since 1940s owing to the increase of anthropogenic activities. The source analysis indicated that natural sources were primary sources of heavy metals in Jiaozhou Bay and anthropogenic sources of heavy metals presented an increasing trend since 1940s. The principal component analysis (PCA) indicated that Cr, Mn, Ni, Cu and Pb were primarily derived from natural sources and that Zn and Cd were influenced by shipbuilding industry. Mn, Cu, Zn and Pb may originate from both natural and anthropogenic sources. As may be influenced by agricultural activities. Moreover, heavy metals in sediments of Jiaozhou Bay were clearly influenced by atmospheric deposition and river input. Copyright © 2017. Published by Elsevier Inc.

Effects of conversion of mangroves into gei wai ponds on sediment heavy metals accumulation in tidal flat estuary, South China

NASA Astrophysics Data System (ADS)

Li, R.; Qiu, G.; Chai, M.; Li, R.

2017-12-01

Gei wai ponds act as important component in mangrove ecosystem, but the conversion of mangroves into gei wai ponds and its ecological function on heavy metal accumulation is still not clear. The study quantified the sediment heavy metal concentration and speciation in gei wai pond, Avicennia marina marsh and mudflat in Futian mangrove wetlands, South China. The results showed that gei wai pond acidified the sediment and reduced its fertility due to reduced pH, electronic conductivity (EC) and total organic carbon (TOC) compared to A. marina marsh and mudflat. The concentrations of Cd, Cu, Zn and Pb at all depth in gei wai pond sediment were also lower than other sites, indicating reduced storage function on heavy metals. Multiple analysis implied that heavy metals in all sites could be attributed to anthropogenic sources, with Cr as natural and anthropogenic sources in gei wai pond. Gei wai pond sediment had lower heavy metal pollution based on multiple evaluation methods, including potential ecological risk coefficient (Eir), potential ecological risk index (RI), geo-accumulation index (Igeo), mean PEL quotients (m-PEL-q), pollution load index (PLI), mean ERM quotients (m-ERM-q) and total toxic unit (∑TU). Heavy metal speciation analysis indicated that gei wai pond improved the conversion from the immobilized Cd and Cr to the mobilized fraction. SEM-AVS analysis indicated no adverse toxicity occurred in all sites, and the role of TOC in relieving sediment heavy metal toxicity of gei wai pond is limited.

The role of arbuscular mycorrhiza on change of heavy metal speciation in rhizosphere of maize in wastewater irrigated agriculture soil.

PubMed

Huang, Yi; Tao, Shu; Chen, You-jian

2005-01-01

To understand the roles of mycorrhiza in metal speciation in the rhizosphere and the impact on increasing host plant tolerance against excessive heavy metals in soil, maize (Zea mays L.) inoculated with arbuscular mycorrhizal fungus (Glomus mosseae) was cultivated in heavy metal contaminated soil. Speciations of copper, zinc and lead in the soil were analyzed with the technique of sequential extraction. The results showed that, in comparison to the bolked soil, the exchangeable copper increased from 26% to 43% in non-infected and AM-infected rhizoshpere respectively; while other speciation (organic, carbonate and Fe-Mn oxide copper) remained constant and the organic bound zinc and lead also increased but the exchangeable zinc and lead were undetectable. The organic bound copper, zinc and lead were higher by 15%, 40% and 20%, respectively, in the rhizosphere of arbuscular mycorrhiza infected maize in comparison to the non-infected maize. The results might indicate that mycorrhiza could protect its host plants from the phytotoxicity of excessive copper, zinc and lead by changing the speciation from bio-available to the non-bio-available form. The fact that copper and zinc accumulation in the roots and shoots of mycorrhia infected plants were significantly lower than those in the non-infected plants might also suggest that mycorrhiza efficiently restricted excessive copper and zinc absorptions into the host plants. Compared to the non-infected seedlings, the lead content of infected seedlings was 60% higher in shoots. This might illustrate that mycorrhiza have a different mechanism for protecting its host from excessive lead phytotoxicity by chelating lead in the shoots.

Distribution and solid-phase speciation of toxic heavy metals of bed sediments of Bharali tributary of Brahmaputra River.

PubMed

Hoque, Raza Rafiqul; Goswami, K G; Kusre, B C; Sarma, K P

2011-06-01

Heavy metal (Fe, Mn, Zn, Cu, Ni, Pb, and Cd) concentrations and their chemical speciations were investigated for the first time in bed sediments of Bharali River, a major tributary of the Brahmaputra River of the Eastern Himalayas. Levels of Fe, Mn, Pb, and Cd in the bed sediments were much below the average Indian rivers; however, Cu and Zn exhibit levels on the higher side. Enrichment factors (EF) of all metals was greater than 1 and a higher trend of EF was seen in the abandoned channel for most metals. Pb showed maximum EF of 32 at site near an urban center. The geoaccumulation indices indicate that Bharali river is moderately polluted. The metals speciations, done by a sequential extraction regime, show that Cd, Cu, and Pb exhibit considerable presence in the exchangeable and carbonate fraction, thereby showing higher mobility and bioavailability. On the other hand, Ni, Mn, and Fe exhibit greater presence in the residual fraction and Zn was dominant in the Fe-Mn oxide phase. Inter-species correlations at three sites did not show similar trends for metal pairs indicating potential variations in the contributing sources.

Heavy metal partitioning of suspended particulate matter-water and sediment-water in the Yangtze Estuary.

PubMed

Feng, Chenghong; Guo, Xiaoyu; Yin, Su; Tian, Chenhao; Li, Yangyang; Shen, Zhenyao

2017-10-01

The partitioning of ten heavy metals (As, Cd, Co, Cr, Cu, Hg, Ni, Pb, Sb, and Zn) between the water, suspended particulate matter (SPM), and sediments in seven channel sections during three hydrologic seasons in the Yangtze Estuary was comprehensively investigated. Special attention was paid to the role of tides, influential factors (concentrations of SPM and dissolved organic carbon, and particle size), and heavy metal speciation. The SPM-water and sediment-water partition coefficients (K p ) of the heavy metals exhibited similar changes along the channel sections, though the former were larger throughout the estuary. Because of the higher salinity, the K p values of most of the metals were higher in the north branch than in the south branch. The K p values of Cd, Co, and As generally decreased from the wet season to the dry season. Both the diagonal line method and paired samples t-test showed that no specific phase transfer of heavy metals existed during the flood and ebb tides, but the sediment-water K p was more concentrated for the diagonal line method, owing to the relatively smaller tidal influences on the sediment. The partition coefficients (especially the K p for SPM-water) had negative correlations with the dissolved organic carbon (DOC) but positive correlations were noted with the particle size for most of the heavy metals in sediment. Two types of significant correlations were observed between K p and metal speciation (i.e., exchangeable, carbonate, reducible, organic, and residual fractions), which can be used to identify the dominant phase-partition mechanisms (e.g., adsorption or desorption) of heavy metals. Copyright © 2017 Elsevier Ltd. All rights reserved.

Speciation and distribution of cadmium and lead in salinized horizons of antrosols

NASA Astrophysics Data System (ADS)

Bulgariu, D.; Bulgariu, L.; Astefanei, D.

2009-04-01

The utilization of intensive technologies for the vegetable cultivation in glass houses by the administration of high doses of organic fertilizes, the supra-dimensional irrigation and the maintaining of soil at high humidity state, in special in case of vicious drainage have as result the rapid degradation of morphological, chemical and physical characteristics of soils, concretized by: (i) decrease of structural aggregates stability; (ii) more dense packing of soil; (iii) accumulation of easy soluble salts (in special at superior horizons level); (iv) limitation of organic compounds and micro-elements biodisponibility. All these determined a significant reduction of productivity and of exploitation duration of soils from glass houses. These phenomena modified continuously the dynamic of speciation processes and inter-phases distribution, of heavy metals in soils from glass houses, and can determined a non-controlled accumulation of heavy metals, in special as mobile forms with high biodisponibility. Ours studied have been performed using soil profiles drawing from Copou-glass house, Iasi (Romania). Has been followed the modification of distribution for speciation forms of cadmium and lead (two heavy metals with high toxicity degree), between hortic antrosol horizons, and between chemical-mineralogical components of this, with the progressive salinization of superior horizons, in 2007-2008 period. The separation, differentiation and determination of cadmium and lead speciation forms was done by combined solid-liquid sequential extraction (SPE) and extraction in aqueous polymer-inorganic salt two-phase systems (ABS) procedure, presented in some of ours previous studies. After extraction, the total contents of the two heavy metals and fractions from these differential bonded by mineral and organic components of hortic antrosol have been determined by atomic absorption spectrometry. The specific interaction mechanisms of Cd and Pb with organic-mineral components of soils have been estimated on the basis of Raman and FT-IR spectra, recorded for fractions obtained after each extraction step. These data were correlated with those obtained by chemical analysis and UV-VIS spectrometry, and were used for to establish the type and weight of Cd and Pb speciation forms in studied antrosol. Our studies have been show that in medium and inferior horizons of hortic antrosols, the heavy metals have a general accumulation tendency, preferential by binding on organic matter and organic-mineral complexes, components with higher abundance in such type of soils. The selectivity and complexation mechanisms are controlled by speciation forms of the two metals. This phenomenon has two important consequences, the strong fixation of heavy metals in hortic antrosol and significant modification of structure and conformation of organic macromolecules. A specific phenomenon of hortic antrosols is that the accumulation rate of heavy metals is higher than levigation rate, and the mobile forms of these have a higher biodisponibility, being relative easy assimilated by plants. The progressive salinization of superior horizons of soils from glass houses, determined a sever perturbation of equilibrium between Cd and Pb speciation forms. In consequence these will have an accentuated migration tendency in superior horizons, as complexes with inorganic ligands, with a high mobility and biodsiponibility. The accumulation of soluble salts in superior horizons, and the formation of frangipane horizon (horizon of geochemical segregation of hortic antrosols) modified the ionic strength from soil solution and the thermodynamic activity of cadmium and lead species. Under these conditions, the levigation rate of cadmium and lead is higher than the accumulation rate, which means that the migration of these metals in soil solution occurs fast and in high concentrations. Acknowledgments The authors would like to acknowledge the financial support from Romanian Ministry of Education and Research (Project PNCDI 2-D5 no. 51045/07 an Project PNCDI 2-D5 no. 52141 / 08).

Dispersion, Speciation, and Pollution Assessment of Heavy Metals Pb and Zn in Surface Sediment from Disturbed Ecosystem of Jeneberang Waters

NASA Astrophysics Data System (ADS)

Najamuddin; Surahman

2017-10-01

Surface sediments were collected from seventeen stations in Jeneberang waters (riverine, estuarine, and marine). Lead (Pb) and zinc (Zn) concentrations were determined by atomic absorption spectrometry, and the speciation of metals was obtained by a sequential extraction procedure. Dispersion of Pb and Zn were found higher in the riverine and marine samples than the estuarine samples. Following speciation, the metals were found similar composition of fraction in the riverine and estuarine samples but any different in the marine samples. The results indicated that there is a change of dispersion pattern and speciation composition of metals due to the presence of the dam that lies at the boundary between the estuary and the river. The toxicity unit was indicated low toxicity level; pollution level was in weakly to moderately polluted while the aquatic environment risk attributed were no risky to light risk.

Supercritical water treatment of heavy metal and arsenic metalloid-bioaccumulating-biomass.

PubMed

Li, Jianxin; Chen, Jinbo; Chen, Shan

2018-08-15

Hyperaccumulator biomass, as a promising resource for renewable energy that can be converted into valuable fuel productions with high conversion efficiency, must be considered as hazardous materials and be carefully treated before further reuse due to the high contents of heavy metals. In this study, Pteris vittata L., an As-hyperaccumulator biomass was treated by an effective and environmental friendly method-supercritical water gasification (SCWG) using a bench-scale batch reactor. The contents of heavy metals (Cd, Pb and Zn) and arsenic metalloid in solid, liquid and gaseous products during SCWG process were thoroughly investigated. The speciation fractions including exchangeable, reducible, oxidizable and residual fractions of each heavy metal as the proportion of the total contents in solid residue were presented and the transformations trend of these heavy metals during the SCWG process was especially demonstrated. The significant operating parameters, including reaction temperature (395-445 °C), pressure (21-27 MPa) and residence time (0-40 min) were varied to explore their effects on the contents and forms. Moreover, the environmental risks of heavy metals in solid residues were evaluated based on risk assessment code, taking into consideration the speciation fractions and bioavailability. It was highlighted that although heavy metals particularly Pb and Zn tended to accumulate in solid residues with a maximum increment of about 50% in the total content, they were mostly converted to more stable oxidizable and residual fractions, and thus the ecotoxicity and bioavailability were greatly mitigated with no obvious increase in direct toxicity fractions. Each tested heavy metal presented no or low risk to the environments after SCWG treatments, meaning that the environmental pollution levels were markedly reduced with no or low risk to the environment. This study highlights the remarkable ability of SCWG for the heavy metal stabilization. Copyright © 2018 Elsevier Inc. All rights reserved.

Defense Coastal/Estuarine Research Program (DCERP) Baseline Monitoring Plan

DTIC Science & Technology

2007-09-19

climatological stress (e.g., temperature, drought) and shorter-term air pollutant stress (oxidants and metals ). Heavy metals of fine PM have been...speciation of the fine and coarse PM fractions will allow distinction between different PM sources such as wind blown soil dust, including dust...emitting 12% of the total PM2.5 mass (U.S. EPA, 2004b). Source apportionment modeling of PM2.5 mass concentrations from 24 Speciation Defense Coastal

Arsenic speciation and heavy metal distribution in polished rice grown in Guangdong Province, Southern China.

PubMed

Ma, Li; Wang, Lin; Tang, Jie; Yang, Zhaoguang

2017-10-15

Arsenic speciation and heavy metal distributions have been investigated in locally grown rice grains from Guangdong Province, Southern China. A total of 41 polished rice grain samples were collected throughout Guangdong Province. Arsenite (As(III)), as the predominant form found in the rice, was positively correlated (p<0.01) with total As (tAs) concentration. However, the percentage of As(III) reduced while tAs concentration increased (r=-0.361, p<0.05), due to restricted accumulation and translocation of As(III) in rice grains at high level of tAs. Statistical and geostatistical analyses were applied to investigate potential origins of heavy metals in rice. Only Cd, Cu and Ni were identified as influenced by anthropogenic sources such as industrial and commercial activities. As and Pb were primarily controlled by natural occurrence. The results of health risk assessment implied that continuous intake of rice grown in Guangdong Province could cause considerably non-carcinogenic and carcinogenic risk to local inhabitants. Copyright © 2017 Elsevier Ltd. All rights reserved.

Changes in heavy metal mobility and availability from contaminated wetland soil remediated with combined biochar-compost.

PubMed

Liang, Jie; Yang, Zhaoxue; Tang, Lin; Zeng, Guangming; Yu, Man; Li, Xiaodong; Wu, Haipeng; Qian, Yingying; Li, Xuemei; Luo, Yuan

2017-08-01

The combination of biochar and compost has been proven to be effective in heavy metals contaminated wetland soil restoration. However, the influence of different proportions between biochar and compost on immobilization of heavy metals in soil has been less studied up to date. Therefore, we investigated the effect of different ratios of biochar-compost mixtures on availability and speciation distribution of heavy metals (Cd, Zn and Cu) in wetland soil. The results showed that applying all amendment combinations into wetland soil increased gradually the total organic carbon (TOC) and water-extract organic carbon (WEOC) as the compost percentage rose in biochar-composts. The higher pH was obtained in a certain biochar addition (20% and 40%) in combinations due to efficient interaction of biochar with compost. All amendments could significantly decrease availability of Cd and Zn mainly from pH change, but increase available Cu concentration as the result of increased water-extract organic carbon and high total Cu content in compost. Moreover, amendments can decrease easily exchangeable fraction and increase reducible of Cd and Zn greatly with increase of compost content in combinations, while amendments containing compost promote transformation of Cu from Fe/Mn oxide and residual fractions to organic bindings. These results demonstrate that different ratios of biochar and compost have a significant effect on availability and speciation of heavy metals in multi-metal-contaminated wetland soil. Copyright © 2017 Elsevier Ltd. All rights reserved.

Transformation and speciation of typical heavy metals in soil aquifer treatment system during long time recharging with secondary effluent: Depth distribution and combination.

PubMed

Wei, Liangliang; Wang, Kun; Noguera, Daniel R; Jiang, Junqiu; Oyserman, Ben; Zhao, Ningbo; Zhao, Qingliang; Cui, Fuyi

2016-12-01

Soil aquifer treatment (SAT) systems rely on extensive physical and biogeochemical processes in the vadose zone and aquifer for water quality improvement. In this study, the distribution, quantitative changes, as well as the speciation characteristics of heavy metals in different depth of soils of a two-year operated lab-scale SAT was explored. A majority of the heavy metals in the recharged secondary effluent were efficiently trapped by the steady-state operated SAT (removal efficiency ranged from 74.7% to 98.2%). Thus, significant accumulations of 31.7% for Cd, 15.9% for Cu, 15.3% for Zn and 8.6% for Cr were observed for the top soil after 730 d operation, leading to the concentration (in μg g -1 ) of those four heavy metals of the packed soil increased from 0.51, 46.7, 61.0 and 35.7 to 0.66, 54.2, 70.4 and 38.8, respectively. By contrast, the accumulation of Mn and Pb were quite low. The residual species were the predominant fraction of the six heavy metals (ranged for 59.8-82.4%), followed by oxidisable species. Although the Zn, Cr, Cd, Cu and Mn were efficiently bounded onto the oxide components within the soil, the percentage of the labile metal fractions (water-, acid-exchangeable and reducible metal fractions) exhibited a slight increasing after 2 Y operation. Significantly heavy metals accumulation and slightly decreasing of the proportion of the stable fractions indicated a potentially higher environmental hazard for those six heavy metals after long-term SAT operation (especially for Cu, Zn and Cd). Finally, a linear relationship between the accumulation rate of metal species and the variation of soil organic carbon concentration and water extractable organic carbon was demonstrated. Copyright © 2016 Elsevier Ltd. All rights reserved.

Source identification of eight heavy metals in grassland soils by multivariate analysis from the Baicheng-Songyuan area, Jilin Province, Northeast China.

PubMed

Chai, Yuan; Guo, Jia; Chai, Sheli; Cai, Jing; Xue, Linfu; Zhang, Qingwei

2015-09-01

The characterization of the concentration, chemical speciation and source of heavy metals in soils is an imperative for pollution monitoring and the potential risk assessment of the metals to animal and human health. A total of 154 surface horizons and 53 underlying horizons of grassland soil were collected from the Baicheng-Songyuan area in Jilin Province, Northeast China, in which the concentrations and chemical fractionations of As, Cd, Cr, Cu, Hg, Ni, Pb, and Zn were investigated. The mean concentrations of heavy metals in grassland topsoil were 7.2, 0.072, 35, 16.7, 0.014, 15.2, 18.3 and 35 mg kg(-)(1) for As, Cd, Cr, Cu, Hg, Ni, Pb and Zn, respectively, and those averaged contents were lower than their China Environmental Quality Standard values for the Soils, implying that heavy metal concentrations in the studied soils were of the safety levels. The mobility sequence of the heavy metals based on the sum of the soluble, exchangeable, carbonate-bound and humic acid-bound fractions among the seven fractions decreased in the order of Cd 50.4%)>Hg (39.8%)>Cu (26.5%)>As (19.9%)>Zn (19.1%)>Ni (15.9%)>Pb (14.1%)>Cr (4.3%), suggesting Cd and Hg may pose more potential risk of soil contamination than other metals. Multivariate statistical analysis suggested that As, Cr, Cu, Ni, Pb, Zn, Cd and Hg had the similar lithogenic sources, however, Cd and Hg were more relevant to organic matter than other heavy metals, which was confirmed by the chemical speciation analysis of the metals. The study provides a base for local authority in the studied area to monitor the long term accession of heavy metals into grassland soil. Copyright © 2015 Elsevier Ltd. All rights reserved.

Distribution of Cd, Pb, Zn and Cu and their chemical speciations in soils from a peri-smelter area in northeast China

NASA Astrophysics Data System (ADS)

Du, Ping; Xue, Nandong; Liu, Li; Li, Fasheng

2008-07-01

An exploratory study on soil contamination of heavy metals was carried out surrounding Huludao zinc smelter in Liaoning province, China. The distribution of total heavy metals and their chemical speciations were investigated. The correlations between heavy metal speciations and soil pH values in corresponding sites were also analyzed. In general, Cd, Zn, Pb, Cu and As presented a significant contamination in the area near the smelter, comparied with Environmental Quality Standards for Soils in China. The geoaccumulation index showed the degree of contamination: Cd > Zn > Pb > Cu > As. There was no obvious pollution of Cr and Ni in the studied area. The speciation analysis showed that the dominant fraction of Cd and Zn was the acid soluble fraction, and the second was the residual fraction. Pb was mostly associated with the residual fraction, which constituted more than 50% of total concentration in all samples. Cu in residual fraction accounted for a high percentage (40-80%) of total concentration, and the proportion of Cu in the oxidizable fraction is higher than that of other metals. The distribution pattern of Pb and Zn was obviously affected by soil pH. It seemed that Pb and Zn content in acid solution fraction increased with increasing soil pH values, while Cd content in acid soluble fraction accounted for more proportion in neutral and alkaline groups than acidic one. The fraction distribution patterns of Cu in three pH groups were very similar and independent of soil pH values. And the residual fraction of Cu took a predominant part (50%) of the total content.

Speciation and distribution characteristics of heavy metals and pollution assessments in the sediments of Nashina Lake, Heilongjiang, China.

PubMed

Li, Miao; Zang, Shuying; Xiao, Haifeng; Wu, Changshan

2014-05-01

Sediment core samples from Nashina Lake, Heilongjiang, China were collected using a gravity sampler. The cores were sliced horizontally at 1 cm each to determine the particle size, total concentrations and speciation of Cd, Cr, Cu, Mn, Ni, Pb, and Zn. Total concentrations of heavy metals were extracted using an acid mixture (containing hydro fluoric acid, nitric acid, and sulphuric acid) and analyzed using an inductively coupled plasma spectrometry. A sequential extraction procedure was employed to separate chemical species. Analysis of results indicate that the concentrations of heavy metals in the sediments of Nashina Lake in descending order are Mn, Cr, Zn, Pb, Ni, Cu, and Cd. The ratios of the average concentrations of four heavy metals (e.g.Cr, Cu, Ni, Zn) to their background values were >1; and those of Mn, Cd, and Pb were >1. Moreover, some toxic metals were mainly distributed in bioavailable fractions. For instance, both Cd and Mn were typically found in Acid-extractable species or Fe-Mn oxide species, and thus can be easily remobilized and enter the food chain. Finally, the analysis of geo-accumulation index showed that anthropogenic pollution levels of Cr, Cu, Mn, Ni, Zn were low, but those of Pb and Cd were at the moderate level. As both Pb and Cd are toxic metals, it is highly necessary to prohibit their transformation and accumulation in the sediments.

[Speciation Distribution and Risk Assessment of Heavy Metals in Typical Material Roof Dusts].

PubMed

Li, Dun-zhu; Guan, Yun-tao; Liu, An; Li, Si-yuan

2015-09-01

With the modified BCR sequential extraction procedure, the chemical speciation and risk for 10 heavy metals (Ba, Co, Cr, Cu, Mn, Ni, Pb, Sb, Sr and Zn) in roof dusts were investigated. The subjects of this study were collected from four typical material paved roofs (i. e., ceramic tile, concrete, metal and asphalt) in southeast China. The results indicated that the average contents of heavy metals in roof dust significantly exceeded road dust. The analysis of chemical fraction showed that the acid soluble/exchangeable fraction of Zn was much higher than other elements, the existence of Pb and Cu was mainly in oxidization fraction, while other heavy metals dominated by the residual fraction. The mobility sequence percentages for all roof dust samples decreased in the order of Pb > Zn > Cu >Mn > Co >Sr > Sb > Ni > Ba > Cr, and it should be noted that Pb, Zn, Cu, Mn and Co all have more than 50% proportion in mobility sequence. Based on environmental risk assessment, the highest values of contamination factors (Cf) and risk assessment code (RAC) consistently was observed in Zn, which indicated that Zn had relatively high ecological risk. Health risk assessment showed that the non-carcinogenic hazard indexes (HI) of heavy metals decreased in the order of Pb > Cr > Sb > Zn > Mn > Cu > Ba > Ni > Co > Sr, the HI of heavy metals for adults were lower than safe value while the HI of Pb for children was higher than safe value, suggesting that they will not harm the adult's health except Pb for children. The carcinogenic risk for Cr, Co and Ni were all below the threshold values, which indicated that there was no carcinogenic risk.

Metal Ion Speciation and Dissolved Organic Matter Composition in Soil Solutions

NASA Astrophysics Data System (ADS)

Benedetti, M. F.; Ren, Z. L.; Bravin, M.; Tella, M.; Dai, J.

2014-12-01

Knowledge of the speciation of heavy metals and the role of dissolved organic matter (DOM) in soil solution is a key to understand metal mobility and ecotoxicity. In this study, soil column-Donnan membrane technique (SC-DMT) was used to measure metal speciation of Cd, Cu, Ni, Pb, and Zn in eighteen soil solutions, covering a wide range of metal sources and concentrations. DOM composition in these soil solutions was also determined. Our results show that in soil solution Pb and Cu are dominant in complex form, whereas Cd, Ni and Zn mainly exist as free ions; for the whole range of soil solutions, only 26.2% of DOM is reactive and consists mainly of fulvic acid (FA). The metal speciation measured by SC-DMT was compared to the predicted ones obtained via the NICA-Donnan model using the measured FA concentrations. The free ion concentrations predicted by speciation modelling were in good agreement with the measurements. Diffusive gradients in thin-films gels (DGT) were also performed to quantify the labile metal species in the fluxes from solid phase to solution in fourteen soils. The concentrations of metal species detected by DGT were compared with the free ion concentrations measured by DMT and the maximum concentrations calculated based on the predicted metal speciation in SC-DMT soil solutions. It is concluded that both inorganic species and a fraction of FA bound species account for the amount of labile metals measured by DGT, consistent with the dynamic features of this technique. The comparisons between measurements using analytical techniques and mechanistic model predictions provided mutual validation in their performance. Moreover, we show that to make accurate modelling of metal speciation in soil solutions, the knowledge of DOM composition is the crucial information, especially for Cu; like in previous studies the modelling of Pb speciation is not optimal and an updated of Pb generic binding parameters is required to reduce model prediction uncertainties.

Modeling of phytoextraction efficiency of microbially stimulated Salix dasyclados L. in the soils with different speciation of heavy metals.

PubMed

Złoch, Michał; Kowalkowski, Tomasz; Tyburski, Jarosław; Hrynkiewicz, Katarzyna

2017-12-02

Bioaugmentation of soils with selected microorganisms during phytoextraction can be the key solution for successful bioremediation and should be accurately calculated for different physicochemical soil properties and heavy metal availability to guarantee the universality of this method. Equally important is the development of an accurate prediction tool to manage phytoremediation process. The main objective of this study was to evaluate the role of three metallotolerant siderophore-producing Streptomyces sp. B1-B3 strains in the phytoremediation of heavy metals with the use of S. dasyclados L. growing in four metalliferrous soils as well as modeling the efficiency of this process based on physicochemical and microbiological properties of the soils using artificial neural network (ANN) analysis. The bacterial inoculation of plants significantly stimulated plant biomass and reduced oxidative stress. Moreover, the bacteria affected the speciation of heavy metals and finally their mobility, thereby enhancing the uptake and bioaccumulation of Zn, Cd, and Pb in the biomass. The best capacity for phytoextraction was noted for strain B1, which had the highest siderophore secretion ability. Finally, ANN model permitted to predict efficiency of phytoextraction based on both the physicochemical properties of the soils and the activity of the soil microbiota with high precision.

Leaching behavior of heavy metals and transformation of their speciation in polluted soil receiving simulated acid rain.

PubMed

Zheng, Shun-an; Zheng, Xiangqun; Chen, Chun

2012-01-01

Heavy metals that leach from contaminated soils under acid rain are of increasing concern. In this study, simulated acid rain (SAR) was pumped through columns of artificially contaminated purple soil. Column leaching tests and sequential extraction were conducted for the heavy metals Cu, Pb, Cd, and Zn to determine the extent of their leaching as well as to examine the transformation of their speciation in the artificially contaminated soil columns. Results showed that the maximum leachate concentrations of Cu, Pb, Cd, and Zn were less than those specified in the Chinese Quality Standards for Groundwater (Grade IV), thereby suggesting that the heavy metals that leached from the polluted purple soil receiving acid rain may not pose as risks to water quality. Most of the Pb and Cd leachate concentrations were below their detection limits. By contrast, higher Cu and Zn leachate concentrations were found because they were released by the soil in larger amounts as compared with those of Pb and Cd. The differences in the Cu and Zn leachate concentrations between the controls (SAR at pH 5.6) and the treatments (SAR at pH 3.0 and 4.5) were significant. Similar trends were observed in the total leached amounts of Cu and Zn. The proportions of Cu, Pb, Cd, and Zn in the EXC and OX fractions were generally increased after the leaching experiment at three pH levels, whereas those of the RES, OM, and CAR fractions were slightly decreased. Acid rain favors the leaching of heavy metals from the contaminated purple soil and makes the heavy metal fractions become more labile. Moreover, a pH decrease from 5.6 to 3.0 significantly enhanced such effects.

Leaching Behavior of Heavy Metals and Transformation of Their Speciation in Polluted Soil Receiving Simulated Acid Rain

PubMed Central

Zheng, Shun-an; Zheng, Xiangqun; Chen, Chun

2012-01-01

Heavy metals that leach from contaminated soils under acid rain are of increasing concern. In this study, simulated acid rain (SAR) was pumped through columns of artificially contaminated purple soil. Column leaching tests and sequential extraction were conducted for the heavy metals Cu, Pb, Cd, and Zn to determine the extent of their leaching as well as to examine the transformation of their speciation in the artificially contaminated soil columns. Results showed that the maximum leachate concentrations of Cu, Pb, Cd, and Zn were less than those specified in the Chinese Quality Standards for Groundwater (Grade IV), thereby suggesting that the heavy metals that leached from the polluted purple soil receiving acid rain may not pose as risks to water quality. Most of the Pb and Cd leachate concentrations were below their detection limits. By contrast, higher Cu and Zn leachate concentrations were found because they were released by the soil in larger amounts as compared with those of Pb and Cd. The differences in the Cu and Zn leachate concentrations between the controls (SAR at pH 5.6) and the treatments (SAR at pH 3.0 and 4.5) were significant. Similar trends were observed in the total leached amounts of Cu and Zn. The proportions of Cu, Pb, Cd, and Zn in the EXC and OX fractions were generally increased after the leaching experiment at three pH levels, whereas those of the RES, OM, and CAR fractions were slightly decreased. Acid rain favors the leaching of heavy metals from the contaminated purple soil and makes the heavy metal fractions become more labile. Moreover, a pH decrease from 5.6 to 3.0 significantly enhanced such effects. PMID:23185399

Kinetics of heavy metal adsorption and desorption in soil: Developing a unified model based on chemical speciation

NASA Astrophysics Data System (ADS)

Peng, Lanfang; Liu, Paiyu; Feng, Xionghan; Wang, Zimeng; Cheng, Tao; Liang, Yuzhen; Lin, Zhang; Shi, Zhenqing

2018-03-01

Predicting the kinetics of heavy metal adsorption and desorption in soil requires consideration of multiple heterogeneous soil binding sites and variations of reaction chemistry conditions. Although chemical speciation models have been developed for predicting the equilibrium of metal adsorption on soil organic matter (SOM) and important mineral phases (e.g. Fe and Al (hydr)oxides), there is still a lack of modeling tools for predicting the kinetics of metal adsorption and desorption reactions in soil. In this study, we developed a unified model for the kinetics of heavy metal adsorption and desorption in soil based on the equilibrium models WHAM 7 and CD-MUSIC, which specifically consider metal kinetic reactions with multiple binding sites of SOM and soil minerals simultaneously. For each specific binding site, metal adsorption and desorption rate coefficients were constrained by the local equilibrium partition coefficients predicted by WHAM 7 or CD-MUSIC, and, for each metal, the desorption rate coefficients of various binding sites were constrained by their metal binding constants with those sites. The model had only one fitting parameter for each soil binding phase, and all other parameters were derived from WHAM 7 and CD-MUSIC. A stirred-flow method was used to study the kinetics of Cd, Cu, Ni, Pb, and Zn adsorption and desorption in multiple soils under various pH and metal concentrations, and the model successfully reproduced most of the kinetic data. We quantitatively elucidated the significance of different soil components and important soil binding sites during the adsorption and desorption kinetic processes. Our model has provided a theoretical framework to predict metal adsorption and desorption kinetics, which can be further used to predict the dynamic behavior of heavy metals in soil under various natural conditions by coupling other important soil processes.

Speciation distribution and mass balance of copper and zinc in urban rain, sediments, and road runoff.

PubMed

Zuo, Xiaojun; Fu, Dafang; Li, He

2012-11-01

Heavy metal pollution in road runoff had caused widespread concern since the last century. However, there are little references on metal speciation in multiple environmental media (e.g., rain, road sediments, and road runoff). Our research targeted the investigation of metal speciation in rain, road sediments, and runoff; the analysis of speciation variation and mass balance of metals among rain, road sediments, and runoff; the selection of main factors by principal component analysis (PCA); and the establishment of equation to evaluate the impact of rain and road sediments to metals in road runoff. Sequential extraction procedure contains five steps for the chemical fractionation of metals. Flame atomic absorption spectrometry (Shimadzu, AA-6800) was used to determine metal speciation concentration, as well as the total and dissolved fractions. The dissolved fractions for both Cu and Zn were dominant in rain. The speciation distribution of Zn was different from that of Cu in road sediments, while speciation distribution of Zn is similar to that of Cu in runoff. The bound to carbonates for both Cu and Zn in road sediments were prone to be dissolved by rain. The levels of Cu and Zn in runoff were not obviously influenced by rain, but significantly influenced by road sediments. The masses for both Cu and Zn among rain, road sediments, and road runoff approximately meet the mass balance equation for all rainfall patterns. Five principal factors were selected for metal regression equation based on PCA, including rainfall, average rainfall intensity, antecedent dry periods, total suspended particles, and temperature. The established regression equations could be used to predict the effect of road runoff on receiving environments.

Chemical speciation of heavy metals by surface-enhanced Raman scattering spectroscopy: identification and quantification of inorganic- and methyl-mercury in water

NASA Astrophysics Data System (ADS)

Guerrini, Luca; Rodriguez-Loureiro, Ignacio; Correa-Duarte, Miguel A.; Lee, Yih Hong; Ling, Xing Yi; García de Abajo, F. Javier; Alvarez-Puebla, Ramon A.

2014-06-01

Chemical speciation of heavy metals has become extremely important in environmental and analytical research because of the strong dependence that toxicity, environmental mobility, persistence and bioavailability of these pollutants have on their specific chemical forms. Novel nano-optical-based detection strategies, capable of overcoming the intrinsic limitations of well-established analytic methods for the quantification of total metal ion content, have been reported, but the speciation of different chemical forms has not yet been achieved. Here, we report the first example of a SERS-based sensor for chemical speciation of toxic metal ions in water at trace levels. Specifically, the inorganic Hg2+ and the more toxicologically relevant methylmercury (CH3Hg+) are selected as analytical targets. The sensing platform consists of a self-assembled monolayer of 4-mercaptopyridine (MPY) on highly SERS-active and robust hybrid plasmonic materials formed by a dense layer of interacting gold nanoparticles anchored onto polystyrene microbeads. The co-ordination of Hg2+ and CH3Hg+ to the nitrogen atom of the MPY ring yields characteristic changes in the vibrational SERS spectra of the organic chemoreceptor that can be qualitatively and quantitatively correlated to the presence of the two different mercury forms.Chemical speciation of heavy metals has become extremely important in environmental and analytical research because of the strong dependence that toxicity, environmental mobility, persistence and bioavailability of these pollutants have on their specific chemical forms. Novel nano-optical-based detection strategies, capable of overcoming the intrinsic limitations of well-established analytic methods for the quantification of total metal ion content, have been reported, but the speciation of different chemical forms has not yet been achieved. Here, we report the first example of a SERS-based sensor for chemical speciation of toxic metal ions in water at trace levels. Specifically, the inorganic Hg2+ and the more toxicologically relevant methylmercury (CH3Hg+) are selected as analytical targets. The sensing platform consists of a self-assembled monolayer of 4-mercaptopyridine (MPY) on highly SERS-active and robust hybrid plasmonic materials formed by a dense layer of interacting gold nanoparticles anchored onto polystyrene microbeads. The co-ordination of Hg2+ and CH3Hg+ to the nitrogen atom of the MPY ring yields characteristic changes in the vibrational SERS spectra of the organic chemoreceptor that can be qualitatively and quantitatively correlated to the presence of the two different mercury forms. Electronic supplementary information (ESI) available: Representative TEM and ESEM images of AuNPs and PS@Au particles. Optical extinction spectra of AuNPs and PS@Au suspensions. SERS spectra of unmodified PS@Au suspension before and after the addition of CH3Hg+. SERS spectra of PS@Au-MPY upon addition of several metal solutions. Detailed SERS study of the MPY response to high concentration of CH3Hg+. See DOI: 10.1039/c4nr01464b

Characterization of changes in floc morphology, extracellular polymeric substances and heavy metals speciation of anaerobically digested biosolid under treatment with a novel chelated-Fe2+ catalyzed Fenton process.

PubMed

He, Juanjuan; Yang, Peng; Zhang, Weijun; Cao, Bingdi; Xia, Hua; Luo, Xi; Wang, Dongsheng

2017-11-01

A novel chelated-Fe 2+ catalyzed Fenton process (CCFP) was developed to enhance dewatering performance of anaerobically digested biosolid, and changes in floc morphology, extracellular polymeric substances (EPS) and heavy metals speciation were also investigated. The results showed that addition of chelating agents caused EPS solubilization by binding multivalent cations. Like traditional Fenton, CCFP performed well in improving anaerobically digested sludge dewatering property. The highly active radicals (OH, O 2 - ) produced in classical Fenton and CCFP were responsible for sludge flocs destruction and consequently degradation of biopolymers into small molecules. Furthermore, more plentiful pores and channels were presented in cake after Fenton treatment, which was conducive to water drainage under mechanical compression. Additionally, a portion of active heavy metals in the form of oxidizable and reducible states were dissolved under CCFP. Therefore, CCFP could greatly simplify the operating procedure of Fenton conditioning and improve its process adaptability for harmless treatment of biological sludge. Copyright © 2017 Elsevier Ltd. All rights reserved.

Heavy metal speciation and toxicity characteristics of tannery sludge

NASA Astrophysics Data System (ADS)

Juel, Md. Ariful Islam; Chowdhury, Zia Uddin Md.; Ahmed, Tanvir

2016-07-01

Heavy metals present in tannery sludge can get mobilized in the environment in various forms and can be a cause for concern for the natural ecosystem and human health. The speciation of metals in sludge provides valuable information regarding their toxicity in the environment and determines their suitability for land application or disposal in landfills. Concentrations of seven heavy metals (Cr, Pb, Cd, Ni, Zn, As and Cu) in tannery sludge were determined to evaluate their toxicity levels. Metal contents ranged over the following intervals: As: 1.52-2.07 mg/kg; Pb: 57.5-67 mg/kg; Cr: 15339-26501 mg/kg; Cu: 261.3-579.5 mg/kg; Zn: 210.2-329.1 mg/kg and Ni: 137.5-141.3 mg/kg (dry weight basis). The concentrations of all heavy metals in the sludge samples were lower compared to EPA guidelines except chromium which was found to be several orders of magnitude higher than the guideline value. Toxicity Characteristics Leaching Procedure (TCLP) test indicated that the leaching potential of chromium was higher compared to the other heavy metals and exceeded the EPA land disposal restriction limits. To quantitatively assess the environmental burden of the chromium associated with tannery sludge, the IMPACT 2002+ methodology was adopted under the SimaPro software environment. Considering the USEPA limit for chromium as the baseline scenario, it was found that chromium in the tannery sludge had 6.41 times higher impact than the baseline in the categories of aquatic ecotoxicity, terrestrial ecotoxicity and non-carcinogens. Chromium has the highest contribution to toxicity in the category of aquatic ecotoxicity while copper is the major contributor to the category of terrestrial ecotoxicity in the tannery sludge.

Heavy metals fluxes and speciation in the surface layer of urban soils in the province of Brescia (Italy)

NASA Astrophysics Data System (ADS)

Peli, Marco; Raffelli, Giulia; Barontini, Stefano; Bostick, Benjamin C.; Donna, Filippo; Lucchini, Roberto G.; Ranzi, Roberto

2017-04-01

For the last forty years (1974-2015), a ferroalloy industry has been working in Bagnolo Mella, a municipality nearby the city of Brescia (Northern Italy), producing particulate emissions enriched in heavy metals: manganese (Mn) in particular, but also lead (Pb), iron (Fe), aluminum (Al) and arsenic (As). Although some of these metals are required trace elements for most living organisms and can be largely found in natural environments (e.g. Mn being the fifth most abundant metal in the Earth crust), they all lead to toxic effects when they contaminate work and life environments of the exposed population. Aiming at contributing to quantify the exposure of the population to environmental pollution near the factory, as well as the heavy metals possible tendency to migrate through the considered soil matrix, in this work we investigated metals speciation and fluxes within the Earth Critical Zone. The factory is located near residential areas in a plain characterised by little wind and shallow water table with a great number of water resurgences. Three test sites were identified among the pronest ones to particulate matter deposition, on the basis of data collected during a previous experimental field campaign and of the local wind rose. One more site was selected upwind to the factory as a reference site minimally prone to particulate matter deposition, on the basis of the previous investigations. Sites where lawns have been maintained at least for the last forty years where selected in order to avoid agriculture—induced effects on the metals movement. Total soil metal concentrations were measured by means of a portable X-Ray Fluorescence (XRF) device along the soil profiles, down to the depth of 40 cm from the soil surface. Four loose soil samples were collected at each site, at depths ranging from 5 to 30 cm, and they were later subjected to sequential extractions procedure and ICP—MS analyses, in order to investigate differences in heavy metals speciation along the considered soil profiles. The XRF metal total content profiles show an accumulation of metals in the subsurface soil layers, around 5 cm under the soil surface (this feature is highlighted in the normalized profiles). They also give evidence of the plant activity consequences, with the closest downwind site showing values which are for all metals at least one order of magnitude -two for Mn- higher than the ones in the test site. The speciation profiles, besides describing loosely the same pattern, show how the amorphous oxides species is always prevalent for Mn and Pb along the whole profile, while for As the species associated with crystalline oxides is always the prevalent one.

Heavy metal toxicity to bacteria - are the existing growth media accurate enough to determine heavy metal toxicity?

PubMed

Rathnayake, I V N; Megharaj, Mallavarapu; Krishnamurti, G S R; Bolan, Nanthi S; Naidu, Ravi

2013-01-01

A new minimal medium was formulated considering the limitations of the existing media for testing heavy metal sensitivity to bacteria. Toxicity of cadmium and copper to three bacteria was investigated in the new medium and compared with three other media commonly used to study the effect of the toxic metals. Based on speciation data arrived at using ion-selective electrodes, the available free-metal concentration in solution was highest in the MES-buffered medium. This finding was strongly supported by the estimated EC(50) values for the metals tested based on the toxicity bioassays. The free-ionic cadmium and copper concentrations in the medium provide more accurate determination of metal concentrations that affects the bacteria, than with most of other existing media. This will avoid doubts on other media and misleading conclusions relevant to the toxicity of heavy metals to bacteria and provides a better option for the study of metal-bacteria interactions. Copyright © 2012 Elsevier Ltd. All rights reserved.

Heavy metal speciation, leaching and toxicity status of a tropical rain-fed river Damodar, India.

PubMed

Pal, Divya; Maiti, Subodh Kumar

2018-03-26

Speciations of metals were assessed in a tropical rain-fed river, flowing through the highly economically important part of the India. The pattern of distribution of heavy metals (Cd, Co, Cr, Cu, Mn, Ni, Pb and Zn) were evaluated in water and sediment along with mineralogical characterization, changes with different water quality parameters and their respective health hazard to the local population along the Damodar River basin during pre-monsoon and post-monsoon seasons. The outcome of the speciation analysis using MINTEQ indicated that free metal ions, carbonate, chloride and sulfate ions were predominantly in anionic inorganic fractions, while in cationic inorganic fractions metal loads were negligible. Metals loads were higher in sediment phase than in the aqueous phase. The estimated values of I geo in river sediment during both the seasons showed that most of the metals were found in the I geo class 0-1 which represents unpolluted to moderately polluted sediment status. The result of partition coefficient indicated the strong retention capability of Cr, Pb, Co and Mn, while Cd, Zn, Cu and Ni have resilient mobility capacity. The mineralogical analysis of sediment samples indicated that in Damodar River, quartz, kaolinite and calcite minerals were dominantly present. The hazard index values of Cd, Co and Cr were > 1 in river water, which suggested potential health risk for the children. A combination of pragmatic, computational and statistical relationship between ionic species and fractions of metals represented a strong persuasion for identifying the alikeness among the different sites of the river.

Chemodynamics of heavy metals in long-term contaminated soils: metal speciation in soil solution.

PubMed

Kim, Kwon-Rae; Owens, Gary

2009-01-01

The concentration and speciation of heavy metals in soil solution isolated from long-term contaminated soils were investigated. The soil solution was extracted at 70% maximum water holding capacity (MWHC) after equilibration for 24 h. The free metal concentrations (Cd2+, CU2+, Pb2+, and Zn2+) in soil solution were determined using the Donnan membrane technique (DMT). Initially the DMT was validated using artificial solutions where the percentage of free metal ions were significantly correlated with the percentages predicted using MINTEQA2. However, there was a significant difference between the absolute free ion concentrations predicted by MINTEQA2 and the values determined by the DMT. This was due to the significant metal adsorption onto the cation exchange membrane used in the DMT with 20%, 28%, 44%, and 8% mass loss of the initial total concentration of Cd, Cu, Pb, and Zn in solution, respectively. This could result in a significant error in the determination of free metal ions when using DMT if no allowance for membrane cation adsorption was made. Relative to the total soluble metal concentrations the amounts of free Cd2+ (3%-52%) and Zn2+ (11%-72%) in soil solutions were generally higher than those of Cu2+ (0.2%-30%) and Pb2+ (0.6%-10%). Among the key soil solution properties, dissolved heavy metal concentrations were the most significant factor governing free metal ion concentrations. Soil solution pH showed only a weak relationship with free metal ion partitioning coefficients (K(p)) and dissolved organic carbon did not show any significant influence on K(p).

Effects of aerobic and anaerobic biological processes on leaching of heavy metals from soil amended with sewage sludge compost.

PubMed

Fang, Wen; Wei, Yonghong; Liu, Jianguo; Kosson, David S; van der Sloot, Hans A; Zhang, Peng

2016-12-01

The risk from leaching of heavy metals is a major factor hindering land application of sewage sludge compost (SSC). Understanding the change in heavy metal leaching resulting from soil biological processes provides important information for assessing long-term behavior of heavy metals in the compost amended soil. In this paper, 180days aerobic incubation and 240days anaerobic incubation were conducted to investigate the effects of the aerobic and anaerobic biological processes on heavy metal leaching from soil amended with SSC, combined with chemical speciation modeling. Results showed that leaching concentrations of heavy metals at natural pH were similar before and after biological process. However, the major processes controlling heavy metals were influenced by the decrease of DOC with organic matter mineralization during biological processes. Mineralization of organic matter lowered the contribution of DOC-complexation to Ni and Zn leaching. Besides, the reducing condition produced by biological processes, particularly by the anaerobic biological process, resulted in the loss of sorption sites for As on Fe hydroxide, which increased the potential risk of As release at alkaline pH. Copyright © 2016 Elsevier Ltd. All rights reserved.

Monitoring of electrokinetic removal of heavy metals in tailing-soils using sequential extraction analysis.

PubMed

Kim, S O; Kim, K W

2001-08-17

This research focused on the monitoring of the electrokinetic removal of heavy metals from tailing-soils, and emphasizes the dependency of removal efficiencies upon their physico-chemical states, as demonstrated by the different extraction methods adopted, which included aqua regia and sequential extraction. The tailing-soils examined contained high concentrations of target metal contaminants (Cd=179mgkg(-1), Cu=207mgkg(-1), Pb=5175mgkg(-1), and Zn=7600mgkg(-1)). The removal efficiencies of the different metals were significantly influenced by their speciations, mobilities and affinities (adsorption capacities) in the soil matrix. The removal efficiencies of mobile and weakly bound fractions, such as the exchangeable fraction were more than 90% by electrokinetic treatment, but strongly bound fractions, such as the organically bound species and residual fraction were not significantly removed (less than 30% removal efficiencies). In accordance with the general sequence of mobilities of heavy metals in soils, the removal efficiencies of more mobile heavy metals (Cd, Cu, and Zn) were higher than that of less mobile heavy metal (Pb).

Combined effects of antimony and sodium diethyldithiocarbamate on soil microbial activity and speciation change of heavy metals. Implications for contaminated lands hazardous material pollution in nonferrous metal mining areas.

PubMed

Zhu, Xiaozhe; Yao, Jun; Wang, Fei; Yuan, Zhimin; Liu, Jianli; Jordan, Gyozo; Knudsen, Tatjana Šolević; Avdalović, Jelena

2018-05-05

The combined effects of antimony (Sb) and sodium diethyldithiocarbamate (DDTC), a common organic flotation reagent, on soil microbial activity and speciation changes of heavy metals were investigated for the first time. The results showed that the exchangeable fraction of Sb was transformed to a stable residual fraction during the incubation period, and the addition of DDTC promoted the transformation compared with single Sb pollution, probably because DDTC can react with heavy metals to form a complex. In addition, the presence of DDTC and Sb inhibited the soil microbial activity to varying degrees. The growth rate constant k of different interaction systems was in the following order on the 28th day: control group ≥ single DDTC pollution > combined pollution > single Sb pollution. A correlation analysis showed that the concentration of exchangeable Sb was the primary factor that affected the toxic reaction under combined pollution conditions, and it significantly affected the characteristics of the soil microorganisms. All the observations provide useful information for a better understanding of the toxic effects and potential risks of combined Sb and DDTC pollution in antimony mining areas. Copyright © 2018 Elsevier B.V. All rights reserved.

Experimental and Theoretical Approaches for the Surface Interaction between Copper and Activated Sludge Microorganisms at Molecular Scale

NASA Astrophysics Data System (ADS)

Luo, Hong-Wei; Chen, Jie-Jie; Sheng, Guo-Ping; Su, Ji-Hu; Wei, Shi-Qiang; Yu, Han-Qing

2014-11-01

Interactions between metals and activated sludge microorganisms substantially affect the speciation, immobilization, transport, and bioavailability of trace heavy metals in biological wastewater treatment plants. In this study, the interaction of Cu(II), a typical heavy metal, onto activated sludge microorganisms was studied in-depth using a multi-technique approach. The complexing structure of Cu(II) on microbial surface was revealed by X-ray absorption fine structure (XAFS) and electron paramagnetic resonance (EPR) analysis. EPR spectra indicated that Cu(II) was held in inner-sphere surface complexes of octahedral coordination with tetragonal distortion of axial elongation. XAFS analysis further suggested that the surface complexation between Cu(II) and microbial cells was the distorted inner-sphere coordinated octahedra containing four short equatorial bonds and two elongated axial bonds. To further validate the results obtained from the XAFS and EPR analysis, density functional theory calculations were carried out to explore the structural geometry of the Cu complexes. These results are useful to better understand the speciation, immobilization, transport, and bioavailability of metals in biological wastewater treatment plants.

In situ reactive zone with modified Mg(OH)2 for remediation of heavy metal polluted groundwater: Immobilization and interaction of Cr(III), Pb(II) and Cd(II).

PubMed

Dong, Jun; Li, Bowen; Bao, Qiburi

2017-04-01

Mg(OH) 2 dissolves slowly and can provide a long-term source of alkalinity, thus a promising alternative reagent for the in situ remediation of heavy metal polluted groundwater. However, the application of Mg(OH) 2 on in situ reactive zone (IRZ) for heavy metal polluted groundwater has never been investigated. In this study, the behaviors of heavy metals in a Mg(OH) 2 IRZ were monitored for 45d. The heavy metals show a sequential precipitation by modified Mg(OH) 2 due to the difference of K sp . Column tests were conducted to investigate the temporal and spatial distribution of heavy metals in Mg(OH) 2 IRZ and evaluate the stabilization effect for multi-heavy metal polluted groundwater. Experimental results indicate that there exist interactions between different heavy metals, and their zoning distribution is attributed either to the competitive adsorption onto porous media (control column) or to the sequential precipitation of heavy metal ions (IRZ column). In contrast with the control column, heavy metal contaminated area in Mg(OH) 2 IRZ significantly shrinks. According to the chemical speciation analysis, when water containing Pb(II), Cd(II) and Cr(III) flows through Mg(OH) 2 IRZ, exchangeable fraction of total concentration significantly reduce and the proportion of carbonate and Fe/Mn oxides fraction increase, indicating the decrease of their mobility and toxicity. Copyright © 2017 Elsevier B.V. All rights reserved.

In situ reactive zone with modified Mg(OH)2 for remediation of heavy metal polluted groundwater: Immobilization and interaction of Cr(III), Pb(II) and Cd(II)

NASA Astrophysics Data System (ADS)

Dong, Jun; Li, Bowen; Bao, Qiburi

2017-04-01

Mg(OH)2 dissolves slowly and can provide a long-term source of alkalinity, thus a promising alternative reagent for the in situ remediation of heavy metal polluted groundwater. However, the application of Mg(OH)2 on in situ reactive zone (IRZ) for heavy metal polluted groundwater has never been investigated. In this study, the behaviors of heavy metals in a Mg(OH)2 IRZ were monitored for 45 d. The heavy metals show a sequential precipitation by modified Mg(OH)2 due to the difference of Ksp. Column tests were conducted to investigate the temporal and spatial distribution of heavy metals in Mg(OH)2 IRZ and evaluate the stabilization effect for multi-heavy metal polluted groundwater. Experimental results indicate that there exist interactions between different heavy metals, and their zoning distribution is attributed either to the competitive adsorption onto porous media (control column) or to the sequential precipitation of heavy metal ions (IRZ column). In contrast with the control column, heavy metal contaminated area in Mg(OH)2 IRZ significantly shrinks. According to the chemical speciation analysis, when water containing Pb(II), Cd(II) and Cr(III) flows through Mg(OH)2 IRZ, exchangeable fraction of total concentration significantly reduce and the proportion of carbonate and Fe/Mn oxides fraction increase, indicating the decrease of their mobility and toxicity.

Speciation, sources, and risk assessment of heavy metals in suburban vegetable garden soil in Xianyang City, Northwest China

NASA Astrophysics Data System (ADS)

Wang, Lijun; Tao, Wendong; Smardon, Richard C.; Xu, Xue; Lu, Xinwei

2017-07-01

Intensive anthropogenic activities can lead to soil heavy metal contamination resulting in potential risks to the environment and to human health. To reveal the concentrations, speciation, sources, pollution level, and ecological risk of heavy metals in vegetable garden soil, a total of 136 soil samples were collected from three vegetable production fields in the suburbs of Xianyang City, Northwest China. These samples were analyzed by inductively coupled plasma- atomic emission spectrometry and atomic fluorescence spectrometry. The results showed that the mean concentrations of Cd, Co, Cu, Mn, Pb, Zn, and Hg in vegetable garden soil were higher than the corresponding soil element background values of Shaanxi Province. The heavy metals studied in vegetable garden soil were primarily found in the residual fraction, averaging from 31.26% (Pb) to 90.23% (Cr). Considering the non-residual fractions, the mobility or potential risk was in the order of Pb (68.74%)>Co (60.54%)>Mn (59.28%) >Cd (53.54%) ≫Ni (23.36%) >Zn (22.73%)>Cu (14.93%)>V (11.81%)>Cr (9.78%). Cr, Mn, Ni, V, and As in the studied soil were related to soilforming parent materials, while Cu, Hg, Zn, Cd, Co, and Pb were associated with the application of plastic films, fertilizers, and pesticides, as well as traffic emissions and industrial fumes. Cr, Ni, V, and As presented low contamination levels, whereas Co, Cu, Mn, Pb, and Zn levels were moderate, and Cd and Hg were high. Ecological risk was low for Co, Cr, Cu, Mn, Pb, Zn, and As, with high risk observed for Cd and Hg. The overall pollution level and ecological risk of these heavy metals were high.

Speciation, sources, and risk assessment of heavy metals in suburban vegetable garden soil in Xianyang City, Northwest China

NASA Astrophysics Data System (ADS)

Wang, Lijun; Tao, Wendong; Smardon, Richard C.; Xu, Xue; Lu, Xinwei

2018-06-01

Intensive anthropogenic activities can lead to soil heavy metal contamination resulting in potential risks to the environment and to human health. To reveal the concentrations, speciation, sources, pollution level, and ecological risk of heavy metals in vegetable garden soil, a total of 136 soil samples were collected from three vegetable production fields in the suburbs of Xianyang City, Northwest China. These samples were analyzed by inductively coupled plasma- atomic emission spectrometry and atomic fluorescence spectrometry. The results showed that the mean concentrations of Cd, Co, Cu, Mn, Pb, Zn, and Hg in vegetable garden soil were higher than the corresponding soil element background values of Shaanxi Province. The heavy metals studied in vegetable garden soil were primarily found in the residual fraction, averaging from 31.26% (Pb) to 90.23% (Cr). Considering the non-residual fractions, the mobility or potential risk was in the order of Pb (68.74%)>Co (60.54%)>Mn (59.28%) >Cd (53.54%) ≫Ni (23.36%) >Zn (22.73%)>Cu (14.93%)>V (11.81%)>Cr (9.78%). Cr, Mn, Ni, V, and As in the studied soil were related to soilforming parent materials, while Cu, Hg, Zn, Cd, Co, and Pb were associated with the application of plastic films, fertilizers, and pesticides, as well as traffic emissions and industrial fumes. Cr, Ni, V, and As presented low contamination levels, whereas Co, Cu, Mn, Pb, and Zn levels were moderate, and Cd and Hg were high. Ecological risk was low for Co, Cr, Cu, Mn, Pb, Zn, and As, with high risk observed for Cd and Hg. The overall pollution level and ecological risk of these heavy metals were high.

Compacted Sewage Sludge as a Barrier for Tailings: The Heavy Metal Speciation and Total Organic Carbon Content in the Compacted Sludge Specimen

PubMed Central

Zhang, Huyuan; Zhang, Qing; Yang, Bo; Wang, Jinfang

2014-01-01

Acid mine drainage (AMD) was the main environmental problem facing the mining industry. For AMD had high heavy metals content and low pH, the compacted sewage sludge might be a barrier for tailings whose oxidation and weathering produced AMD, with its own carbon source, microorganism reduction ability and impermeability. To study the heavy metals environmental risk, under the simulate AMD, the deionized water (DW), and the pH 2.1 sulfuric acid water (SA) seepage conditions, respectively, the changes of the chemical speciation of heavy metals Cd, Cu, Fe, Ni, Zn and total organic carbon (TOC) content in the compacted sewage sludge were assessed in the different periods. The results indicated according to the distribution of heavy metals, the potential mobility was for Cd: 6.08 under AMD, 7.48 under SA, ∞ under DW; for Cu: 0.08 under AMD, 0.17 under SA, 0.59 under DW; for Fe: 0.15 under AMD, 0.22 under SA, 0.22 under DW; for Ni: 2.60 under AMD, 1.69 under SA, 1.67 under DW; and for Zn: 0.15 under AMD, 0.23 under SA and 0.21 under DW at the second checking time. TOC content firstly decreased from 67.62±0% to 66.29±0.35%, then increased to 67.74±0.65% under the AMD seepage while TOC decreased to 63.30±0.53%, then to 61.33±0.37% under the DW seepage, decreased to 63.86±0.41%, then to 63.28±0.49% under SA seepage. That indicated under the AMD seepage, the suitable microorganisms communities in the compacted sewage sludge were activated. And the heavy metals environmental risk of compacted sewage sludge was lower with AMD condition than with other two. So the compacted sewage sludge as a barrier for tailings was feasible as the aspect of environmental risk assessment. PMID:24979755

Distribution, speciation, environmental risk, and source identification of heavy metals in surface sediments from the karst aquatic environment of the Lijiang River, Southwest China.

PubMed

Xu, Daoquan; Wang, Yinghui; Zhang, Ruijie; Guo, Jing; Zhang, Wei; Yu, Kefu

2016-05-01

The distribution and speciation of several heavy metals, i.e., As, Cd, Cr, Cu, Hg, Pb, and Zn, in surface sediments from the karst aquatic environment of the Lijiang River, Southwest China, were studied comparatively. The mean contents of Cd, Cu, Hg, Pb, and Zn were 1.72, 38.07, 0.18, 51.54, and 142.16 mg/kg, respectively, which were about 1.5-6 times higher than their corresponding regional sediment background values. Metal speciation obtained by the optimized BCR protocol highlighted the bioavailable threats of Cd, Cu, and Zn, which were highly associated with the exchangeable fraction (the labile phase). Hierarchical cluster analysis indicated that in sediments, As and Cr were mainly derived from natural and industrial sources, whereas fertilizer application might lead to the elevated level of Cd. Besides, Cu, Hg, Pb, and Zn were related to traffic activities. The effects-based sediment quality guidelines (SQGs) showed that Hg, Pb, and Zn could pose occasional adverse effects on sediment-dwelling organisms. However, based on the potential ecological risk assessment (PER) and risk assessment code (RAC), Cd was the most outstanding pollutant and posed the highest ecological hazard and bioavailable risk among the selected metals. Moreover, the metal partitioning between water and sediments was quantified through the calculation of the pseudo-partitioning coefficient (K P), and result implied that the sediments in this karst aquatic environment cannot be used as stable repositories for the metal pollutants.

Heavy metals in red crabs, Chaceon quinquedens, from the Gulf of Mexico.

PubMed

Perry, Harriet; Isphording, Wayne; Trigg, Christine; Riedel, Ralf

2015-12-30

The red crab, Chaceon quinquedens, is distributed in deep waters of the Gulf of Mexico (GOM) and is most abundant in an area associated with sediment deposition from the Mississippi River. Sediment geochemistry and biological and ecological traits of red crabs favor accumulation of contaminants. Red crabs, sediment, and bottom water samples were taken from three distinct geographic locations representing areas with differing exposure to contaminant laden effluents from the Mississippi River. Inductively coupled plasma spectrophotometry and atomic absorption spectrophotometry were employed to determine levels of heavy metals in red crab muscle tissue. Ion site partitioning was used to determine metal speciation in sediments. Red crabs showed evidence of heavy metal bioaccumulation in all sample areas with high variability in contaminant levels in individual crabs for some metals. Bioavailability of metals in sediment did not always result in accumulation in muscle tissue. Copyright © 2015 Elsevier Ltd. All rights reserved.

Speciation analysis and leaching behaviors of selected trace elements in spent SCR catalyst.

PubMed

Dai, Zejun; Wang, Lele; Tang, Hao; Sun, Zhijun; Liu, Wei; Sun, Yi; Su, Sheng; Hu, Song; Wang, Yi; Xu, Kai; Liu, Liang; Ling, Peng; Xiang, Jun

2018-09-01

This study investigated heavy metal chemical speciation and leaching behavior from a board-type spent selective catalytic reduction (SCR) catalyst containing high concentrations of vanadium, chromium, nickel, copper, zinc, and lead. A three-step sequential extraction method, standard toxicity characteristic leaching procedure (TCLP), and leaching characteristic tests have been performed. It was found that the mobility of six heavy metals in the spent SCR catalyst was significantly different. The mobility of the six heavy metals exhibited the following order: Ni > Zn > V > Cr > As > Cu. Meanwhile, TCLP test results revealed relatively high Zn and Cr leaching rate of 83.20% and 10.35%, respectively. It was found that leaching rate was positively correlated with available contents (sum of acid soluble, reducible and oxidizable fractions). Leaching characteristics tests indicated that pH substantially affected the leaching of these heavy metals. In particular, the leaching of Cr, Ni, Cu, and Zn was positively influenced by strong acid, while V and As were easily released in the presence of strong acid and strong alkali (pH < 3 or pH > 11). In terms of kinetics, the leaching of Cr, Ni, Cu, Zn, and As within the spent catalyst was dominated by erosion and dissolution processes, which were rapid reaction processes. V was released in large amounts within 1 h, but its leaching amount sharply decreased with time due to readsorption. Copyright © 2018 Elsevier Ltd. All rights reserved.

Quantitative analysis and reduction of the eco-toxicity risk of heavy metals for the fine fraction of automobile shredder residue (ASR) using H2O2.

PubMed

Singh, Jiwan; Yang, Jae-Kyu; Chang, Yoon-Young

2016-02-01

Automobile shredder residue (ASR) fraction (size <0.25mm) can be considered as hazardous due to presence of high concentrations of heavy metals. Hydrogen peroxide combined with nitric acid has been used for the recovery of heavy metals (Zn, Cu, Mn, Fe, Ni, Pb, Cd and Cr) from the fine fraction of ASR. A sequential extraction procedure has also been used to determine the heavy metal speciation in the fine fraction of ASR before and after treatment. A risk analysis of the fine fraction of ASR before and after treatment was conducted to assess the bioavailability and eco-toxicity of heavy metals. These results showed that the recovery of heavy metals from ASR increased with an increase in the hydrogen peroxide concentration. A high concentration of heavy metals was found to be present in Cbio fractions (the sum of the exchangeable and carbonate fractions) in the fine fraction of ASR, indicating high toxicity risk. The Cbio rate of all selected heavy metals was found to range from 8.6% to 33.4% of the total metal content in the fine fraction of ASR. After treatment, Cbio was reduced to 0.3-3.3% of total metal upon a treatment with 2.0% hydrogen peroxide. On the basis of the risk assessment code (RAC), the environmental risk values for heavy metals in the fine fraction of ASR reflect high risk/medium risk. However, after treatment, the heavy metals would be categorized as low risk/no risk. The present study concludes that hydrogen peroxide combined with nitric acid is a promising treatment for the recovery and reduction of the eco-toxicity risk of heavy metals in ASR. Copyright © 2015 Elsevier Ltd. All rights reserved.

Selected heavy metals speciation in chemically stabilised sewage sludge

NASA Astrophysics Data System (ADS)

Wiśniowska, Ewa; Włodarczyk-Makuła, Marła

2017-11-01

Selected heavy metals (Pb, Ni, Cd) were analysed in soil, digested sewage sludge as well as in the sludge stabilised with CaO or Fenton's reagent. The dose of Fenton's reagent was as follows: Fe2+ = 1g.L-1, Fe2+/H2O2=1:100; stabilisation lasted for 2 h. Dose of CaO was equal to 1 g CaO.g d.m.-1 Total concentration of all metals in the digested sewage sludge was higher than in the soil. Chemical stabilisation of sludge with Fenton's reagent increased total metal content in the sludge as a result of total solids removal. Opposite effect was stated when the sludge was mixed with CaO. Also chemical fractions of heavy metals were identified (exchangeable, carbonate bound, iron oxides bound, organic and residual). The results indicate that stabilisation of the sludge with Fenton's reagent increased mobility of heavy metals compared to the digested sludge. Amendment of CaO increased percent share of examined metals in residual fraction, thus immobilised them and decreased their bioavailability.

Direct identification of trace metals in fine and ultrafine particles in the Detroit urban atmosphere.

PubMed

Utsunomiya, Satoshi; Jensen, Keld A; Keeler, Gerald J; Ewing, Rodney C

2004-04-15

Exposure to airborne particulates containing low concentrations of heavy metals, such as Pb, As, and Se, may have serious health effects. However, little is known about the speciation and particle size of these airborne metals. Fine- and ultrafine particles with heavy metals in aerosol samples from the Detroit urban area, Michigan, were examined in detail to investigate metal concentrations and speciation. The characterization of individual particles was completed using high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) combined with conventional high-resolution TEM techniques. The trace elements, Pb, As, La, Ce, Sr, Zn, Cr, Se, Sn, Y, Zr, Au, and Ag, were detected, and the elemental distributions were mapped in situ atthe nanoscale. The crystal structures of the particles containing Pb, Sr, Zn, and Au were determined from their electron diffraction patterns. Based on the characterization of the representative trace element particles, the potential health effects are discussed. Most of the trace element particles detected in this study were within a range of 0.01-1.0 microm in size, which has the longest atmospheric residence time (approximately 100 days). Increased chemical reactivity owing to the size of nanoparticles may be expected for most of the trace metal particles observed.

Heavy Metals in Marine Pollution Perspective-A Mini Review

NASA Astrophysics Data System (ADS)

Ansari, T. M.; Marr, I. L.; Tariq, N.

Anthropogenic inputs of pollutants such as heavy metals into the marine environment have increased their levels to large extents within past a few decades. These pollutants tend to accumulate in the bottom sediments. As a result, ecosystems such as seaports or other industrialized coastal areas that have chronic inputs of metals have highly contaminated sediments. This characteristic has led to concerns over the ecological effects that may be associated with sediment quality. Of particular concern are toxic effects and the potential for bioaccumulation of metals in biota exposed to the sediments. The availability of heavy metals to the biomass of a polluted region is the prime concern both in terms of the prediction of the effects of metal pollution on an ecosystem and in terms of possible human health risks. With growing interest on environmental issues, several intriguing questions related to heavy metals are often raised. This review addresses the basic concepts, sources, speciation, mode of action, levels, analytical measurement, bioavailability, bioaccumulation, biological role and toxicity of heavy metals in the marine environment. Lead, Cadmium, Zinc, Copper, Manganese, Iron, Mercury, Arsenic and Barium are selected because these metals are common and are often at measurable levels in marine samples. An attempt has been made to answer the queries presented by the environmentalists working on various aspects of heavy metal pollution in the marine environment

The Environment Quality, Speciation and their Origins of Heavy Metals in Surficial Sediments in Central Bohai Sea, China

NASA Astrophysics Data System (ADS)

Liu, M.; Fan, D.; Han, Z.; Liao, Y.; Chen, B.; Yang, Z.

2016-02-01

The concentrations and speciations of heavy metals (Cu, Co, Ni, Zn, Pb, Cr and Cd) in surface and core sediments collected from the central Bohai Sea were analyzed by ICP-MS, to evaluate their distribution / fractionation, pollution status and sources. The results showed that Cd exhibited gradual increasing vertically, while others were stable or declined slightly in core sediments. Metals showed higher values in `central mud area of the Bohai Sea' and the coastal area of the Bohai Bay in surface sediments. Residual fractions were the dominant forms of Cu, Co, Ni, Zn and Cr in the surface sediments, while Cd and Pb had large proportions of the total concentration in the non-residual fractions. Both the contamination factors and the geo-accumulation index indicated that Cu, Co, Ni, Cr were not polluted, while Pb, Zn, Cd were in moderate contamination. The ecological risk assessment (by sepeciations) indicated that the sediments were unpolluted with respect to the heavy metals Co, Ni and Cr and unpolluted to moderately polluted with respect to Cu, Zn, Cd and Pb. Compared with sediment quality guidelines (SQGs), Cu, Zn, Cr, Pb, Cd were likely to produce occasional adverse biological effects, while Ni showed possible ecotoxicological risks. The combined levels of the metals have a 21% probability of being toxic. Elements Cr, Co and Ni were mainly natural origined and significantly affected by the composition of sediments. Cu, Zn, Pb and especially Cd may be influenced by human activities.

Transport, speciation, toxicity, and treatability of highway stormwater discharged to receiving waters in Louisiana.

DOT National Transportation Integrated Search

2013-01-01

Stormwater from transportation land uses is a complex heterogeneous mixture of particulate matter, nutrients (phosphorus and nitrogen), heavy metals, inorganic, and organic compounds with variations in flow and mass loadings by orders of magnitude du...

[Evaluation of compounding EDTA and citric acid on remediation of heavy metals contaminated soil].

PubMed

Yin, Xue; Chen, Jia-Jun; Cai, Wen-Min

2014-08-01

As commonly used eluents, Na2EDTA (EDTA) and citric acid (CA) have been widely applied in remediation of soil contaminated by heavy metals. In order to evaluate the removal of arsenic, cadmium, copper, and lead in the contaminated soil collected in a chemical plant by compounding EDTA and CA, a series of stirring experiments were conducted. Furthermore, the changes in speciation distribution of heavy metals before and after washing were studied. The results showed that, adopting the optimal molar ratio of EDTA/CA (1:1), when the pH of the solution was 3, the stirring time was 30 min, the stirring rate was 150 r x min(-1) and the L/S was 5:1, the removal rates of arsenic, cadmium, copper and lead could reach 11.72%, 43.39%, 24.36% and 27.17%, respectively. And it was found that after washing, for arsenic and copper, the content of acid dissolved fraction rose which increased the percentage of available contents. Fe-Mn oxide fraction mainly contributed to the removal of copper. As for cadmium, the percentages of acid dissolved fraction, Fe-Mn oxide fraction and organic fraction also decreased. In practical projects, speciation changes would pose certain environmental risk after soil washing, which should be taken into consideration.

Toxic heavy metal contamination assessment and speciation in sugarcane soil

NASA Astrophysics Data System (ADS)

Wang, Xiaofei; Deng, Chaobing; Yin, Juan; Tang, Xiang

2018-01-01

The increasing heavy metal pollution in the sugarcane soils along the Great Huanjiang River was caused by leakage and spills of Lead (Pb) and Zinc (Zn) tailing dams during a flood event. Copper (Cu), Zn, Pb, Cadmium (Cd), and Arsenic (As) concentrations of soil samples collected from 16 different sites along the Great Huanjiang River coast typical pollution area were analyzed by Inductive Coupled Plasma Mass Spectrometry (ICP-MS). The mean concentrations of Pb, Cd, Zn, Cu, and As in the sugarcane soils were 151.57 mg/kg, 0.33 mg/kg, 155.52 mg/kg, 14.19 mg/kg, and 18.74 mg/kg, respectively. Results from the analysis of heavy metal speciation distribution showed that Cu, Zn, Pb, and Cd existed in weak acid, reducible, and oxidizable fractions, and the sum of these fractions accounted for significant proportions in sugarcane soils. However, the residual fraction of As with high proportion of reducible fraction indicated that this trace element still poses some environmental risk in the sugarcane soils because of its high content. Assessments of pollution levels revealed that the highest environmental risk was arouse by Pb. In addition, moderate to strong Cd and Zn pollution were found, while As has zero to medium level of pollution and Cu has zero level.

Speciation of heavy metals Cu, Ni and Zn by modified BCR sequential extraction procedure in sediments from Banten Bay, Banten Province, Indonesia

NASA Astrophysics Data System (ADS)

Lestari; Budiyanto, F.; Hindarti, D.

2018-02-01

Banten Bay is categorized as a marine area that is busy with marine tourism activities, settlements and also industries. One potential impact of the condition is the occurrence of pollution from both industrial and domestic sources, erosion and sedimentation in the coastal environment. Samples were collected from 25 representative stations in April 2016. Chemical speciation of three heavy metals (Cu, Ni, and Zn) was studied using a modified sequential extraction procedure proposed by the European Standard, Measurements and Testing (SM&T) program, formerly the Community Bureau of Reference (BCR). The aims of this study are to determine geochemical speciation of 4 bounds of metal: acid-soluble, reducible, oxidizable and residual, and to assess their impacts in the sediments of Banten Bay, Indonesia. The result shows that the percentage of Copper (45.90-83.75%), Nickel (18.28-65.66%), and Zinc (30.45-79.51%) were mostly accumulated in residual fraction of the total concentrations. The Risk Assessment Code (RAC) reveals that about 0-7.07% of Copper and 1.11-24.35 % of Zinc at sites exist in exchangeable fraction and therefore, they are in low risk category. While 7.34-34.90 of Ni at sites exists in exchangeable fraction and therefore, it is in medium risk category to aquatic environment.

Heavy metal tolerance in plants: A model evolutionary system.

PubMed

Macnair, M R

1987-12-01

Evolved tolerance to toxic concentrations of heavy metals in plants inhabiting spoil heaps of mines is a well known phenomenon that has been the subject of much research in the last two decades. These plants are useful models for studying processes involved in the early stages of the speciation of edaphic endemics. Recent work has revealed the importance of several phenomena in the differentiation of tolerant populations, including natural selection, founder effects and 'hitch-hiking', and has demonstrated the early evolution of morphological differentiation and reproductive isolating mechanisms. Further studies of the biochemistry and molecular biology of heavy metal tolerance will help to show why some plant groups, such as Agrostis, are far more prone to evolve tolerance than others. Copyright © 1987. Published by Elsevier Ltd.

Environmental variation between habitats and uptake of heavy metals by Urtica dioica.

PubMed

Otte, M L; Wijte, A H

1993-12-01

The observation from previous surveys, that Urtica dioica plants that had grown in metal contaminated soil in the floodplains of the former Rhine estuary in different habitats, but at comparable total soil metal concentrations, showed significant differences in tissue metal concentrations, led to the hypothesis that variation in other environmental characteristics than soil composition and chemical speciation of metals between habitats is also important in determining uptake and translocation of metals in plants. A field survey indicated that differences in root Cd, Cu and Zn concentrations might partly be explained by variation in speciation of metals in different habitats. However, shoot concentrations showed a different pattern that did not relate to variation in soil metal concentrations. In a habitat experiment Urtica dioica plants were grown in artificially contaminated soil in pots that were placed in the four habitats (grassland, pure reed, mixed reed, osier bed) that were also included in the field survey. After seven weeks the plants showed significant differences in Cu and Zn concentrations in roots and aboveground plant parts and in distribution of the metals in the plants between habitats. It was concluded that variation between habitats in environmental characteristics other than soil composition can explain as much variation in plants as can variation in soil metal concentrations and/or speciation. The implications for assessment of soil metal contamination and uptake by plants are discussed.

Effects of wood vinegar on properties and mechanism of heavy metal competitive adsorption on secondary fermentation based composts.

PubMed

Liu, Ling; Guo, Xiaoping; Wang, Shuqi; Li, Lei; Zeng, Yang; Liu, Guanhong

2018-04-15

In this study, secondary municipal solid waste composts (SC) and wood vinegar treated secondary compost (WV-SC) was prepared to investigate the capability for single-heavy metals and multi-metal systems adsorption. The adsorption sequence of WV-SC for the maximum single metals sorption capacities was Cd (42.7mgg -1 ) > Cu (38.6mgg -1 ) > Zn (34.9mgg -1 ) > Ni (28.7mgg -1 ) and showed higher than that of SC adsorption isotherm. In binary/quaternary-metal systems, Ni adsorption showed a stronger inhibitory effect compared with Zn, Cd and Cu on both SC and WV-SC. According to Freundlich and Langmuir adsorption isotherm models, as well as desorption behaviors and speciation analysis of heavy metals, competitive adsorption behaviors were differed from single-metal adsorption. Especially, the three-dimensional simulation of competitive adsorption indicated that the Ni was easily exchanged and desorbed. The amount of exchangeable heavy metal fraction were in the lowest level for the metal-loaded adsorbents, composting treated by wood vinegar improved the adsorbed metals converted to the residue fraction. This was an essential start in estimating the multiple heavy metal adsorption behaviors of secondary composts, the results proved that wood vinegar was an effective additive to improve the composts quality and decrease the metal toxicity. Copyright © 2017 Elsevier Inc. All rights reserved.

Removal of heavy metals from polluted soil using the citric acid fermentation broth: a promising washing agent.

PubMed

Zhang, Hongjiao; Gao, Yuntao; Xiong, Huabin

2017-04-01

The citric acid fermentation broth was prepared and it was employed to washing remediation of heavy metal-polluted soil. A well-defined washing effect was obtained, the removal percentages using citric acid fermentation broth are that 48.2% for Pb, 30.6% for Cu, 43.7% for Cr, and 58.4% for Cd and higher than that using citric acid solution. The kinetics of heavy metals desorption can be described by the double constant equation and Elovich equation and is a heterogeneous diffusion process. The speciation analysis shows that the citric acid fermentation broth can effectively reduce bioavailability and environmental risk of heavy metals. Spectroscopy characteristics analysis suggests that the washing method has only a small effect on the mineral composition and does not destroy the framework of soil system. Therefore, the citric acid fermentation broth is a promising washing agent and possesses a potential practical application value in the field of remediation of soils with a good washing performance.

Levels and speciation of heavy metals in soils of industrial Southern Nigeria.

PubMed

Olajire, A A; Ayodele, E T; Oyedirdan, G O; Oluyemi, E A

2003-06-01

A knowledge of the total content of trace metals is not enough to fully assess the environmental impact of polluted soils. For this reason, the determination of metal species in solution is important to evaluate their behaviour in the environment and their mobilization capacity. Sequential extraction procedure was used to speciate five heavy metals (Cd, Pb, Cu, Ni and Zn) from four contaminated soils of Southern Nigeria into six operationally defined geochemical species: water soluble, enchangeable, carbonates, Fe-Mn oxide, organic and residual. Metal recoveries were within +/- 10% of the independently determined total Cd, Pb, Cu, Ni and Zn concentrations. The highest amount of Cd (avg. 30%) in the nonresidual fractions was found in the exchangeable fraction, while Cu and Zn were significantly associated with the organic fraction. The carbonate fraction contained on average 14, 18.6, 12.6, 13 and 11% and the residual fraction contained on average 47, 18, 33, 50 and 25% of Cd, Pb, Cu, Ni and Zn respectively. Assuming that mobility and bioavailability of these metals are related to the solubility of the geochemical form of the metals, and that they decrease in the order of extraction sequence, the apparent mobility and potential bioavailability for these five metals in the soil were: Pb > Zn > Cu > Ni > Cd. The mobility indexes of copper and nickel correlated positively and significantly with the total content of metals, while mobility indexes of cadmium and zinc correlated negatively and significantly with the total content of metals.

Insight into the heavy metal binding potential of dissolved organic matter in MSW leachate using EEM quenching combined with PARAFAC analysis.

PubMed

Wu, Jun; Zhang, Hua; He, Pin-Jing; Shao, Li-Ming

2011-02-01

Dissolved organic matter (DOM) plays an important role in heavy metal migration from municipal solid waste (MSW) to aquatic environments via the leachate pathway. In this study, fluorescence excitation-emission matrix (EEM) quenching combined with parallel factor (PARAFAC) analysis was adopted to characterize the binding properties of four heavy metals (Cu, Pb, Zn and Cd) and DOM in MSW leachate. Nine leachate samples were collected from various stages of MSW management, including collection, transportation, incineration, landfill and subsequent leachate treatment. Three humic-like components and one protein-like component were identified in the MSW-derived DOM by PARAFAC. Significant differences in quenching effects were observed between components and metal ions, and a relatively consistent trend in metal quenching curves was observed among various leachate samples. Among the four heavy metals, Cu(II) titration led to fluorescence quenching of all four PARAFAC-derived components. Additionally, strong quenching effects were only observed in protein-like and fulvic acid (FA)-like components with the addition of Pb(II), which suggested that these fractions are mainly responsible for Pb(II) binding in MSW-derived DOM. Moreover, the significant quenching effects of the FA-like component by the four heavy metals revealed that the FA-like fraction in MSW-derived DOM plays an important role in heavy metal speciation; therefore, it may be useful as an indicator to assess the potential ability of heavy metal binding and migration. © 2010 Elsevier Ltd. All rights reserved.

How can we take advantage of halophyte properties to cope with heavy metal toxicity in salt-affected areas?

PubMed Central

Lutts, Stanley; Lefèvre, Isabelle

2015-01-01

Background Many areas throughout the world are simultaneously contaminated by high concentrations of soluble salts and by high concentrations of heavy metals that constitute a serious threat to human health. The use of plants to extract or stabilize pollutants is an interesting alternative to classical expensive decontamination procedures. However, suitable plant species still need to be identified for reclamation of substrates presenting a high electrical conductivity. Scope Halophytic plant species are able to cope with several abiotic constraints occurring simultaneously in their natural environment. This review considers their putative interest for remediation of polluted soil in relation to their ability to sequester absorbed toxic ions in trichomes or vacuoles, to perform efficient osmotic adjustment and to limit the deleterious impact of oxidative stress. These physiological adaptations are considered in relation to the impact of salt on heavy metal bioavailabilty in two types of ecosystem: (1) salt marshes and mangroves, and (2) mine tailings in semi-arid areas. Conclusions Numerous halophytes exhibit a high level of heavy metal accumulation and external NaCl may directly influence heavy metal speciation and absorption rate. Maintenance of biomass production and plant water status makes some halophytes promising candidates for further management of heavy-metal-polluted areas in both saline and non-saline environments. PMID:25672360

Assessment of mechanisms of metal-induced reproductive toxicity in aquatic species as a biomarker of exposure

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

Anderson, M.; George, W.; Preslan, J.

1996-05-02

This project discusses the following studies: identification and quantitation of heavy metals and petroleum products present in Bayou Trepagnier relative to control sites; assessment of the uptake and bioaccumulation of metals and organic contaminants of interest in aquatic species; establishment and use of polarographic methods for use in metal speciation studies to identify specific chemical forms present in sediments, waters and organism; and evaluation of contaminants on reproductive function of aquatic species as potential biomarkers of exposure. 14 refs.

Electrochemical sensors and devices for heavy metals assay in water: the French groups' contribution

PubMed Central

Pujol, Luca; Evrard, David; Groenen-Serrano, Karine; Freyssinier, Mathilde; Ruffien-Cizsak, Audrey; Gros, Pierre

2014-01-01

A great challenge in the area of heavy metal trace detection is the development of electrochemical techniques and devices which are user-friendly, robust, selective, with low detection limits and allowing fast analyses. This review presents the major contribution of the French scientific academic community in the field of electrochemical sensors and electroanalytical methods within the last 20 years. From the well-known polarography to the up-to-date generation of functionalized interfaces, the different strategies dedicated to analytical performances improvement are exposed: stripping voltammetry, solid mercury-free electrode, ion selective sensor, carbon based materials, chemically modified electrodes, nano-structured surfaces. The paper particularly emphasizes their advantages and limits face to the last Water Frame Directive devoted to the Environmental Quality Standards for heavy metals. Recent trends on trace metal speciation as well as on automatic “on line” monitoring devices are also evoked. PMID:24818124

BIOCHEM-ORCHESTRA: a tool for evaluating chemical speciation and ecotoxicological impacts of heavy metals on river flood plain systems.

PubMed

Vink, J P M; Meeussen, J C L

2007-08-01

The chemical speciation model BIOCHEM was extended with ecotoxicological transfer functions for uptake of metals (As, Cd, Cu, Ni, Pb, and Zn) by plants and soil invertebrates. It was coupled to the object-oriented framework ORCHESTRA to achieve a flexible and dynamic decision support system (DSS) to analyse natural or anthropogenic changes that occur in river systems. The DSS uses the chemical characteristics of soils and sediments as input, and calculates speciation and subsequent uptake by biota at various scenarios. Biotic transfer functions were field-validated, and actual hydrological conditions were derived from long-term monitoring data. The DSS was tested for several scenarios that occur in the Meuse catchment areas, such as flooding and sedimentation of riverine sediments on flood plains. Risks are expressed in terms of changes in chemical mobility, and uptake by flood plain key species (flora and fauna).

Sources, distribution, bioavailability, toxicity, and risk assessment of heavy metal(loid)s in complementary medicines.

PubMed

Bolan, Shiv; Kunhikrishnan, Anitha; Seshadri, Balaji; Choppala, Girish; Naidu, Ravi; Bolan, Nanthi S; Ok, Yong Sik; Zhang, Ming; Li, Chun-Guang; Li, Feng; Noller, Barry; Kirkham, Mary Beth

2017-11-01

The last few decades have seen the rise of alternative medical approaches including the use of herbal supplements, natural products, and traditional medicines, which are collectively known as 'Complementary medicines'. However, there are increasing concerns on the safety and health benefits of these medicines. One of the main hazards with the use of complementary medicines is the presence of heavy metal(loid)s such as arsenic (As), cadmium (Cd), lead (Pb), and mercury (Hg). This review deals with the characteristics of complementary medicines in terms of heavy metal(loid)s sources, distribution, bioavailability, toxicity, and human risk assessment. The heavy metal(loid)s in these medicines are derived from uptake by medicinal plants, cross-contamination during processing, and therapeutic input of metal(loid)s. This paper discusses the distribution of heavy metal(loid)s in these medicines, in terms of their nature, concentration, and speciation. The importance of determining bioavailability towards human health risk assessment was emphasized by the need to estimate daily intake of heavy metal(loid)s in complementary medicines. The review ends with selected case studies of heavy metal(loid) toxicity from complementary medicines with specific reference to As, Cd, Pb, and Hg. The future research opportunities mentioned in the conclusion of review will help researchers to explore new avenues, methodologies, and approaches to the issue of heavy metal(loid)s in complementary medicines, thereby generating new regulations and proposing fresh approach towards safe use of these medicines. Copyright © 2017 Elsevier Ltd. All rights reserved.

Does Diffusion Sequester Heavy Metals in Old Contamination Soils?

NASA Astrophysics Data System (ADS)

Ma, J.; Jennings, A. A.

2002-12-01

Old soil contamination refers to soil contamination that has aged over a long period of time. For example, at some brownfields, the soil heavy metal contamination can be one hundred or more years old. When contamination is young, the heavy metals are bound relatively weakly to the soil. However, the speciation and/or mechanisms of association evolve with aging into much more stable forms. It also appears that the metals migrate deeper into the bulk soil matrix where they are less available to participate in surface-related phenomena. Previous research showed elevated heavy metal extraction result after the soil was pulverized, with all other experiment conditions remaining unchanged. This indicates the presence of sequestered heavy metal contamination within the large soil particles (aggregate). The mechanisms of sequestering are uncertain, but diffusion appears to be a major factor. There are two possible pathways of diffusion that can account for heavy metal sequestering: solid-state diffusion through the bulk aggregate or liquid-phase diffusion through micro-pores within the aggregate structure. The second diffusion mechanism can be coupled with sorption (or other surface-related phenomena) on the pore walls. The remediation of sequestered heavy metals is also impacted by diffusion. Grinding a soil significantly reduces its average particle size. This exposes more of its internal bulk volume to extraction and results in much shorter diffusion pathway for the sequestered heavy metals to be released. Evidence has illustrated that this both improves remediation efficiency and provides a method by which the degree of sequestering can be quantified. This paper will present the results of ongoing research that is developing methods to identify the mechanisms of, quantify the magnitude of and determine the relative importance of (i.e. risk analysis) heavy metals sequestered in old contamination soils.

Metal transformation as a strategy for bacterial detoxification of heavy metals.

PubMed

Essa, Ashraf M M; Al Abboud, Mohamed A; Khatib, Sayeed I

2018-01-01

Microorganisms can modify the chemical and physical characters of metals leading to an alteration in their speciation, mobility, and toxicity. Aqueous heavy metals solutions (Hg, Cd, Pb, Ag, Cu, and Zn) were treated with the volatile metabolic products (VMPs) of Escherichia coli Z3 for 24 h using aerobic bioreactor. The effect of the metals treated with VMPs in comparison to the untreated metals on the growth of E. coli S1 and Staphylococcus aureus S2 (local isolates) was examined. Moreover, the toxic properties of the treated and untreated metals were monitored using minimum inhibitory concentration assay. A marked reduction of the treated metals toxicity was recorded in comparison to the untreated metals. Scanning electron microscopy and energy dispersive X-ray analysis revealed the formation of metal particles in the treated metal solutions. In addition to heavy metals at variable ratios, these particles consisted of carbon, oxygen, sulfur, nitrogen elements. The inhibition of metal toxicity was attributed to the existence of ammonia, hydrogen sulfide, and carbon dioxide in the VMPs of E. coli Z3 culture that might responsible for the transformation of soluble metal ions into metal complexes. This study clarified the capability of E. coli Z3 for indirect detoxification of heavy metals via the immobilization of metal ions into biologically unavailable species. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Occurrence, speciation and transportation of heavy metals in 9 coastal rivers from watershed of Laizhou Bay, China.

PubMed

Xu, Li; Wang, Tieyu; Wang, Jihua; Lu, Anxiang

2017-04-01

The occurrence, speciation and transport of heavy metals in 9 coastal rivers from watershed of Laizhou Bay were investigated. The largest dissolved concentrations of Cd, Cu and Zn in water were 6.26, 2755.00, 2076.00 μg/L, respectively, much higher than several drinking water guidelines. The greatest concentrations of Cu, Zn, Cr, Ni, Pb and Cd in sediments were 1462, 1602, 196, 67.2, 63.5 and 1.41 mg/kg, dw, respectively. Correlation and principal component analysis was also conducted to determine the extent between the concentrations of metals in water and sediment, as well as relevant parameters. Throughout the river stretch, most of Cr Zn, Cr, Ni and Pb bound to residual fraction, however, Cd was preferentially bound to the exchangeable phase. Among the 9 rivers, Yellow river account for 72.5%, 67.5%, 55.4%, 59.4%, 79.4% and 85.5% for Cr, Ni, Cu, Zn. Cd and Pb, respectively. The combined potential ecological risk indexes were used to evaluate potential risks. The majority of sampling sites from watershed of Laizhou Bay have moderate ecological risk from metals. The government should pay more attention to the ecological risk of river ecosystem which flow to Laizhou Bay. Copyright © 2017 Elsevier Ltd. All rights reserved.

Bioremediation of industrial effluents containing heavy metals using brewing cells of Saccharomyces cerevisiae as a green technology: a review.

PubMed

Soares, Eduardo V; Soares, Helena M V M

2012-05-01

The release of heavy metals into the environment, mainly as a consequence of anthropogenic activities, constitutes a worldwide environmental pollution problem. Unlike organic pollutants, heavy metals are not degraded and remain indefinitely in the ecosystem, which poses a different kind of challenge for remediation. It seems that the "best treatment technologies" available may not be completely effective for metal removal or can be expensive; therefore, new methodologies have been proposed for the detoxification of metal-bearing wastewaters. The present work reviews and discusses the advantages of using brewing yeast cells of Saccharomyces cerevisiae in the detoxification of effluents containing heavy metals. The current knowledge of the mechanisms of metal removal by yeast biomass is presented. The use of live or dead biomass and the influence of biomass inactivation on the metal accumulation characteristics are outlined. The role of chemical speciation for predicting and optimising the efficiency of metal removal is highlighted. The problem of biomass separation, after treatment of the effluents, and the use of flocculent characteristics, as an alternative process of cell-liquid separation, are also discussed. The use of yeast cells in the treatment of real effluents to bridge the gap between fundamental and applied studies is presented and updated. The convenient management of the contaminated biomass and the advantages of the selective recovery of heavy metals in the development of a closed cycle without residues (green technology) are critically reviewed.

Influence of organic amendments on nickel phytoextraction and growth effects to Trifolium alexandrinum

NASA Astrophysics Data System (ADS)

Shahid, Muhammad; Sabir, Muhammad; Ghafoor, Abdul

2013-04-01

Heavy metal pollution of soil and other environmental compartments through anthropogenic activities and/or natural processes is a widespread and serious problem confronting society, scientists, and regulators worldwide (Shahid et al., 2011). Among the heavy metals, Ni is an essential heavy metal and plays many functions in living organisms (Khoshgoftarmanesh et al., 2011). The presence of this metal in soil or growth medium may have positive biological effects on plant growth. However, Ni may interfere with various morphological, physiological and biochemical process in plants when its concentration rises to supra-optimal values i.e., 100 mg kg-1 in plants and 420 kg ha-I in soil (Tucker, 2005). The use of organic amendments is a common practice in Pakistan to improve soil fertility. Organic amendments are known to affect chemical speciation and bioavailability of heavy metals and in turn their uptake and toxicity to plants (Shahid et al., 2012). The present study evaluate the influence of organic amendments viz. farm yard manure (FM), poultry manure (PM), press mud (PrM) and activated carbon (AC) on Ni bioavailability in soil as well as its uptake and growth responses of Trifolium alexandrinum. A pot experiment was conducted where T. alexandrinum was exposed to three different Ni level i.e., 30, 60 and 90 mg kg-1 in the form of NiCl2 solution in the presence and absence of organic amendments each applied at 15 g kg-1 soil. The results showed that the effect of organic amendments on Ni bioavailability and uptake by T. alexandrinum depend on Ni levels in soil and amendment type. Application of organic amendments generally increased Ni phytoavailability in soil and Ni uptake by plants at low Ni levels (Ni-0 and Ni-30) but decreased at higher levels (Ni-60 and Ni-90). It is proposed that the soil Ni levels and amendment type must be considered while using these amendments in Ni remediation and risk assessment studies. Keywords: Nickel, organic amendments, bioavailability, Trifolium alexandrinum, plant growth. REFERENCES Shahid M, Pinelli E, Dumat C, 2012. Review of Pb availability and toxicity to plants in relation with metal speciation; role of synthetic and natural organic ligands. Journal of Hazardous Materials, 219-220: 1-12. Shahid M, Pinelli E, Pourrut B, Silvestre J, Dumat C, 2011. Lead-induced genotoxicity to Vicia faba L. roots in relation with metal cell uptake and initial speciation. Ecotoxicology and Environmental Safety, 74(1): 78-84. Khoshgoftarmanesh, A.H. Hosseini, F. and Afyuni, M. (2011) Nickel supplementation effect on the growth, urease activity and urea and nitrate concentrations in lettuce supplied with different nitrogen sources. Sci. Horti., 130, 381-385. Tucker, M.R. Hardy, D.H. and Stokes, C.E. (2005) Heavy metals in North Carolina soils: occurrence and significance. North Carolina Department of Agriculture and Consumer Services, Agronomic Division.

Flotation as a remediation technique for heavily polluted dredged material. 2. Characterisation of flotated fractions.

PubMed

Cauwenberg, P; Verdonckt, F; Maes, A

1998-01-19

The particle size distribution and the metal speciation of the heavy metals were investigated on dredged sediment and on the fractions obtained by mechanical agitated (Denver) flotation. The transition metal ions (cadmium, copper, lead and zinc) were flotated specifically independent of the particle size. Particle size analysis, EDTA extraction and sequential extracts indicated that during flotation a redistribution of metals occurred due to the oxidation of metal sulphides. This oxidation process was more pronounced when the flotation was performed at higher pH values and resulted in a decrease in flotation specificity.

Simultaneous Removal of Lindane, Lead and Cadmium from Soils by Rhamnolipids Combined with Citric Acid.

PubMed

Wan, Jinzhong; Meng, Die; Long, Tao; Ying, Rongrong; Ye, Mao; Zhang, Shengtian; Li, Qun; Zhou, Yan; Lin, Yusuo

2015-01-01

This study investigated the performance of rhamnolipids-citric acid mixed agents in simultaneous desorption of lindane and heavy metals from soils. The capacity of the mixed agents to solubilize lindane, lead and cadmium in aqueous solution was also explored. The results showed that the presence of citric acid greatly enhanced the solubilization of lindane and cadmium by rhamnolipids. A combined effect of the mixed agents on lindane and heavy metals removal from soils was observed. The maximum desorption ratios for lindane, cadmium and lead were 85.4%, 76.4% and 28.1%, respectively, for the mixed agents containing 1% rhamnolipidsand 0.1 mol/L citric acid. The results also suggest that the removal efficiencies of lead and cadmium were strongly related to their speciations in soils, and metals in the exchangeable and carbonate forms were easier to be removed. Our study suggests that the combining use of rhamnolipids and citric acid is a promising alternative to simultaneously remove organochlorine pesticides and heavy metals from soils.

Simultaneous Removal of Lindane, Lead and Cadmium from Soils by Rhamnolipids Combined with Citric Acid

PubMed Central

Long, Tao; Ying, Rongrong; Ye, Mao; Zhang, Shengtian; Li, Qun; Zhou, Yan; Lin, Yusuo

2015-01-01

This study investigated the performance of rhamnolipids-citric acid mixed agents in simultaneous desorption of lindane and heavy metals from soils. The capacity of the mixed agents to solubilize lindane, lead and cadmium in aqueous solution was also explored. The results showed that the presence of citric acid greatly enhanced the solubilization of lindane and cadmium by rhamnolipids. A combined effect of the mixed agents on lindane and heavy metals removal from soils was observed. The maximum desorption ratios for lindane, cadmium and lead were 85.4%, 76.4% and 28.1%, respectively, for the mixed agents containing 1% rhamnolipidsand 0.1 mol/L citric acid. The results also suggest that the removal efficiencies of lead and cadmium were strongly related to their speciations in soils, and metals in the exchangeable and carbonate forms were easier to be removed. Our study suggests that the combining use of rhamnolipids and citric acid is a promising alternative to simultaneously remove organochlorine pesticides and heavy metals from soils. PMID:26087302

Removal of arsenic and cadmium with sequential soil washing techniques using Na2EDTA, oxalic and phosphoric acid: Optimization conditions, removal effectiveness and ecological risks.

PubMed

Wei, Meng; Chen, Jiajun; Wang, Xingwei

2016-08-01

Testing of sequential soil washing in triplicate using typical chelating agent (Na2EDTA), organic acid (oxalic acid) and inorganic weak acid (phosphoric acid) was conducted to remediate soil contaminated by heavy metals close to a mining area. The aim of the testing was to improve removal efficiency and reduce mobility of heavy metals. The sequential extraction procedure and further speciation analysis of heavy metals demonstrated that the primary components of arsenic and cadmium in the soil were residual As (O-As) and exchangeable fraction, which accounted for 60% and 70% of total arsenic and cadmium, respectively. It was determined that soil washing agents and their washing order were critical to removal efficiencies of metal fractions, metal bioavailability and potential mobility due to different levels of dissolution of residual fractions and inter-transformation of metal fractions. The optimal soil washing option for arsenic and cadmium was identified as phosphoric-oxalic acid-Na2EDTA sequence (POE) based on the high removal efficiency (41.9% for arsenic and 89.6% for cadmium) and the minimal harmful effects of the mobility and bioavailability of the remaining heavy metals. Copyright © 2016 Elsevier Ltd. All rights reserved.

Insights into metals in individual fine particles from municipal solid waste using synchrotron radiation-based micro-analytical techniques.

PubMed

Zhu, Yumin; Zhang, Hua; Shao, Liming; He, Pinjing

2015-01-01

Excessive inter-contamination with heavy metals hampers the application of biological treatment products derived from mixed or mechanically-sorted municipal solid waste (MSW). In this study, we investigated fine particles of <2mm, which are small fractions in MSW but constitute a significant component of the total heavy metal content, using bulk detection techniques. A total of 17 individual fine particles were evaluated using synchrotron radiation-based micro-X-ray fluorescence and micro-X-ray diffraction. We also discussed the association, speciation and source apportionment of heavy metals. Metals were found to exist in a diffuse distribution with heterogeneous intensities and intense hot-spots of <10 μm within the fine particles. Zn-Cu, Pb-Fe and Fe-Mn-Cr had significant correlations in terms of spatial distribution. The overlapped enrichment, spatial association, and the mineral phases of metals revealed the potential sources of fine particles from size-reduced waste fractions (such as scraps of organic wastes or ceramics) or from the importation of other particles. The diverse sources of heavy metal pollutants within the fine particles suggested that separate collection and treatment of the biodegradable waste fraction (such as food waste) is a preferable means of facilitating the beneficial utilization of the stabilized products. Copyright © 2014. Published by Elsevier B.V.

Combination of bioleaching by gross bacterial biosurfactants and flocculation: A potential remediation for the heavy metal contaminated soils.

PubMed

Yang, Zhihui; Shi, Wei; Yang, Weichun; Liang, Lifen; Yao, Wenbin; Chai, Liyuan; Gao, Shikang; Liao, Qi

2018-09-01

Combining bioleaching by the gross biosurfactants of Burkholderia sp. Z-90 and flocculation by poly aluminium chloride (PAC) was proposed to develop a potential environment-friendly and cost-effective technique to remediate the severely contaminated soils by heavy metals. The factors affecting soil bioleaching by the gross biosurfactants of Burkholderia sp. Z-90 were optimized. The results showed the optimal removing efficiencies of Zn, Pb, Mn, Cd, Cu, and As by the Burkholderia sp. Z-90 leachate were 44.0, 32.5, 52.2, 37.7, 24.1 and 31.6%, respectively at soil liquid ratio of 1:20 (w/v) for 5 d, which were more efficient than that by 0.1% of rhamnolipid. The amounts of the bioleached heavy metals by the Burkholderia sp. Z-90 leachate were higher than that by other biosurfactants in the previous studies, although the removal efficiencies of the metals by the leachate were relatively lower. It was suggested that more heavy metals caused more competitive to chelate with function groups of the gross biosurfactants and the metal removal efficiencies by biosurfactants in natural soils were lower than in the artificially contaminated soils. Moreover, the Burkholderia sp. Z-90 leachate facilitated the metals to be transformed to the easily migrating speciation fractions. Additional, the results showed that PAC was efficient in the following flocculation to remove heavy metals in the waste bio-leachates. Our study will provide support for developing a bioleaching technique model to remediate the soils extremely contaminated by heavy metals. Copyright © 2018 Elsevier Ltd. All rights reserved.

Geochemical speciation and pollution assessment of heavy metals in surface sediments from Nansi Lake, China.

PubMed

Yang, Liyuan; Wang, Longfeng; Wang, Yunqian; Zhang, Wei

2015-05-01

Sixteen surface sediment samples were collected from Nansi Lake to analyze geochemical speciation of heavy metals including Cd, As, Pb, Cr, and Zn, assess their pollution level, and determine the spatial distribution of the non-residual fraction. Results showed that Cd had higher concentrations in water-soluble and exchangeable fractions. As and Pb were mainly observed as humic acid and reducible fractions among the non-residual fractions, while Cr and Zn were mostly locked up in a residual fraction. The mean pollution index (P i) values revealed that the lower lake generally had a higher enrichment degree than the upper lake. Cd (2.73) and As (2.05) were in moderate level of pollution, while the pollution of Pb (1.80), Cr (1.27), and Zn (1.02) appeared at low-level pollution. The calculated pollution load index (PLI) suggested the upper lake suffered from borderline moderate pollution, while the lower lake showed moderate to heavy pollution. Spatial principle component analysis showed that the first principal component (PC1) including Cd, As, and Pb could explain 56.18 % of the non-residual fraction. High values of PC1 were observed mostly in the southern part of Weishan Lake, which indicated greater bioavailability and toxicity of Cd, As, and Pb in this area.

Soil-solution speciation of Cd as affected by soil characteristics in unpolluted and polluted soils.

PubMed

Meers, Erik; Unamuno, Virginia; Vandegehuchte, Michiel; Vanbroekhoven, Karolien; Geebelen, Wouter; Samson, Roeland; Vangronsveld, Jaco; Diels, Ludo; Ruttens, Ann; Du Laing, Gijs; Tack, Filip

2005-03-01

Total metal content by itself is insufficient as a measure to indicate actual environmental risk. Understanding the mobility of heavy metals in the soil and their speciation in the soil solution is of great importance for accurately assessing environmental risks posed by these metals. In a first explorative study, the effects of general soil characteristics on Cd mobility were evaluated and expressed in the form of empirical formulations. The most important factors influencing mobility of Cd proved to be pH and total soil content. This may indicate that current legislation expressing the requirement for soil sanitation in Flanders (Belgium) as a function of total soil content, organic matter, and clay does not successfully reflect actual risks. Current legal frameworks focusing on total content, therefore, should be amended with criteria that are indicative of metal mobility and availability and are based on physicochemical soil properties. In addition, soil-solution speciation was performed using two independent software packages (Visual Minteq 2.23 and Windermere Humic Aqueous model VI [WHAM VI]). Both programs largely were in agreement in concern to Cd speciation in all 29 soils under study. Depending on soil type, free ion and the organically complexed forms were the most abundant species. Additional inorganic soluble species were sulfates and chlorides. Minor species in solution were in the form of nitrates, hydroxides, and carbonates, the relative importance of which was deemed insignificant in comparison to the four major species.

Heavy metal concentrations and speciation in riverine sediments and the risks posed in three urban belts in the Haihe Basin.

PubMed

Zhang, Chao; Shan, Baoqing; Tang, Wenzhong; Dong, Lixin; Zhang, Wenqiang; Pei, Yuansheng

2017-05-01

Heavy metal (Cr, Cu, Ni, Pb, and Zn) pollution and the risks posed by the heavy metals in riverine sediments in a mountainous urban-belt area (MB), a mountain-plain urban-belt area (MPB), and a plain urban-belt area (PB) in the Haihe Basin, China, were assessed. The enrichment factors indicated that the sediments were more polluted with Cu and Zn than with the other metals, especially in the MPB. The sediments in the MPB were strongly affected by Cu and Zn inputs from anthropogenic sources. The risk assessment codes and individual contamination factors showed that Zn was mobile and posed ecological risks, the exchangeable fractions being 21.1%, 21.2%, and 19.2% of the total Zn concentrations in the samples from the MB, MPB, and PB, respectively. Cr, Cu, and Zn in the sediments from the MPB were potentially highly bioavailable because the non-residual fractions were 56.2%, 54.9%, and 56.5%, respectively, of the total concentrations. The potential risks posed by the heavy metals (determined from the chemical fractions of the heavy metals) in the different areas generally decreased in the order MPB > MB > PB. Pictorial representation of cluster analysis results showed that urbanization development level could cause Cr and Zn pollution in the urban riverine sediments to become more severe. Copyright © 2017 Elsevier Inc. All rights reserved.

A Novel Permeable Reactive Barrier (PRB) for Simultaneous and Rapid Removal of Heavy Metal and Organic Matter - A Systematic Chemical Speciation Approach on Sustainable Technique for Pallikarani Marshland Remediation

NASA Astrophysics Data System (ADS)

Selvaraj, A.; Nambi, I. M.

2014-12-01

In this study, an innovative technique of ZVI mediated 'coupling of Fenton like oxidation of phenol and Cr(VI) reduction technique' was attempted. The hypothesis is that Fe3+ generated from Cr(VI) reduction process acts as electron acceptor and catalyst for Fenton's Phenol oxidation process. The Fe2+ formed from Fenton reactions can be reused for Cr(VI) reduction. Thus iron can be made to recycle between two reactions, changing back and forth between Fe2+ and Fe3+ forms, makes treatment sustainable.(Fig 1) This approach advances current Fenton like oxidation process by (i)single system removal of heavy metal and organic matter (ii)recycling of iron species; hence no additional iron required (iii)more contaminant removal to ZVI ratio (iv)eliminating sludge related issues. Preliminary batch studies were conducted at different modes i) concurrent removal ii) sequential removal. The sequential removal was found better for in-situ PRB applications. PRB was designed based on kinetic rate slope and half-life time, obtained from primary column study. This PRB has two segments (i)ZVI segment[Cr(VI)] (ii)iron species segment[phenol]. This makes treatment sustainable by (i) having no iron ions in outlet stream (ii)meeting hypothesis and elongates the life span of PRB. Sequential removal of contaminates were tested in pilot scale PRB(Fig 2) and its life span was calculated based on the exhaustion of filling material. Aqueous, sand and iron aliquots were collected at various segments of PRB and analyzed for precipitation and chemical speciation thoroughly (UV spectrometer, XRD, FTIR, electron microscope). Chemical speciation profile eliminates the uncertainties over in-situ PRB's long term performance. Based on the pilot scale PRB study, 'field level PRB wall construction' was suggested to remove heavy metal and organic compounds from Pallikaranai marshland(Fig 3)., which is contaminated with leachate coming from nearby Perungudi dumpsite. This research provides (i)deeper insight into the environmental friendly, accelerated, sustainable technique for combined removal of organic matter and heavy metal (ii)evaluation of the novel technique in PRB, which resulted in PRB's increased life span (iii)designing of PRB to remediate the marshland and its ecosystem, thus save the habitats related to it.

[Immobilization remediation of Cd and Pb contaminated soil: remediation potential and soil environmental quality].

PubMed

Sun, Yue-Bing; Wang, Peng-Chao; Xu, Ying-Ming; Sun, Yang; Qin, Xu; Zhao, Li-Jie; Wang, Lin; Liang, Xue-Feng

2014-12-01

A pot experiment was conducted to investigate the immobilization remediation effects of sepiolite on soils artificially combined contamination by Cd and Pb using a set of various pH and speciation of Cd and Pb in soil, heavy metal concentration in Oryza sativa L., and soil enzyme activity and microbial quantity. Results showed that the addition of sepiolite increased the soil pH, and the exchangeable fraction of heavy metals was converted into Fe-Mn oxide, organic and residual forms, the concentration of exchangeable form of Cd and Pb reduced by 1.4% - 72.9% and 11.8% - 51.4%, respectively, when compared with the control. The contents of heavy metals decreased with increasing sepiolite, with the maximal Cd reduction of 39.8%, 36.4%, 55.2% and 32.4%, respectively, and 22.1%, 54.6%, 43.5% and 17.8% for Pb, respectively, in the stems, leaves, brown rice and husk in contrast to CK. The addition of sepiolite could improve the soil environmental quality, the catalase and urease activities and the amount of bacteria and actinomycete were increased to some extents. Although the fungi number and invertase activity were inhibited compared with the control group, it was not significantly different (P > 0.05). The significant correlation between pH, available heavy metal content, urease and invertase activities and heavy metal concentration in the plants indicated that these parameters could be used to evaluate the effectiveness of stabilization remediation of heavy metal contaminated soil.

[XANES study of lead speciation in duckweed].

PubMed

Chu, Bin-Bin; Luo, Li-Qiang; Xu, Tao; Yuan, Jing; Sun, Jian-Ling; Zeng, Yuan; Ma, Yan-Hong; Yi, Shan

2012-07-01

Qixiashan lead-zinc mine of Nanjing was one of the largest lead zinc deposits in East China Its exploitation has been over 50 years, and the environmental pollution has also been increasing. The lead concentration in the local environment was high, but lead migration and toxic mechanism has not been clear. Therefore, biogeochemistry research of the lead zinc mine was carried out. Using ICP-MS and Pb-L III edge XANES, lead concentration and speciation were analyzed respectively, and duckweed which can tolerate and enriched heavy metals was found in the pollution area. The results showed that the lead concentration of duckweed was 39.4 mg x kg(-1). XANES analysis and linear combination fit indicated that lead stearate and lead sulfide accounted for 65% and 36.9% respectively in the lead speciation of duckweed, suggesting that the main lead speciation of duckweed was sulfur-containing lead-organic acid.

Chemical fractionation of heavy metals in urban soils of Guangzhou, China.

PubMed

Lu, Ying; Zhu, Feng; Chen, Jie; Gan, Haihua; Guo, Yanbiao

2007-11-01

Knowledge of the total concentration of heavy metals is not enough to fully assess the environmental impact of urban soils. For this reason, the determination of metal speciation is important to evaluate their environment and the mobilization capacity. Sequential extraction technique proposed by the former European Community Bureau of Reference (BCR) was used to speciate Cd, Cu, Fe, Mn, Ni, Pb, and Zn in urban soils from Guangzhou into four operationally defined fractions: HOAc extractable, reducible, oxidizable, and residual. The Cu, Fe, Ni, and Zn were predominantly located in the residual fraction, Pb in the reducible fraction, and Cd and Mn within the HOAc extractable fraction. The order of Cd in each fraction was generally HOAc extractable > reducible > residual > oxidizable; Cu and Fe were residual > reducible > oxidizable > HOAc extractable; Mn was HOAc extractable > residual > reducible > oxidizable; Ni and Zn were residual > reducible > HOAc extractable > oxidizable; and Pb was reducible > residual > oxidizable > HOAc extractable. Cadmium was identified as being the most mobile of the elements, followed by Mn, Zn, Ni, Cu, Pb and Fe. Iron-Mn oxides can play an important role in binding Cd, Cu, Ni, Pb, and Zn and in decreasing their proportion associated with the residual fraction in the soils. With total concentrations of Cd, Cu, Ni, Pb, Zn, and Mn increase, these metals more easily release and may produce more negative effects on the urban environment.

Insights into aquatic toxicities of the antibiotics oxytetracycline and ciprofloxacin in the presence of metal: complexation versus mixture.

PubMed

Zhang, Yu; Cai, Xiyun; Lang, Xianming; Qiao, Xianliang; Li, Xuehua; Chen, Jingwen

2012-07-01

Co-contamination of ligand-like antibiotics (e.g., tetracyclines and quinolones) and heavy metals prevails in the environment, and thus the complexation between them is involved in environmental risks of antibiotics. To understand toxicological significance of the complex, effects of metal coordination on antibiotics' toxicity were investigated. The complexation of two antibiotics, oxytetracycline and ciprofloxacin, with three heavy metals, copper, zinc, and cadmium, was verified by spectroscopic techniques. The antibiotics bound metals via multiple coordination sites and rendered a mixture of various complexation speciations. Toxicity analysis indicated that metal coordination did modify the toxicity of the antibiotics and that antibiotic, metal, and their complex acted primarily as concentration addition. Comparison of EC(50) values revealed that the complex commonly was highest toxic and predominately correlated in toxicity to the mixture. Finally, environmental scenario analysis demonstrated that ignoring complexation would improperly classify environmental risks of the antibiotics. Copyright © 2012 Elsevier Ltd. All rights reserved.

Speciation of the trivalent f-elements Eu(III) and Cm(III) in digestive media.

PubMed

Wilke, Claudia; Barkleit, Astrid; Stumpf, Thorsten; Ikeda-Ohno, Atsushi

2017-10-01

In case radioactive materials are released into the environment, their incorporation into our digestive system would be a significant concern. Trivalent f-elements, i.e., trivalent actinides and lanthanides, could potentially represent a serious health risk due to their chemo- and radiotoxicity, nevertheless the biochemical behavior of these elements are mostly unknown even to date. This study, therefore, focuses on the chemical speciation of trivalent f-elements in the human gastrointestinal tract. To simulate the digestive system artificial digestive juices (saliva, gastric juice, pancreatic juice and bile fluid) were prepared. The chemical speciation of lanthanides (as Eu(III)) and actinides (as Cm(III)) was determined experimentally by time-resolved laser-induced fluorescence spectroscopy (TRLFS) and the results were compared with thermodynamic modeling. The results indicate a dominant inorganic species with phosphate/carbonate in the mouth, while the aquo ion is predominantly formed with a minor contribution of the enzyme pepsin in the stomach. In the intestinal tract the most significant species are with the protein mucin. We demonstrated the first experimental results on the chemical speciation of trivalent f-elements in the digestive media by TRLFS. The results highlight a significant gap in chemical speciation between experiments and thermodynamic modeling due to the limited availability of thermodynamic stability constants particularly for organic species. Chemical speciation strongly influences the in vivo behavior of metal ions. Therefore, the results of this speciation study will help to enhance the assessment of health risks and to improve decorporation strategies after ingestion of these (radio-)toxic heavy metal ions. Copyright © 2017 Elsevier Inc. All rights reserved.

Exploiting the genetic and biochemical capacities of bacteria for the remediation of heavy metal pollution.

PubMed

Valls, Marc; de Lorenzo, Víctor

2002-11-01

The threat of heavy metal pollution to public health and wildlife has led to an increased interest in developing systems that can remove or neutralise its toxic effects in soil, sediments and wastewater. Unlike organic contaminants, which can be degraded to harmless chemical species, heavy metals cannot be destroyed. Remediating the pollution they cause can therefore only be envisioned as their immobilisation in a non-bioavailable form, or their re-speciation into less toxic forms. While these approaches do not solve the problem altogether, they do help to protect afflicted sites from noxious effects and isolate the contaminants as a contained and sometimes recyclable residue. This review outlines the most important bacterial phenotypes and properties that are (or could be) instrumental in heavy metal bioremediation, along with what is known of their genetic and biochemical background. A variety of instances are discussed in which valuable properties already present in certain strains can be combined or improved through state-of-the-art genetic engineering. In other cases, knowledge of metal-related reactions catalysed by some bacteria allows optimisation of the desired process by altering the physicochemical conditions of the contaminated area. The combination of genetic engineering of the bacterial catalysts with judicious eco-engineering of the polluted sites will be of paramount importance in future bioremediation strategies.

Comparison of leaching characteristics of heavy metals in APC residue from an MSW incinerator using various extraction methods.

PubMed

Chiang, Kung-Yuh; Tsai, Chen-Chiu; Wang, Kuen-Sheng

2009-01-01

This study investigates four extraction methods (water extraction, toxicity characteristics leaching procedure (TCLP), modified TCLP with pH control, and sequential chemical extraction (SCE)), each representing different liquid-to-solid (L/S) ratios, pH controls, and types of leachant, and their effects on the leaching concentration of heavy metals in municipal solid waste (MSW) incinerator air pollution control (APC) residue. The results indicated that for extraction with distilled water, the heavy metal leaching concentration (mg/l) decreased with L/S ratio, but the amount of heavy metal released (AHMR), defined as the leached amount of heavy metals to the weight of the tested sample (mg/kg), increased with an increase in L/S ratio, in the range of 2-100. The results also showed that both the leaching concentration and the amount of released metals were strongly pH-dependent in the TCLP and modified TCLP tests. In the case of pHs lower than 6.5, the leaching concentrations of Cd, Pb, Cu, Zn, and Cr decreased with an increase in pH. As pH increased higher than 6.5, Cr and Zn were almost insoluble. Meanwhile, Cd and Cu also showed a similar trend but at pHs of 8.5 and 7.5, respectively. Due to the nature of amphoteric elements, in the case of pHs higher than 7, the Pb leaching concentration increased with increasing pH. In modified TCLP tests with the pH value controlled at the same level as in the SCE test, the heavy metal speciation approached the extractable carbonate bound fraction by the SCE. Both amounts of targeted metals leached from the SCE and modified TCLP tests were much higher than those for the regular TCLP and water extraction tests.

[Remediation efficiency of lead-contaminated soil at an industrial site by ultrasonic-assisted chemical extraction].

PubMed

Wang, Xin-jie; Huang, Jin-lou; Liu, Zhi-qiang; Yue, Xi

2013-09-01

This research chose five lead-contaminated sites of a lead-acid battery factory to analyze the speciation distribution and concentration of lead. Under the same conditions (0.1 mol x L(-1) EDTA,30 min, 25 degrees C), the removal effect of heavy metal was compared between ultrasonic-assisted chemical extraction (UCE) and conventional chemical extraction ( CCE), and the variation of lead speciation was further explored. The results showed that the lead removal efficiency of UCE was significantly better than CCE. The lead removal efficiency of WS, A, B, C and BZ was 10.06%, 48.29%, 48.69%, 53.28% and 36.26% under CCE. While the removal efficiency of the UCE was 22.42%, 69.31%, 71.00%, 74.49% and 71.58%, with the average efficiency higher by 22%. By comparing the speciation distribution of the two washing methods, it was found that the acid extractable content maintained or decreased after UCE, whereas it showed an increasing trend after CCE. The reduction effect of the reducible was as high as 98% by UCE. UCE also showed a more efficient reduction effect of the organic matter-sulfite bounded form and the residual form. Hence, it is feasible to improve the washing efficiency of heavy metal contained in soil by conducting the cleaning process with the help of ultrasonic wave, which is a simple and fast mean to remove lead from contaminated sites.

Heavy metals in the volcanic environment and thyroid cancer.

PubMed

Vigneri, R; Malandrino, P; Gianì, F; Russo, M; Vigneri, P

2017-12-05

In the last two decades thyroid cancer incidence has increased worldwide more than any other cancer. Overdiagnosis of subclinical microcarcinomas has certainly contributed to this increase but many evidences indicate that a true increase, possibly due to environmental factors, has also occurred. Thyroid cancer incidence is markedly increased in volcanic areas. Thus, the volcanic environment is a good model to investigate the possible factors favoring thyroid cancer. In the volcanic area of Mt. Etna in Sicily, as well as in other volcanic areas, a non-anthropogenic pollution with heavy metals has been documented, a consequence of gas, ash and lava emission. Soil, water and atmosphere contamination, via the food chain, biocontaminate the residents as documented by high levels in the urines and the scalp hair compared to individuals living in adjacent non-volcanic areas. Trace amounts of metals are essential nutrients but, at higher concentrations, can be toxic for living cells. Metals can behave both as endocrine disruptors, perturbing the hormonal system, and as carcinogens, promoting malignant transformation. Similarly to other carcinogens, the transforming effect of heavy metals is higher in developing organisms as the fetus (contaminated via the mother) and individuals in early childhood. In the last decades environment metal pollution has greatly increased in industrialized countries. Although still within the "normal" limits for each single metal the hormesis effect (heavy metal activity at very low concentration because of biphasic, non linear cell response) and the possible potentiation effect resulting from the mixture of different metals acting synergistically can explain cell damage at very low concentrations. The effect of metals on the human thyroid is poorly studied: for some heavy metals no data are available. The scarce studies that have been performed mainly focus on metal effect as thyroid endocrine disruptors. The metal concentration in tissues has been rarely measured in the thyroid. Heavy metal accumulation and metabolism in the thyroid or the carcinogenic activity of different doses and different speciation of metals has not been investigated. These studies are now warranted to better understand thyroid biology and heavy metal role in human thyroid carcinogenesis. Copyright © 2016 Elsevier Ireland Ltd. All rights reserved.

Stabilization of heavy metals in MSWI fly ash using silica fume

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

Li, Xinying; Chen, Quanyuan; State Environmental Protection Engineering Center for Pollution Treatment and Control in Textile Industry, Donghua University, Shanghai 201620

Highlights: • The stabilization of heavy metals in MSWI fly ash was investigated. • The addition of silica fume effectively reduced the leaching of Pb and Cd. • The relation of solid phase transformation and leaching behavior of heavy metals was discussed. - Abstract: The objective of this work was to investigate the feasibility and effectiveness of silica fume on stabilizing heavy metals in municipal solid waste incineration (MSWI) fly ash. In addition to compressive strength measurements, hydrated pastes were characterized by X-ray diffraction (XRD), thermal-analyses (DTA/TG), and MAS NMR ({sup 27}Al and {sup 29}Si) techniques. It was found thatmore » silica fume additions could effectively reduce the leaching of toxic heavy metals. At the addition of 20% silica fume, leaching concentrations for Cu, Pb and Zn of the hydrated paste cured for 7 days decreased from 0.32 mg/L to 0.05 mg/L, 40.99 mg/L to 4.40 mg/L, and 6.96 mg/L to 0.21 mg/L compared with the MSWI fly ash. After curing for 135 days, Cd and Pb in the leachates were not detected, while Cu and Zn concentrations decreased to 0.02 mg/L and 0.03 mg/L. The speciation of Pb and Cd by the modified version of the European Community Bureau of Reference (BCR) extractions showed that these metals converted into more stable state in hydrated pastes of MSWI fly ash in the presence of silica fume. Although exchangeable and weak-acid soluble fractions of Cu and Zn increased with hydration time, silica fume addition of 10% can satisfy the requirement of detoxification for heavy metals investigated in terms of the identification standard of hazardous waste of China.« less

The effects of artificial ageing on the leaching behaviour of heavy metals in stabilized/solidified industrial sludge.

PubMed

Keskes, M; Choura, M; Rouis, J

2009-12-01

The use of a hydraulic binder for the treatment of mineral-based industrial wastes, containing heavy metals, by the chemical fixation and solidification (CFS) technique has raised serious questions regarding the prediction of the behaviour of these pollutants in the obtained solid matrix. It seems necessary, for this reason, to study the behaviour of these metals in response to leaching in order to evaluate their chemical speciation within the solidified sludge over the medium and long-terms. Within the framework of the current research, we applied the CFS technique to metallic hydroxide sludge, produced by the electrotyping surface treatment industry, by using Portland artificial cement (PAC). Compaction at the paste phase of this treated sludge resulted in up to 35% enhancement of the retention of pollutants, mainly trivalent chromium, in a cementing matrix, as compared with the classical technique that uses a simple vibration of sludge at the paste phase. The implemented process led to an improvement in the compactness of the sludge, and thus assured a better retention of heavy metals in response to the leaching of this treated sludge. The evaluation of the chemical properties of the materials obtained after an artificial ageing process using humidity variation cycles and thermal chocks also revealed a significant improvement in the retention capacity of heavy metals in the solidified sludge, which was mainly favoured by the development of carbonation. In fact, the release of the heavy metals from the above mentioned treated sludge was reduced by 58% for zinc and 51% for trivalent chromium after the artificial ageing process.

Fate of Metals in Relation to Water and Sediment Properties in a Subtropical Lake in Central Himalaya, India.

PubMed

Inaotombi, Shaikhom; Gupta, Prem Kumar

2017-04-01

Lakes of Himalaya are one of the most fragile ecosystems on earth. Tourism and urban development in the upland region strongly affect its water resources. The high rate of sedimentation and organic matter deposition alters the ecological state of sediment bed, which indirectly influences on dynamics of metallic elements. We investigated spatial and temporal variations of water and sediment characteristic in Lake Sattal of Central Himalaya, India. Samples were collected seasonally from four sampling locations from January 2011 to December 2012. Pearson's correlation and Canonical correspondence analysis (CCAs) were applied to examine the dynamics and behaviors of heavy metals. Concentrations of elements were in the order of fluoride (Fl) > zinc (Zn) > copper (Cu) > iron (Fe) > manganese (Mn). Sand size fraction was higher in the littoral zone while clay particle was dominant in the profundal zone of the lake. Dissolved oxygen at sediment-water-interface (SWI) and water temperature were the major factors influencing the dynamics of metallic contents in the water column. Spatially, total organic matter (TOM) was higher in the deeper portion of the lake. Our study revealed that mobility of Fe is temperature-dependent, whereas speciation of Mn and Cu are primarily controlled by the suboxic condition of SWI in organic-rich site. Upland lakes are more vulnerable to anoxic condition and have severe implications on heavy metals speciation. Proper implementation of land use policies and management practices, including stormwater detention, can be integrated into resolving such problems.

Chelant extraction of heavy metals from contaminated soils.

PubMed

Peters, R W

1999-04-23

The current state of the art regarding the use of chelating agents to extract heavy metal contaminants has been addressed. Results are presented for treatability studies conducted as worst-case and representative soils from Aberdeen Proving Ground's J-Field for extraction of copper (Cu), lead (Pb), and zinc (Zn). The particle size distribution characteristics of the soils determined from hydrometer tests are approximately 60% sand, 30% silt, and 10% clay. Sequential extractions were performed on the 'as-received' soils (worst case and representative) to determine the speciation of the metal forms. The technique speciates the heavy metal distribution into an easily extractable (exchangeable) form, carbonates, reducible oxides, organically-bound, and residual forms. The results indicated that most of the metals are in forms that are amenable to soil washing (i.e. exchangeable+carbonate+reducible oxides). The metals Cu, Pb, Zn, and Cr have greater than 70% of their distribution in forms amenable to soil washing techniques, while Cd, Mn, and Fe are somewhat less amenable to soil washing using chelant extraction. However, the concentrations of Cd and Mn are low in the contaminated soil. From the batch chelant extraction studies, ethylenediaminetetraacetic acid (EDTA), citric acid, and nitrilotriacetic acid (NTA) were all effective in removing copper, lead, and zinc from the J-Field soils. Due to NTA being a Class II carcinogen, it is not recommended for use in remediating contaminated soils. EDTA and citric acid appear to offer the greatest potential as chelating agents to use in soil washing the Aberdeen Proving Ground soils. The other chelating agents studied (gluconate, oxalate, Citranox, ammonium acetate, and phosphoric acid, along with pH-adjusted water) were generally ineffective in mobilizing the heavy metals from the soils. The chelant solution removes the heavy metals (Cd, Cu, Pb, Zn, Fe, Cr, As, and Hg) simultaneously. Using a multiple-stage batch extraction, the soil was successfully treated passing both the Toxicity Characteristics Leaching Procedure (TCLP) and EPA Total Extractable Metal Limit. The final residual Pb concentration was about 300 mg/kg, with a corresponding TCLP of 1.5 mg/l. Removal of the exchangeable and carbonate fractions for Cu and Zn was achieved during the first extraction stage, whereas it required two extraction stages for the same fractions for Pb. Removal of Pb, Cu, and Zn present as exchangeable, carbonates, and reducible oxides occurred between the fourth- and fifth-stage extractions. The overall removal of copper, lead, and zinc from the multiple-stage washing were 98.9%, 98.9%, and 97.2%, respectively. The concentration and operating conditions for the soil washing extractions were not necessarily optimized. If the conditions had been optimized and using a more representative Pb concentration (approximately 12000 mg/kg), it is likely that the TCLP and residual heavy metal soil concentrations could be achieved within two to three extractions. The results indicate that the J-Field contaminated soils can be successfully treated using a soil washing technique. Copyright 1999 Published by Elsevier Science B.V.

Bunker Hill Sediment Characterization Study

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

Neal A. Yancey; Debby F. Bruhn

2009-12-01

The long history of mineral extraction in the Coeur d’Alene Basin has left a legacy of heavy metal laden mine tailings that have accumulated along the Coeur d’Alene River and its tributaries (U.S. Environmental Protection Agency, 2001; Barton, 2002). Silver, lead and zinc were the primary metals of economic interest in the area, but the ores contained other elements that have become environmental hazards including zinc, cadmium, lead, arsenic, nickel, and copper. The metals have contaminated the water and sediments of Lake Coeur d’Alene, and continue to be transported downstream to Spokane Washington via the Spokane River. In 1983, themore » EPA listed the Bunker Hill Mining and Metallurgical Complex on the National Priorities List. Since that time, many of the most contaminated areas have been stabilized or isolated, however metal contaminants continue to migrate through the basin. Designation as a Superfund site causes significant problems for the economically depressed communities in the area. Identification of primary sources of contamination can help set priorities for cleanup and cleanup options, which can include source removal, water treatment or no action depending on knowledge about the mobility of contaminants relative to water flow. The mobility of contaminant mobility under natural or engineered conditions depends on multiple factors including the physical and chemical state (or speciation) of metals and the range of processes, some of which can be seasonal, that cause mobilization of metals. As a result, it is particularly important to understand metal speciation (National Research Council, 2005) and the link between speciation and the rates of metal migration and the impact of natural or engineered variations in flow, biological activity or water chemistry.« less

Enhanced stabilization of Pb, Zn, and Cd in contaminated soils using oxalic acid-activated phosphate rocks.

PubMed

Zhang, Zhuo; Guo, Guanlin; Wang, Mei; Zhang, Jia; Wang, Zhixin; Li, Fasheng; Chen, Honghan

2018-01-01

Phosphate amendments, especially phosphate rock (PR), are one of the most commonly used materials to stabilize heavy metals in contaminated soils. However, most of PR reserve consists of low-grade ore, which limits the efficiency of PR for stabilizing heavy metals. This study was to enhance the stabilization of heavy metals through improving the available phosphorous (P) release of PR by oxalic acid activation. Raw PR and activated PR (APR) were characterized by scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM-EDS), X-ray powder diffraction (XRD), Brunauer-Emmett-Teller (BET) surface analysis, and laser diffraction to determine the changes of structure and composition of APR. The stabilization effectiveness of lead (Pb), zinc (Zn), and cadmium (Cd) in soils by APR was investigated through toxicity leaching test and speciation analysis. The results indicated that after treatment by oxalic acid, (1) the crystallinity of the fluorapatite phase of PR transformed into the weddellite phase; (2) the surface area of PR increased by 37%; (3) the particle size of PR became homogenized (20-70 μm); and (4) the available P content in PR increased by 22 times. These changes of physicochemical characteristics of PR induced that APR was more effective to transform soil heavy metals from the non-residual fraction to the residual fraction and enhance the stabilization efficiency of Pb, Zn, and Cd than PR. These results are significant for the future use of low-grade PR to stabilize heavy metals.

Geochemical distribution, fractionation and contamination assessment of heavy metals in marine sediments of the Asaluyeh port, Persian Gulf.

PubMed

Delshab, Hossein; Farshchi, Parvin; Keshavarzi, Behnam

2017-02-15

In this study, total concentration and speciation of heavy metals in sediments of the Asaluyeh, one of the Iran's largest commercial ports, are investigated. 48 sediment samples were collected and analyzed for trace and major elements. Sediment quality guidelines along with calculated enrichment factors and trace metal profiles indicate that Asaluyeh port is threated by contamination, especially with respect to Hg and Cu. Normalization to Sc indicated high enrichment factors in the sediments following the decreasing order of: Hg>Cu>As>Ni>Zn>Pb≈Cr≈Mn>Co≈V≈Fe≈Al. Hg displayed the greatest potential ecological risk factor among sampling stations. The results of sequential extraction procedure revealed that in some stations >50% of Mn, V, Cu and Zn occur in potentially mobile phases and therefore are more readily mobilized in the sediments of the study area. Copyright © 2016 Elsevier Ltd. All rights reserved.

Dissolved and labile concentrations of Cd, Cu, Pb, and Zn in the South Fork Coeur d'Alene River, Idaho: Comparisons among chemical equilibrium models and implications for biotic ligand models

USGS Publications Warehouse

Balistrieri, L.S.; Blank, R.G.

2008-01-01

In order to evaluate thermodynamic speciation calculations inherent in biotic ligand models, the speciation of dissolved Cd, Cu, Pb, and Zn in aquatic systems influenced by historical mining activities is examined using equilibrium computer models and the diffusive gradients in thin films (DGT) technique. Several metal/organic-matter complexation models, including WHAM VI, NICA-Donnan, and Stockholm Humic model (SHM), are used in combination with inorganic speciation models to calculate the thermodynamic speciation of dissolved metals and concentrations of metal associated with biotic ligands (e.g., fish gills). Maximum dynamic metal concentrations, determined from total dissolved metal concentrations and thermodynamic speciation calculations, are compared with labile metal concentrations measured by DGT to assess which metal/organic-matter complexation model best describes metal speciation and, thereby, biotic ligand speciation, in the studied systems. Results indicate that the choice of model that defines metal/organic-matter interactions does not affect calculated concentrations of Cd and Zn associated with biotic ligands for geochemical conditions in the study area, whereas concentrations of Cu and Pb associated with biotic ligands depend on whether the speciation calculations use WHAM VI, NICA-Donnan, or SHM. Agreement between labile metal concentrations and dynamic metal concentrations occurs when WHAM VI is used to calculate Cu speciation and SHM is used to calculate Pb speciation. Additional work in systems that contain wide ranges in concentrations of multiple metals should incorporate analytical speciation methods, such as DGT, to constrain the speciation component of biotic ligand models. ?? 2008 Elsevier Ltd.

Modelling the leaching of Pb, Cd, As, and Cr from cementitious waste using PHREEQC.

PubMed

Halim, Cheryl E; Short, Stephen A; Scott, Jason A; Amal, Rose; Low, Gary

2005-10-17

A leaching model was developed using the United States Geological Survey public domain PHREEQC geochemical package to simulate the leaching of Pb, Cd, As, and Cr from cementitious wastes. The model utilises both kinetic terms and equilibrium thermodynamics of key compounds and provides information on leachate and precipitate speciation. The model was able to predict the leaching of Pb, Cd, As, and Cr from cement in the presence of both simple (0.1 and 0.6M acetic acid) and complex municipal landfill leachates. Heavy metal complexation by the municipal landfill leachate was accounted for by the introduction of a monoprotic organic species into the model. The model indicated Pb and As were predominantly incorporated within the calcium silicate hydrate matrix while a greater portion of Cd was seen to exist as discrete particles in the cement pores and Cr (VI) existed mostly as free CrO4(2-) ions. Precipitation was found to be the dominant mechanism controlling heavy metal solubility with carbonate and silicate species governing the solubility of Pb and carbonate, silicate and hydroxide species governing the solubility of Cd. In the presence of acetic acid, at low pH values Pb and Cd acetate complexes were predominant whereas, at high pH values, hydroxide species dominated. At high pH values, the concentration of As in the leachate was governed by the solubility of Ca3(AsO4)2 with the presence of carbonate alkalinity competing with arsenate for Ca ions. In the presence of municipal landfill leachate, Pb and Cd organic complexes dominated the heavy metal species in solution. The reduction of As and Cr in municipal landfill leachate was crucial for determining aqueous speciation, with typical municipal landfill conditions providing the reduced forms of As and Cr.

Assessment of the distribution, bioavailability and ecological risks of heavy metals in the lake water and surface sediments of the Caohai plateau wetland, China.

PubMed

Hu, Jing; Zhou, Shaoqi; Wu, Pan; Qu, Kunjie

2017-01-01

In this study, selected heavy metals (Hg, As, Cd, Pb, Cr, Cu and Zn) in the lake water and sediments from the Caohai wetland, which is a valuable state reserve for migrant birds in China, were investigated to assess the spatial distribution, sources, bioavailability and ecological risks. The results suggested that most of the higher concentrations were found in the eastern region of the lakeshore. The concentration factor (CF) revealed that Hg, Cd and Zn were present from moderate risk levels to considerable risk levels in this study; thus, based on the high pollution load index (PLI) values, the Caohai wetland can be considered polluted. According to the associated effects-range classification, Cd may present substantial environmental hazards. An investigation of the chemical speciation suggested that Cd and Zn were unstable across most of the sites, which implied a higher risk of quick desorption and release. Principal component analysis (PCA) indicated that the heavy metal contamination originated from both natural and anthropogenic sources.

Assessment of the distribution, bioavailability and ecological risks of heavy metals in the lake water and surface sediments of the Caohai plateau wetland, China

PubMed Central

Hu, Jing; Zhou, Shaoqi; Wu, Pan; Qu, Kunjie

2017-01-01

In this study, selected heavy metals (Hg, As, Cd, Pb, Cr, Cu and Zn) in the lake water and sediments from the Caohai wetland, which is a valuable state reserve for migrant birds in China, were investigated to assess the spatial distribution, sources, bioavailability and ecological risks. The results suggested that most of the higher concentrations were found in the eastern region of the lakeshore. The concentration factor (CF) revealed that Hg, Cd and Zn were present from moderate risk levels to considerable risk levels in this study; thus, based on the high pollution load index (PLI) values, the Caohai wetland can be considered polluted. According to the associated effects-range classification, Cd may present substantial environmental hazards. An investigation of the chemical speciation suggested that Cd and Zn were unstable across most of the sites, which implied a higher risk of quick desorption and release. Principal component analysis (PCA) indicated that the heavy metal contamination originated from both natural and anthropogenic sources. PMID:29253896

Heavy metal speciation in solid-phase materials from a bacterial sulfate reducing bioreactor using sequential extraction procedure combined with acid volatile sulfide analysis.

PubMed

Jong, Tony; Parry, David L

2004-04-01

Heavy metal mobility, bioavailability and toxicity depends largely on the chemical form of metals and ultimately determines potential for environmental pollution. For this reason, determining the chemical form of heavy metals and metalloids, immobilized in sludges by biological mediated sulfate reduction, is important to evaluate their mobility and bioavailability. A modified Tessier sequential extraction procedure (SEP), complemented with acid volatile sulfide (AVS) and simultaneous extracted metals (SEM) measurements, were applied to determine the partitioning of five heavy metals (defined as Fe, Ni, Zn and Cu, and the metalloid As) in anoxic solid-phase material (ASM) from an anaerobic, sulfate reducing bioreactor into six operationally defined fractions. These fractions were water soluble, exchangeable, bound to carbonates (acid soluble), bound to Fe-Mn oxides (reducible), bound to organic matter and sulfides (oxidizable) and residual. It was found that the distribution of Fe, Ni, Zn, Cu and As in ASM was strongly influenced by its association with the above solid fractions. The fraction corresponding to organic matter and sulfides appeared to be the most important scavenging phases of As, Fe, Ni, Zn and Cu in ASM (59.8-86.7%). This result was supported by AVS and SEM (Sigma Zn, Ni and Cu) measurements, which indicated that the heavy metals existed overwhelmingly as sulfides in the organic matter and sulfide fraction. A substantial amount of Fe and Ni at 16.4 and 20.1%, respectively, were also present in the carbonate fraction, while an appreciable portion of As (18.3%) and Zn (19.4%) was bound to Fe-Mn oxides. A significant amount of heavy metals was also associated with the residual fraction, ranging from 2.1% for Zn to 18.8% for As. Based on the average total extractable heavy metal (TEHM) values, the concentration of heavy metals in the ASM was in the order of Cu > Ni > Zn > Fe > As. If the mobility and bioavailability of heavy metals are assumed to be related to their solubility and chemical forms, and that they decrease with each successive extraction step, then the apparent mobility and bioavailability of these five heavy metals in ASM increase in the order of Cu < As < Ni < Fe < Zn. The SEM/AVS ratio was less than one in eight replicate ASM samples, indicating that the ASM was non-toxic with regards to having a low probability of bioavailable metals in the pore water.

Speciation and environmental risk assessment of heavy metal in bio-oil from liquefaction/pyrolysis of sewage sludge.

PubMed

Yuan, Xingzhong; Leng, Lijian; Huang, Huajun; Chen, Xiaohong; Wang, Hou; Xiao, Zhihua; Zhai, Yunbo; Chen, Hongmei; Zeng, Guangming

2015-02-01

Liquefaction bio-oil (LBO) produced with ethanol (or acetone) as the solvent and pyrolysis bio-oil (PBO) produced at 550°C (or 850°C) from sewage sludge (SS) were produced, and were characterized and evaluated in terms of their heavy metal (HM) composition. The total concentration, speciation and leaching characteristic of HMs (Cu, Cr, Pb, Zn, Cd, and Ni) in both LBO and PBO were investigated. The total concentration and exchangeable fraction of Zn and Ni in bio-oils were at surprisingly high levels. Quantitative risk assessment of HM in bio-oils was performed by the method of risk assessment code (RAC), potential ecological risk index (PERI) and geo-accumulation index (GAI). Ni in bio-oil produced by pyrolysis at 850°C (PBO850) and Zn in bio-oil by liquefaction at 360°C with ethanol as solvent (LBO-360E) were evaluated to possess very high risk to the environment according to RAC. Additionally, Cd in PBO850 and LBO-360E were evaluated by PERI to have very high risk and high risk, respectively, while Cd in all bio-oils was assessed moderately contaminated according to GAI. Copyright © 2014 Elsevier Ltd. All rights reserved.

The heavy metal partition in size-fractions of the fine particles in agricultural soils contaminated by waste water and smelter dust.

PubMed

Zhang, Haibo; Luo, Yongming; Makino, Tomoyuki; Wu, Longhua; Nanzyo, Masami

2013-03-15

The partitioning of pollutant in the size-fractions of fine particles is particularly important to its migration and bioavailability in soil environment. However, the impact of pollution sources on the partitioning was seldom addressed in the previous studies. In this study, the method of continuous flow ultra-centrifugation was developed to separate three size fractions (<1 μm, <0.6 μm and <0.2 μm) of the submicron particles from the soil polluted by wastewater and smelter dust respectively. The mineralogy and physicochemical properties of each size-fraction were characterized by X-ray diffraction, transmission electron microscope etc. Total content of the polluted metals and their chemical speciation were measured. A higher enrichment factor of the metals in the fractions of <1 μm or less were observed in the soil contaminated by wastewater than by smelter dust. The organic substance in the wastewater and calcite from lime application were assumed to play an important role in the metal accumulation in the fine particles of the wastewater polluted soil. While the metal accumulation in the fine particles of the smelter dust polluted soil is mainly associated with Mn oxides. Cadmium speciation in both soils is dominated by dilute acid soluble form and lead speciation in the smelter dust polluted soil is dominated by reducible form in all particles. This implied that the polluted soils might be a high risk to human health and ecosystem due to the high bioaccessibility of the metals as well as the mobility of the fine particles in soil. Copyright © 2013 Elsevier B.V. All rights reserved.

Chemical speciation and potential mobility of heavy metals in the soil of former tin mining catchment.

PubMed

Ashraf, M A; Maah, M J; Yusoff, I

2012-01-01

This study describes the chemical speciation of Pb, Zn, Cu, Cr, As, and Sn in soil of former tin mining catchment. Total five sites were selected for sampling and subsequent subsamples were collected from each site in order to create a composite sample for analysis. Samples were analysed by the sequential extraction procedure using optical emission spectrometry (ICP OES). Small amounts of Cu, Cr, and As retrieved from the exchangeable phase, the ready available for biogeochemical cycles in the ecosystem. Low quantities of Cu and As could be taken up by plants in these kind of acidic soils. Zn not detected in the bioavailable forms while Pb is only present in negligible amounts in very few samples. The absence of mobile forms of Pb eliminates the toxic risk both in the trophic chain and its migration downwards the soil profile. The results also indicate that most of the metals have high abundance in residual fraction indicating lithogenic origin and low bioavailability of the metals in the studied soil. The average potential mobility for the metals giving the following order: Sn > Cu > Zn > Pb > Cr > As.

Chemical Speciation and Potential Mobility of Heavy Metals in the Soil of Former Tin Mining Catchment

PubMed Central

Ashraf, M. A.; Maah, M. J.; Yusoff, I.

2012-01-01

This study describes the chemical speciation of Pb, Zn, Cu, Cr, As, and Sn in soil of former tin mining catchment. Total five sites were selected for sampling and subsequent subsamples were collected from each site in order to create a composite sample for analysis. Samples were analysed by the sequential extraction procedure using optical emission spectrometry (ICP OES). Small amounts of Cu, Cr, and As retrieved from the exchangeable phase, the ready available for biogeochemical cycles in the ecosystem. Low quantities of Cu and As could be taken up by plants in these kind of acidic soils. Zn not detected in the bioavailable forms while Pb is only present in negligible amounts in very few samples. The absence of mobile forms of Pb eliminates the toxic risk both in the trophic chain and its migration downwards the soil profile. The results also indicate that most of the metals have high abundance in residual fraction indicating lithogenic origin and low bioavailability of the metals in the studied soil. The average potential mobility for the metals giving the following order: Sn > Cu > Zn > Pb > Cr > As. PMID:22566758

Does biodiversity of macroinvertebrates and genome response of Chironomidae larvae (Diptera) reflect heavy metal pollution in a small pond?

PubMed

Michailova, Paraskeva; Warchałowska-Śliwa, Elzbieta; Szarek-Gwiazda, Ewa; Kownacki, Andrzej

2012-01-01

The investigation was carried out on a small pond situated on a recent mine spoil at Bolesław in the Olkusz region with Zn-Pb ore deposits. Water of the pond had pH 7.2-8.5 and low concentrations of heavy metals. Concentrations of Pb (487 μg g( - 1)) and Zn (1,991 μg g( - 1)) in the sediment were very high and potentially could lead to toxicological effects. In the pond, 48 taxa of macroinvertebrates belonging to Oligochaeta and water stages of Ephemeroptera, Odonata, Megaloptera, Trichoptera, Heteroptera, Coleoptera and Diptera (mainly Chironomidae family) were found. The influence of heavy metals on macroinvertebrates diversity was not found. Effect of heavy metal pollution was observed on the appearance of chromosome aberrations in the polytene chromosomes of Chironomidae larvae. It was manifested by two ways: (1) in Kiefferulus tendipediformis and Chironomus sp. chromosome rearrangements in fixed state (tandem fusion and homozygous inversions), indicated intensive process of speciation; (2) in Chironomus sp., K. tendipediformis, Glyptotendipes gripekoveni (Chironomidae) somatic chromosome rearrangements (inversions, deficiencies, specific puffs, polyploidy) affected few cells of every individual. The somatic functional and structural alterations in Chironomidae species are particular suitable as biomarkers-they can be easily identified and used for detecting toxic agents in the environment.

Stabilization of chromium-bearing electroplating sludge with MSWI fly ash-based Friedel matrices.

PubMed

Qian, Guangren; Yang, Xiaoyan; Dong, Shixiang; Zhou, Jizhi; Sun, Ying; Xu, Yunfeng; Liu, Qiang

2009-06-15

This work investigated the feasibility and effectiveness of MSWI fly ash-based Friedel matrices on stabilizing/solidifying industrial chromium-bearing electroplating sludge using MSWI fly ash as the main raw material with a small addition of active aluminum. The compressive strength, leaching behavior and chemical speciation of heavy metals and hydration phases of matrices were characterized by TCLP, XRD, FTIR and other experimental methods. The results revealed that MSWI fly ash-based Friedel matrices could effectively stabilize chromium-bearing electroplating sludge, the formed ettringite and Friedel phases played a significant role in the fixation of heavy metals in electroplating sludge. The co-disposal of chromium-bearing electroplating sludge and MSWI fly ash-based Friedel matrices with a small addition of active aluminum is promising to be an effective way of stabilizing chromium-bearing electroplating sludge.

Assessment of the hazard posed by metal forms in water and sediments.

PubMed

Wojtkowska, Małgorzata; Bogacki, Jan; Witeska, Anna

2016-05-01

This study aimed to describe the prevalence heavy metals (Zn, Cu, Pb, and Cd) forms in the ecosystem of the Utrata river in order to determine the mobile forms and bioavailability of metals. To extract the dissolved forms of metals in the water of the Utrata PHREEQC2 geochemical speciation model was used. The river waters show a high percentage of mobile and eco-toxic forms of Zn, Cu and Pb. The percentage of carbonate forms for all the studied metals was low (<1%). The content of carbonates in the water and the prevailing physical and chemical conditions (pH, hardness, alkalinity) reduce the share of toxic metal forms, which precipitate as hardly soluble carbonate salts of Zn, Cu, Cd and Pb. Cu in the water in 90% of cases appeared in the form of hydroxyl compounds. To identify the forms of metal occurrence in the sediments Tessier's sequential extraction was used, allowing to assay bound metals in five fractions (ion exchange, carbonate, adsorption, organic, residual), whose nature and bioavailability varies in aquatic environments. The study has shown a large share of metals in labile and bioavailable forms. The speciation analysis revealed an absolute dominance of the organic fraction in the binding of Cu and Pb. Potent affinity for this fraction was also exhibited by Cd. The rations of exchangeable Zn and Cu forms in the sediments were similar. Both these metals had the lowest share in the most mobile ion exchange fraction. Copyright © 2016. Published by Elsevier B.V.

Heavy metals in marine fish meat and consumer health: a review.

PubMed

Bosch, Adina C; O'Neill, Bernadette; Sigge, Gunnar O; Kerwath, Sven E; Hoffman, Louwrens C

2016-01-15

The numerous health benefits provided by fish consumption may be compromised by the presence of toxic metals and metalloids such as lead, cadmium, arsenic and mercury, which can have harmful effects on the human body if consumed in toxic quantities. The monitoring of metal concentrations in fish meat is therefore important to ensure compliance with food safety regulations and consequent consumer protection. The toxicity of these metals may be dependent on their chemical forms, which requires metal speciation processes for direct measurement of toxic metal species or the identification of prediction models in order to determine toxic metal forms from measured total metal concentrations. This review addresses various shortcomings in current knowledge and research on the accumulation of metal contaminants in commercially consumed marine fish globally and particularly in South Africa, affecting both the fishing industry as well as fish consumers. © 2015 Society of Chemical Industry.

Bioavailability of Pb, Zn, Cu, Cd, Ni and Cr in the sediments of the Tessa River: A mining area in the North-West Tunisia

NASA Astrophysics Data System (ADS)

Sebei, Abdelaziz; Helali, Mohamed Amine; Oueslati, Walid; Abdelmalek-Babbou, Chiraz; Chaabani, Fredj

2018-01-01

Tessa River is seen as one of the important rivers in Tunisia. Its catchment is known for its agricultural and mining activities, especially the Bougrine and Fedj Lahdhoum mines. Eighteen (18) surface sediments and five (5) water samples were collected from the Tessa River, near these two mining sites. Sediments are essentially sandy (>80%), the most important mineral is quartz (20-73%), then calcite (41%) and dolomites (4%). Heavy metal contents are relatively high near the mining sites, 356 μg g-1 for Pb, 3000 μg g-1 for Zn, and 5 μg g-1 for Cd. These values are lower downstream due to watercourse dilution effects. Other heavy metals: Cu, Ni and Cr, are low, and values are relatively constant in all the studied samples, even near the mining sites. The metals originate from natural sources and not from mining activities. This trend is confirmed by the enrichment factor (EF) where EFNi, EFCu and EFCr are lower or equal to 1, unlike EFPb, EFZn or EFCd where values are much higher (>20). Chemical speciation of these metals does not show any spatial variation. Except for cadmium which is bound to the residual fraction and in the carbonates; all other heavy metals are bound to the five sediment chemical fractions: the residual fraction (>52%), followed by the oxyhydroxides fraction (21%) and carbonates (16%), and finally bound to the organic matter and to the exchangeable fraction (<10%). The bioavailable fraction of the studied heavy metals exceeds 45%, which present risk of toxicity.

Pollution, toxicity, and ecological risk of heavy metals in surface river sediments of a large basin undergoing rapid economic development.

PubMed

Tang, Wenzhong; Zhang, Chao; Zhao, Yu; Shan, Baoqing; Song, Zhixin

2017-05-01

A comprehensive and detailed investigation of heavy metal pollution, toxicity, and ecological risk assessment was conducted for the surface river sediments of the Haihe Basin in China based on 220 sampling sites selected in 2013. The average concentrations of Cr, Cu, Ni, Pb, and Zn in the sediments were 129 mg/kg, 63.4 mg/kg, 36.6 mg/kg, 50.0 mg/kg, and 202 mg/kg, respectively. As indicated by the geoaccumulation and pollution load indices, most surface river sediments of the Haihe Basin were contaminated with the investigated metals, especially in the junction region of the Zi Ya He and Hei Long Gang watersheds. The 5 heavy metals in the sediments all had anthropogenic sources, and the enrichment degrees followed the order Cu > Pb > Zn > Cr > Ni, with mean enrichment factors of 3.27, 2.77, 2.58, 1.81, and 1.44, respectively. According to the mean index of comprehensive potential ecological risk (38.9), the studied sediments of the Haihe Basin showed low potential ecological risk, but the sediments were potentially biologically toxic based on the mean probable effect concentration quotient (0.547), which may be the result of speciation of the 5 metals in the sediments. The results indicate that heavy metal pollution should be considered during the development of ecological restoration strategies in the Haihe Basin. Environ Toxicol Chem 2017;36:1149-1155. © 2016 SETAC. © 2016 SETAC.

Finger printing of mixed contaminants from former manufactured gas plant (MGP) site soils: Implications to bioremediation.

PubMed

Thavamani, Palanisami; Megharaj, Mallavarapu; Krishnamurti, G S R; McFarland, Ross; Naidu, Ravi

2011-01-01

Contaminants in general do not occur as single chemicals but as mixtures at any contaminated site. Gasworks sites are the typical mixed contaminated sites. These sites are not only subjected to PAH contamination but also varying degrees of heavy metal contamination. Bioremediation in these sites is often hindered by the presence of heavy metals. The co-occurrence of PAHs with heavy metals has not been systematically investigated. Metals are reported to inhibit the general soil microbiological processes. The total concentration of soluble metal in the system includes both free metal ion and complexed forms. Within bioavailable fraction, the most toxic form is the free metal species, which was not addressed well so far in gas works site characterisation. This study underpins the science and importance of metal bioavailability and speciation based site characterisation in mixed contaminated sites. In this study a detailed elemental chemistry of the gas works site soils are discussed using different methods. The PAH contamination was contributed by both low and high molecular weight PAHs. The total PAHs concentration ranged from 335 to 8645 mg/kg. Among most toxic metals Pb was found in high concentration ranging from 88 to 671 mg/kg, Cd 8 to 112 mg/kg and Zn varied from 64 to 488 mg/kg. Thermodynamic chemical equilibrium model VMINTEQ (Ver 2.52) was used to calculate the free metal species in gas works site soils. The percentage free metal species showed a different trend compared to total metal concentrations, free Zn species ranged 18-86%, free Cd was 26-87% and Pb showed lowest free metal percentage (0-17%). The bioavailable metal species and its implications to bioremediation have also been discussed. Copyright © 2010 Elsevier Ltd. All rights reserved.

Simultaneous enhancement of sludge dewaterability and removal of sludge-borne heavy metals through a novel oxidative leaching induced by nano-CaO2.

PubMed

Wu, Boran; Dai, Xiaohu; Chai, Xiaoli

2017-07-01

The production of sewage sludge with the presence of various contaminants has been a serious issue for the operation of wastewater treatment plants on both the economical and environmental sides. To minimize the sludge volume to be handled and limit the potential environmental risk, this study developed a novel oxidative leaching process for enhanced sewage sludge dewatering and simultaneous removal of heavy metals based on nano-CaO 2 . Response surface methodology determined the following optimal conditioning parameters in terms of capillary suction time reduction: 0.0906 g/g dry solid (DS) nano-CaO 2 , 0.9969 mmol/g DS Fe 2+ , and pH of 5.59. The speciation partitioning analysis of the heavy metals pre and post nano-CaO 2 peroxidation indicated that the content of organically bound metals decreased and the percentage of soluble fraction increased substantially, which was beneficial for the removal of heavy metals through the dewatering unit. Nano-CaO 2 peroxidation could also induce the transformation of extracellular polymeric substances (EPS) from the tightly bound layers to the loosely bound layers of sewage sludge flocs. Through the decline of the Ryan-Weber constant of fluorescence titration and the pseudo-first-order kinetic constant of complexation, it was verified that the binding capacity of EPS with metal ions could be damaged by nano-CaO 2 peroxidation, which was the primary mechanism behind the substantial reduction of organically bound metals. This study is believed to provide novel insights into the application of nanotechnology in terms of the simultaneous volume and toxicity reduction of sewage sludge. Graphical abstract.

Heavy metals in estuarine surface sediments of the Hai River Basin, variation characteristics, chemical speciation and ecological risk.

PubMed

Lei, Pei; Zhang, Hong; Shan, Baoqing; Lv, Shucong; Tang, Wenzhong

2016-04-01

The Hai River Basin (HRB) is considered to be one of the most polluted areas in China due to the high regional population density and rapid economic development. The estuaries of the HRB, which receive pollutants from terrestrial rivers, may subsequently suffer potential pollution and result in ecological risk of heavy metals. Six heavy metals (Cd, Cr, Cu, Ni, Pb, and Zn) were measured in estuarine surface sediments from 10 estuaries of the HRB to investigate their variation characteristics and ecological risks. The spatial difference of Cr, Ni, Pb, and Zn in sediments was higher than that of the rest two elements. The Yongdingxin Estuary (YDX) and Ziyaxin Estuary (ZYX) in the Northern Hai River System (NHRS) were the most severe in terms of heavy metal contamination. According to the Risk Assessment Code (RAC) classification, Cd associated with the exchangeable and carbonate fraction (the average of 21.3 %) indicated medium risk to high risk. More than 50 % of Cr, Cu, Ni, and Zn on average were associated with the residual fraction. Based on the sum of the first three fractions (exchangeable and carbonate + reducible + oxidizable), the mobility order of these heavy metals was Cd >Pb > Zn ≈ Cu > Ni > Cr. Compared to the background values of cinnamon soil, the potential ecological risk index (RI) values ranged from 25.6 to 168, with an average of 91.2, indicating a low ecological risk in estuarine sites of the HRB. Cd and Pb were the dominant contributors to the toxic-response factor (45.8 and 25.5 %, respectively). The results give insight into the different control measures pertaining to heavy metal pollution and risk for both relatively clean estuaries and urban seriously polluted areas, respectively, for the formation of protect strategies of aquatic environment in the HRB.

Influence of carbonation under oxy-fuel combustion flue gas on the leachability of heavy metals in MSWI fly ash.

PubMed

Ni, Peng; Xiong, Zhuo; Tian, Chong; Li, Hailong; Zhao, Yongchun; Zhang, Junying; Zheng, Chuguang

2017-09-01

Due to the high cost of pure CO 2 , carbonation of MSWI fly ash has not been fully developed. It is essential to select a kind of reaction gas with rich CO 2 instead of pure CO 2 . The CO 2 uptake and leaching toxicity of heavy metals in three typical types of municipal solid waste incinerator (MSWI) fly ash were investigated with simulated oxy-fuel combustion flue gas under different reaction temperatures, which was compared with both pure CO 2 and simulated air combustion flue gas. The CO 2 uptake under simulated oxy-fuel combustion flue gas were similar to that of pure CO 2 . The leaching concentration of heavy metals in all MSWI fly ash samples, especially in ash from Changzhou, China (CZ), decreased after carbonation. Specifically, the leached Pb concentration of the CZ MSWI fly ash decreased 92% under oxy-fuel combustion flue gas, 95% under pure CO 2 atmosphere and 84% under the air combustion flue gas. After carbonation, the leaching concentration of Pb was below the Chinese legal limit. The leaching concentration of Zn from CZ sample decreased 69% under oxy-fuel combustion flue gas, which of Cu, As, Cr and Hg decreased 25%, 33%, 11% and 21%, respectively. In the other two samples of Xuzhou, China (XZ) and Wuhan, China (WH), the leaching characteristics of heavy metals were similar to the CZ sample. The speciation of heavy metals was largely changed from the exchangeable to carbonated fraction because of the carbonation reaction under simulated oxy-fuel combustion flue gas. After carbonation reaction, most of heavy metals bound in carbonates became more stable and leached less. Therefore, oxy-fuel combustion flue gas could be a low-cost source for carbonation of MSWI fly ash. Copyright © 2017 Elsevier Ltd. All rights reserved.

Toxic metals (Ni2+, Pb2+, Hg2+) binding affinity of dissolved organic matter (DOM) derived from different ages municipal landfill leachate

NASA Astrophysics Data System (ADS)

Rikta, S. Y.; Tareq, Shafi M.; Uddin, M. Khabir

2018-03-01

Solid waste production is rapidly increasing in Bangladesh and landfill leachate is the consequence of the decomposition of this waste. These leachates contain heavy metals and significant amount of dissolved organic matter (DOM). DOM is known to have considerable role in heavy metals speciation. Hence, it is important to characterize DOM/leachate and evaluate toxic metals binding affinity of DOM. The objectives of this study were to characterize the DOM in landfill leachate through physico-chemical and optical analyses and to investigate the toxic metals (Ni2+, Pb2+ and Hg2+) binding affinity of three different ages (fresh sample L-1, young sample L-2 and mature sample L-3) DOM samples. Results suggested that leachate is a potential pollutant which contained very high organic pollutant load. Conditional stability constant (Log K) and percentages of fluorophores that correspond to metal binding (% f) values indicated that young DOM sample (L-2) had the highest binding affinity to all the three metals ions. In general, DOM samples showed the following order affinity to the metal ions; Ni2+ binding affinity: L-2 > L-3 > L-1, Pb2+ binding affinity: L-2 > L-3 > L-1 and Hg2+ binding affinity: L-2 > L-1 > L-3.

Determining the speciation of Zn in soils around the sediment ponds of chemical plants by XRD and XAFS spectroscopy and sequential extraction.

PubMed

Minkina, Tatiana; Nevidomskaya, Dina; Bauer, Tatiana; Shuvaeva, Victoria; Soldatov, Alexander; Mandzhieva, Saglara; Zubavichus, Yan; Trigub, Alexander

2018-09-01

For a correct assessment of risk of polluted soil, it is crucial to establish the speciation and mobility of the contaminants. The aim of this study was to investigate the speciation and transformation of Zn in strongly technogenically transformed contaminated Spolic Technosols for a long time in territory of sludge collectors by combining analytical techniques and synchrotron techniques. Sequential fractionation of Zn compounds in studied soils revealed increasing metal mobility. Phyllosilicates and Fe and Mn hydroxides were the main stabilizers of Zn mobility. A high degree of transformation was identified for the composition of the mineral phase in Spolic Technosols by X-ray powder diffraction. Technogenic phases (Zn-containing authigenic minerals) were revealed in Spolic Technosols samples through the analysis of their Zn K-edge EXAFS and XANES spectra. In one of the samples Zn local environment was formed by predominantly oxygen atoms, and in the other one mixed ZnS and ZnO bonding was found. Zn speciation in the studied technogenically transformed soils was due to the composition of pollutants contaminating the floodplain landscapes for a long time, and, second, this is the combination of physicochemical properties controlling the buffer properties of investigated soils. X-ray spectroscopic and X-ray powder diffraction analyses combined with sequential extraction assays is an effective tool to check the affinity of the soil components for heavy metal cations. Copyright © 2018 Elsevier B.V. All rights reserved.

Speciation of Cu and Zn in drainage water from agricultural soils.

PubMed

Aldrich, Annette P; Kistler, David; Sigg, Laura

2002-11-15

Inputs of copper and zinc from agricultural soils into the aquatic system were investigated in this study, because of their heavy agricultural usage as feed additives and components of fertilizers and fungicides. As the mobility and bioavailability of these metals are affected by their speciation, the lipophilic, colloidal and organic fractions were determined in drainage water from a loamy and a humic soil treated with fungicides or manure. This study therefore investigates the impact of agricultural activity on a natural environment and furthers our understanding of the mobility of metals in agricultural soils and aquatic pollution in rural areas. Marked increases in the total dissolved metal concentrations were observed in the drainage water during rain events with up to 0.3 microM Cu and 0.26 microM Zn depending on the intensity of the rainfall and soil type. The mobile metal fractions were of a small molecular size (<10 kD) and mainly hydrophilic. Lipophilic complexes originating from a dithiocarbamate (DTC) fungicide could not be observed in the drainage water; however, small amounts of lipophilic metal complexes may be of natural origin. Cu was organically complexed to > 99.9% by abundant organic ligands (log K 10.5-11.0). About 50% of dissolved Zn were electrochemically labile, and the other 50% were complexed by strong organic ligands (log K 8.2-8.6). Therefore very little free metal species were found suggesting a low bioavailability of these metals in the drainage water even at elevated metal concentrations.

Trace metal speciation in natural waters: Computational vs. analytical

USGS Publications Warehouse

Nordstrom, D. Kirk

1996-01-01

Improvements in the field sampling, preservation, and determination of trace metals in natural waters have made many analyses more reliable and less affected by contamination. The speciation of trace metals, however, remains controversial. Chemical model speciation calculations do not necessarily agree with voltammetric, ion exchange, potentiometric, or other analytical speciation techniques. When metal-organic complexes are important, model calculations are not usually helpful and on-site analytical separations are essential. Many analytical speciation techniques have serious interferences and only work well for a limited subset of water types and compositions. A combined approach to the evaluation of speciation could greatly reduce these uncertainties. The approach proposed would be to (1) compare and contrast different analytical techniques with each other and with computed speciation, (2) compare computed trace metal speciation with reliable measurements of solubility, potentiometry, and mean activity coefficients, and (3) compare different model calculations with each other for the same set of water analyses, especially where supplementary data on speciation already exist. A comparison and critique of analytical with chemical model speciation for a range of water samples would delineate the useful range and limitations of these different approaches to speciation. Both model calculations and analytical determinations have useful and different constraints on the range of possible speciation such that they can provide much better insight into speciation when used together. Major discrepancies in the thermodynamic databases of speciation models can be evaluated with the aid of analytical speciation, and when the thermodynamic models are highly consistent and reliable, the sources of error in the analytical speciation can be evaluated. Major thermodynamic discrepancies also can be evaluated by simulating solubility and activity coefficient data and testing various chemical models for their range of applicability. Until a comparative approach such as this is taken, trace metal speciation will remain highly uncertain and controversial.

The positive relationship between ocean acidification and pollution.

PubMed

Zeng, Xiangfeng; Chen, Xijuan; Zhuang, Jie

2015-02-15

Ocean acidification and pollution coexist to exert combined effects on the functions and services of marine ecosystems. Ocean acidification can increase the biotoxicity of heavy metals by altering their speciation and bioavailability. Marine pollutants, such as heavy metals and oils, could decrease the photosynthesis rate and increase the respiration rate of marine organisms as a result of biotoxicity and eutrophication, facilitating ocean acidification to varying degrees. Here we review the complex interactions between ocean acidification and pollution in the context of linkage of multiple stressors to marine ecosystems. The synthesized information shows that pollution-affected respiration acidifies coastal oceans more than the uptake of anthropogenic carbon dioxide. Coastal regions are more vulnerable to the negative impact of ocean acidification due to large influxes of pollutants from terrestrial ecosystems. Ocean acidification and pollution facilitate each other, and thus coastal environmental protection from pollution has a large potential for mitigating acidification risk. Copyright © 2014 Elsevier Ltd. All rights reserved.

Arsenic species analysis in porewaters and sediments using hydride generation atomic fluorescence spectrometry.

PubMed

Liao, Meng-xia; Deng, Tian-long

2006-01-01

It was observed that the atomic fluorescence emission due to As(V) could has a 10% to 40% of fluorescence emission signal during the determination of As(III) in the mixture of As(III) and As(V). Besides, interferes from heavy metals such as Pb(lIl), Cu(ll) can cause severe increase of the signals as compared to the insignificant effects caused by Cd(II), Zn(ll), Mn(II) and Fe(Ill). On the basis of further studies, the masking agent of 8-hydroxyquinoline was used as an efficient agent to eliminate interference of As(V) emission and the heavy metal of Cu2+ and Pb2+ in the measurements of arsenic species. After a series standard additions and CRM researches, a sensitive and interference-free analytical procedure was developed for the speciation of arsenic in samples of porewaters and sediments in Poyang Lake, China.

Heavy metal contamination status and source apportionment in sediments of Songhua River Harbin region, Northeast China.

PubMed

Li, Ning; Tian, Yu; Zhang, Jun; Zuo, Wei; Zhan, Wei; Zhang, Jian

2017-02-01

The Songhua River represents one of the seven major river systems in China. It flows through Harbin city with 66 km long, locating in the northern China with a longer winter time. This paper aimed to study concentration distributions, stability, risk assessment, and source apportionment of heavy metals including chromium (Cr), cadmium (Cd), lead (Pb), mercury (Hg), arsenic (As), copper (Cu), zinc (Zn), and nickel (Ni) in 11 selected sections of the Songhua River Harbin region. Results showed that Cr, Cd, Pb, Hg, and As exceeded their respective geochemical background values in sediments of most monitoring sections. Compared with other important rivers and lakes in China, Cr, Hg, Cd, and As pollutions in surface sediments were above medium level. Further analysis of chemical speciation indicated that Cr and As in surface sediments were relatively stable while Pb and Cd were easily bioavailable. Correlation analysis revealed sources of these metals except As might be identical. Pollution levels and ecological risks of heavy metals in surface sediments presented higher in the mainstream region (45° 47.0' N ~ 45° 53.3' N, 126° 37.0' E ~ 126° 42.1' E). Source apportionment found Hejiagou and Ashi River were the main contributors to metal pollution of this region. Thus, anthropogenic activities along the Hejiagou and Ashi River should be restricted in order to protect the Songhua River Harbin region from metal contamination.

Comparative evaluation of short-term leach tests for heavy metal release from mineral processing waste

USGS Publications Warehouse

Al-Abed, S. R.; Hageman, P.L.; Jegadeesan, G.; Madhavan, N.; Allen, D.

2006-01-01

Evaluation of metal leaching using a single leach test such as the Toxicity Characteristic Leaching Procedure (TCLP) is often questionable. The pH, redox potential (Eh), particle size and contact time are critical variables in controlling metal stability, not accounted for in the TCLP. This paper compares the leaching behavior of metals in mineral processing waste via short-term extraction tests such as TCLP, Field Leach Test (FLT) used by USGS and deionized water extraction tests. Variation in the extracted amounts was attributed to the use of different particle sizes, extraction fluid and contact time. In the controlled pH experiments, maximum metal extraction was obtained at acidic pH for cationic heavy metals such as Cu, Pb and Zn, while desorption of Se from the waste resulted in high extract concentrations in the alkaline region. Precipitation of iron, caused by a pH increase, probably resulted in co-precipitation and immobilization of Cu, Pb and Zn in the alkaline pH region. A sequential extraction procedure was performed on the original waste and the solid residue from the Eh-pH experiments to determine the chemical speciation and distribution of the heavy metals. In the as-received waste, Cu existed predominantly in water soluble or sulfidic phases, with no binding to carbonates or iron oxides. Similar characteristics were observed for Pb and Zn, while Se existed mostly associated with iron oxides or sulfides. Adsorption/co-precipitation of Cu, Se and Pb on precipitated iron hydroxides was observed in the experimental solid residues, resulting in metal immobilization above pH 7.

Immobilization of Pb, Cd, and Zn in a contaminated soil using eggshell and banana stem amendments: metal leachability and a sequential extraction study.

PubMed

Ashrafi, Mehrnaz; Mohamad, Sharifah; Yusoff, Ismail; Shahul Hamid, Fauziah

2015-01-01

Heavy-metal-contaminated soil is one of the major environmental pollution issues all over the world. In this study, two low-cost amendments, inorganic eggshell and organic banana stem, were applied to slightly alkaline soil for the purpose of in situ immobilization of Pb, Cd, and Zn. The artificially metal-contaminated soil was treated with 5% eggshell or 10% banana stem. To simulate the rainfall conditions, a metal leaching experiment for a period of 12 weeks was designed, and the total concentrations of the metals in the leachates were determined every 2 weeks. The results from the metal leaching analysis revealed that eggshell amendment generally reduced the concentrations of Pb, Cd, and Zn in the leachates, whereas banana stem amendment was effective only on the reduction of Cd concentration in the leachates. A sequential extraction analysis was carried out at the end of the experiment to find out the speciation of the heavy metals in the amended soils. Eggshell amendment notably decreased mobility of Pb, Cd, and Zn in the soil by transforming their readily available forms to less accessible fractions. Banana stem amendment also reduced exchangeable form of Cd and increased its residual form in the soil.

[Application of in vitro bionic digestion and biomembrane extraction for metal speciation analysis, bioavailability and risk assessment in lianhua qingwen capsule].

PubMed

Lin, Lu-Xiu; Li, Shun-Xing; Zheng, Feng-Ying

2014-06-01

One of the causes of the high cost of pharmaceuticals and the major obstacles to rapidly assessing the bioavailability and risk of a chemical is the lack of experimental model systems. A new pre-treatment technology, in vitro bionic digestion was designed for metal analysis in Lianhua Qingwen capsule. The capsule was digested on 37 degrees C under the acidity of the stomach or intestine, and with the inorganic and organic compounds (including digestive enzymes) found in the stomach or intestine, and then the chyme was obtained. Being similar to the biomembrane between the gastrointestinal tract and blood vessels, monolayer liposome was used as biomembrane model Affinity-monolayer liposome metals (AMLMs) and water-soluble metals were used for metal speciation analysis in the capsule. Based on the concentration of AMLMs, the main absorption site of trace metals was proposed. The metal total contents or the concentration of AMLMs in the capsule were compared to the nutritional requirements, daily permissible dose and heavy metal total contents from the "import and export of medicinal plants and preparation of green industry state standards". The metal concentrations in the capsule were within the safety baseline levels for human consumption. After in vitro bionic digestion, most of trace metals were absorbed mainly in intestine. The concentration of As, Cd, Pb was 0.38, 0.07, 1.60 mg x kg(-1), respectively, far less than the permissible dose from the "import and export of medicinal plants and preparation of green industry state standards".

When soils become sediments: Large-scale storage of soils in sandpits and lakes and the impact of reduction kinetics on heavy metals and arsenic release to groundwater.

PubMed

Vink, Jos P M; van Zomeren, Andre; Dijkstra, Joris J; Comans, Rob N J

2017-08-01

Simulating the storage of aerobic soils under water, the chemical speciation of heavy metals and arsenic was studied over a long-term reduction period. Time-dynamic and redox-discrete measurements in reactors were used to study geochemical changes. Large kinetic differences in the net-complexation quantities of heavy metals with sulfides was observed, and elevated pore water concentrations remained for a prolonged period (>1 year) specifically for As, B, Ba, Co, Mo, and Ni. Arsenic is associated to the iron phases as a co-precipitate or sorbed fraction to Fe-(hydr)oxides, and it is being released into solution as a consequence of the reduction of iron. The composition of dissolved organic matter (DOM) in reducing pore water was monitored, and relative contributions of fulvic, humic and hydrophylic compounds were measured via analytical batch procedures. Quantitative and qualitative shifts in organic compounds occur during reduction; DOM increased up to a factor 10, while fulvic acids become dominant over humic acids which disappear altogether as reduction progresses. Both the hydrophobic and hydrophilic fractions increase and may even become the dominant fraction. Reactive amorphous and crystalline iron phases, as well as dissolved FeII/FeIII speciation, were measured and used as input for the geochemical model to improve predictions for risk assessment to suboxic and anaerobic environments. The release of arsenic is related to readily reducible iron fractions that may be identified by 1 mM CaCl 2 extraction procedure. Including DOM concentration shifts and compositional changes during reduction significantly improved model simulations, enabling the prediction of peak concentrations and identification of soils with increased emission risk. Practical methods are suggested to facilitate the practice of environmentally acceptable soil storage under water. Copyright © 2017 Elsevier Ltd. All rights reserved.

Characterization of typical metal particles during haze episodes in Shanghai, China.

PubMed

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.

Metal speciation in soil and health risk due to vegetables consumption in Bangladesh.

PubMed

Islam, Md Saiful; Ahmed, Md Kawser; Habibullah-Al-Mamun, Md

2015-05-01

This study was conducted to investigate the contamination level of heavy metals in soil and vegetables, chemical speciation, and their transfer to the edible part of vegetables. Metals were analyzed using inductively coupled plasma mass spectrometer (ICP-MS). The ranges of Cr, Ni, Cu, As, Cd, and Pb in agricultural soils were 3.7-41, 3.9-36, 3.7-46, 2.3-26, 0.6-13, and 4.5-32 mg/kg, respectively. The metals were predominantly associated with the residual fractions of 39, 41, 40, 40, 34, and 41 % for Cr, Ni, Cu, As, Cd, and Pb, respectively. Considering the metal transfer from soil to the edible part of vegetables, the mean transfer factors (TFs) were in the descending order of Cu > Ni > Cr > Pb > As > Cd. In the edible tissues of vegetables, the concentrations of As, Cd, and Pb in most vegetable samples exceeded the maximum permissible levels, indicating not safe for human consumption. Total target hazard quotient (THQ) of the studied metals (except Cr) from all vegetables were higher than 1, indicated that if people consume these types of vegetables in their diet, they might pose risk to these metals. Total values of carcinogenic risk (CR) were 3.2 for As and 0.15 for Pb which were higher than the US Environmental Protection Agency (USEPA) threshold level (0.000001), indicating that the inhabitants consuming these vegetables are exposed to As and Pb with a lifetime cancer risk.

Heavy metals distribution and risk assessment in soil from an informal E-waste recycling site in Lagos State, Nigeria.

PubMed

Isimekhai, Khadijah A; Garelick, Hemda; Watt, John; Purchase, Diane

2017-07-01

Informal E-waste recycling can pose a risk to human health and the environment which this study endeavours to evaluate. The distribution of a number of heavy metals in soil from an informal recycling site in the largest market for used and new electronics and electrical equipment in West Africa was investigated. The potential bioavailability of heavy metals, extent of contamination, potential risk due to the recycling activities and impact of external factors such as rainfall were also assessed. The concentrations of all the heavy metals tested were higher in the area where burning of the waste occurred than at the control site, suggesting an impact of the recycling activities on the soil. The order of total metal concentrations was Cu > Pb > Zn > Mn > Ni > Sb > Cr > Cd for both the dry and wet seasons. The total concentrations of Cd, Cu, Mn, Ni and Zn were all significantly higher (p < 0.001) in the dry season than in the wet season. The concentrations of Cu (329-7106 mg kg -1 ), Pb (115-9623 mg kg -1 ) and Zn (508-8178 mg kg -1 ) were consistently higher than international soil guideline values. Using a sequential extraction method, the potential bioavailability of the heavy metals was indicated as Cd > Sb > Zn > Cu > Ni > Pb > Cr. When the risk was assessed using the Potential Ecological Risk Index (PERI), Cu was found to contribute the most to the potential ecological risk and Cd gave rise to the greatest concern due to its high toxic-response factor within the study site. Similarly, utilising the Risk Assessment Code (RAC) suggested that Cd posed the most risk in this site. This research establishes a high level of contamination in the study site and underscores the importance of applying the appropriate chemical speciation in risk assessment.

The determination of trace elements in crude oil and its heavy fractions by atomic spectrometry

NASA Astrophysics Data System (ADS)

Duyck, Christiane; Miekeley, Norbert; Porto da Silveira, Carmem L.; Aucélio, Ricardo Q.; Campos, Reinaldo C.; Grinberg, Patrícia; Brandão, Geisamanda P.

2007-09-01

A literature review on the determination of trace elements in crude oil and heavy molecular mass fractions (saturates, aromatics, resins and asphaltenes) by ICP-MS, ICP OES and AAS is presented. Metal occurrences, forms and distributions are examined as well as their implications in terms of reservoir geochemistry, oil refining and environment. The particular analytical challenges for the determination of metals in these complex matrices by spectrochemical techniques are discussed. Sample preparation based on ashing, microwave-assisted digestion and combustion decomposition procedures is noted as robust and long used. However, the introduction of non-aqueous solvents and micro-emulsions into inductively coupled plasmas is cited as a new trend for achieving rapid and accurate analysis. Separation procedures for operationally defined fractions in crude oil are more systematically applied for the observation of metal distributions and their implications. Chemical speciation is of growing interest, achieved by the coupling of high efficiency separation techniques (e.g., HPLC and GC) to ICP-MS instrumentation, which allows the simultaneous determination of multiple organometallic species of geochemical and environmental importance.

Bioleaching of heavy metals from sewage sludge by indigenous iron-oxidizing microorganisms using ammonium ferrous sulfate and ferrous sulfate as energy sources: a comparative study.

PubMed

Pathak, Ashish; Dastidar, M G; Sreekrishnan, T R

2009-11-15

The potential of indigenous iron-oxidizing microorganisms enriched at initial neutral pH of the sewage sludge for bioleaching of heavy metals was investigated at initial neutral pH of the sludge using ammonium ferrous sulfate (FAS) and ferrous sulfate (FS) as an energy sources in two different sets of experiments. After 16 days of bioleaching, 56% Cu, 48% Ni, 68% Zn and 42% C were removed from the sludge using ammonium ferrous sulfate as an energy source. On the other hand, 64% Cu, 58% Ni, 76% Zn and 52% Cr were removed using ferrous sulfate. Further, 32% nitrogen and 24% phosphorus were leached from the sludge using ferrous sulfate, whereas only 22% nitrogen and 17% phosphorus were removed using ammonium ferrous sulfate. The BCR sequential extraction study on speciation of metals showed that using ammonium ferrous sulfate and ferrous sulfate, all the metals remained in bioleached sludge as stable form (F4 fraction). The results of the present study indicate that the bioleached sludge would be safer for land application. Also, the fertilizing property was largely conserved in the bioleached sludge using both the substrates.

Metal releases from a municipal solid waste incineration air pollution control residue mixed with compost.

PubMed

Van Praagh, M; Persson, K M

2008-08-01

The influence of 10 wt.% mature compost was tested on the heavy metal leachate emissions from a calcium-rich municipal solid waste incineration air pollution control residue (MSWI APC). Apart from elongated columns (500 and 1250 mm), an otherwise norm compliant European percolation test setup was used. More than 99% of the metals Al, As, Cd, Cr, Cu, Fe and Ni were left in the APC residue after leaching to a liquid-to-solid ratio (L/S) of 10. Apparent short-term effects of elevated leachate DOC concentrations on heavy metal releases were not detected. Zn and Pb leachate concentrations were one order of magnitude lower for L/S 5 and 10 from the pure APC residue column, which suggests a possible long-term effect of compost on the release of these elements. Prolonging the contact time between the pore water and the material resulted in elevated leachate concentrations at L/S 0.1 to L/S 1 by a factor of 2. Only Cr and Pb concentrations were at their maxima in the first leachates at L/S 0.1. Equilibrium speciation modelling with the PHREEQC code suggested portlandite (Ca(OH)2) to control Ca solubility and pH.

A field survey of metal binding to metallothionein and other cytosolic ligands in liver of eels using an on-line isotope dilution method in combination with size exclusion (SE) high pressure liquid chromatography (HPLC) coupled to Inductively Coupled Plasma time-of-flight Mass Spectrometry (ICP-TOFMS).

PubMed

Van Campenhout, Karen; Goenaga Infante, Heidi; Goemans, Geert; Belpaire, Claude; Adams, Freddy; Blust, Ronny; Bervoets, Lieven

2008-05-15

The effect of metal exposure on the accumulation and cytosolic speciation of metals in livers of wild populations of European eel with special emphasis on metallothioneins (MT) was studied. Four sampling sites in Flanders showing different degrees of heavy metal contamination were selected for this purpose. An on-line isotope dilution method in combination with size exclusion (SE) high pressure liquid chromatography (HPLC) coupled to Inductively Coupled Plasma time-of-flight Mass Spectrometry (ICP-TOFMS) was used to study the cytosolic speciation of the metals. The distribution of the metals Cd, Cu, Ni, Pb and Zn among cytosolic fractions displayed strong differences. The cytosolic concentration of Cd, Ni and Pb increased proportionally with the total liver levels. However, the cytosolic concentrations of Cu and Zn only increased above a certain liver tissue threshold level. Cd, Cu and Zn, but not Pb and Ni, were largely associated with the MT pool in correspondence with the environmental exposure and liver tissue concentrations. Most of the Pb and Ni and a considerable fraction of Cu and Zn, but not Cd, were associated to High Molecular Weight (HMW) fractions. The relative importance of the Cu and Zn in the HMW fraction decreased with increasing contamination levels while the MT pool became progressively more important. The close relationship between the cytosolic metal load and the total MT levels or the metals bound on the MT pool indicates that the metals, rather than other stress factors, are the major factor determining MT induction.

Relationship between metal speciation in soil solution and metal adsorption at the root surface of ryegrass.

PubMed

Kalis, Erwin J J; Temminghoff, Erwin J M; Town, Raewyn M; Unsworth, Emily R; van Riemsdijk, Willem H

2008-01-01

The total metal content of the soil or total metal concentration in the soil solution is not always a good indicator for metal availability to plants. Therefore, several speciation techniques have been developed that measure a defined fraction of the total metal concentration in the soil solution. In this study the Donnan Membrane Technique (DMT) was used to measure free metal ion concentrations in CaCl(2) extractions (to mimic the soil solution, and to work under standardized conditions) of 10 different soils, whereas diffusive gradients in thin-films (DGT) and scanning chronopotentiometry (SCP) were used to measure the sum of free and labile metal concentrations in the CaCl(2) extracts. The DGT device was also exposed directly to the (wetted) soil (soil-DGT). The metal concentrations measured with the speciation techniques are related to the metal adsorption at the root surface of ryegrass (Lolium perenne L.), to be able to subsequently predict metal uptake. In most cases the metal adsorption related pH-dependently to the metal concentrations measured by DMT, SCP, and DGT in the CaCl(2) extract. However, the relationship between metal adsorption at the root surface and the metal concentrations measured by the soil-DGT was not-or only slightly-pH dependent. The correlations between metal adsorption at the root surface and metal speciation detected by different speciation techniques allow discussion about rate limiting steps in biouptake and the contribution of metal complexes to metal bioavailability.

Urban legacies and soil management affect the concentration and speciation of trace metals in Los Angeles community garden soils.

PubMed

Clarke, Lorraine Weller; Jenerette, G Darrel; Bain, Daniel J

2015-02-01

Heavy metals in urban soils can compromise human health, especially in urban gardens, where gardeners may ingest contaminated dust or crops. To identify patterns of urban garden metal contamination, we measured concentrations and bioavailability of Pb, As, and Cd in soils associated with twelve community gardens in Los Angeles County, CA. This included sequential extractions to partition metals among exchangeable, reducible, organic, or residual fractions. Proximity to road increased all metal concentrations, suggesting vehicle emissions sources. Reducible Pb increased with neighborhood age, suggesting leaded paint as a likely pollutant source. Exchangeable Cd and As both increased with road proximity. Only cultivated soils showed an increase in exchangeable As with road proximity, potentially due to reducing humic acid interactions while Cd bioavailability was mitigated by organic matter. Understanding the geochemical phases and metal bioavailability allows incorporation of contamination patterns into urban planning. Copyright © 2014 Elsevier Ltd. All rights reserved.

Assessment of a sequential extraction protocol by examining solution chemistry and mineralogical evolution

NASA Astrophysics Data System (ADS)

Maubec, Nicolas; Pauwels, Hélène; Noël, Hervé; Bourrat, Xavier

2015-04-01

Knowledge of the behavior of heavy metals, such as copper and zinc in sediments, is a key factor to improve the management of rivers. The mobility of these metals, which may be harmful to the environment, depends directly on their concentration and speciation , which in turn depend on physico-chemical parameters such as mineralogy of the sediment fraction, pH, redox potential, salinity etc ... (Anderson et al., 2000; Sterckeman et al., 2004; Van Oort et al., 2008). Several methods based on chemical extractions are currently applied to assess the behavior of heavy metals in soils and sediments. Among them, sequential extraction procedure is widely used in soil and sediment science and provides details about the origin, biological and physicochemical availability, mobilization and transports of trace metals elements. It is based on the use of a series of extracting reagents to extract selectively heavy metals according to their association within the solid phase (Cornu and Clozel, 2000) including the following different fraction : exchangeable, bound to carbonates, associated to oxides (reducible fraction), linked to organic matter and sulfides (oxidizable fraction) as well as silicate minerals so called residual fraction (Hickey and Kittrick, 1984; Tessier et al., 1979). Consequently sequential extraction method is expected to simulate a lot of potential natural and anthropogenic modifications of environmental conditions (Arey et al., 1999; Brannon and Patrick, 1987; Hickey and Kittrick, 1984; La Force et al., 1999; Tessier et al., 1979). For three decades, a large number of protocols has been proposed, characterized by specific reagents and experimental conditions (concentrations, number of steps, extraction orders and solid/solution ratio) (Das et al., 1995; Gomez Ariza et al., 2000; Quevauviller et al., 1994; Rauret, 1998; Tack and Verloo, 1995), but it appeared that several of them suffer from a lack of selectivity of applied reagents: besides target ones, some of them are able to leach several solid phases. In this context, the aim of the present study is to investigate the effectiveness and the selectivity of different reagents for metal extraction from target geochemical fraction. It is based on solid analyses with the use of X-ray diffraction and a scanning electron microscopy (SEM) coupled to a microRaman spectrometer in conjunction with chemical analyses of extracting solutions at each step. This methodology provides the opportunity to assess more accurately the effect of each reagent. The study focuses on extraction of Cu and Zn from sediment samples collected at two sites from river banks and characterized by presence of Quartz, Feldspar K, Micas, Kaolinite but with differences regarding accessory phases (pyrite, organic matter, iron oxy- hydroxide, calcite). The interaction of the samples with eight different reagents was assessed and compared (Ca(NO3)2 and CaCl2 for the exchangeable fraction; buffered solutions of sodium acetate/acetic acid at pH = 5.5 and pH = 5 for the acido-soluble fraction; hydroxylamine hydrochloride and a solution of ammonium oxalate/oxalic acid for reducible fraction; hydrogen peroxide and sodium hypochlorite for the oxidizable fraction. In-depth characterization of solid residue at each step allowed proposing the best protocol for both metals. Anderson, P., Davidson, C. M., Duncan, A. L., Littlejohn, D., Ure, A. M., and Garden, L. M. (2000). Column leaching and sorption experiments to assess the mobility of potentially toxic elements in industrially contaminated land. Journal of Environmental Monitoring, 2. Arey, J. S., Seaman, J. C., and Bertsch, P. M. (1999). Immobilization of uranium in contaminated sediments by hydroxyapatite addition. Environmental Science & Technology, 33, 337-342. Brannon, J. M., and Patrick, W. H. (1987). Fixation, transformation, and mobilization of arsenic in sediments.Environmental Science & Technology, 21, 450-459. Cornu, S., and Clozel, B. (2000). Extractions séquentielles et spéciation des éléments trace métalliques dans les sols naturels. Analyse critique. 7, 179-189. Das, A. K., Chakraborty, R., Cervera, M. L., and Delaguardia, M. (1995). Metal speciation in solid matrices. Talanta, 42. Gomez Ariza, J. L., Giraldez, I., Sanchez-Rodas, D., and Morales, E. (2000). Selectivity assessment of a sequential extraction procedure for metal mobility characterization using model phases. Talanta, 52, 545-554. Hickey, M. G., and Kittrick, J. A. (1984). Chemical partitioning of cadmium, copper, nickel and zinc in soils and sediments containing high-levels of heavy metals. Journal of Environmental Quality, 13, 372-376. La Force, M. J., Fendorf, S., Li, G. C., and Rosenzweig, R. F. (1999). Redistribution of trace elements from contaminated sediments of Lake Coeur d'Alene during oxygenation. Journal of Environmental Quality, 28, 1195-1200. Quevauviller, P., Rauret, G., Muntau, H., Ure, A. M., Rubio, R., Lopezsanchez, J. F., Fiedler, H. D., and Griepink, B. (1994). Evaluation of a sequential extraction procedure for the determination of extractable trace-metal contents in sediments. Fresenius Journal of Analytical Chemistry, 349. Rauret, G. (1998). Extraction procedures for the determination of heavy metals in contaminated soil and sediment. Talanta, 46(3), 449-455. Sterckeman, T., Douay, F., Baize, D., Fourrier, H., Proix, N., and Schvartz, C. (2004). Factors affecting trace element concentrations in soils developed on recent marine deposits from northern France. Applied Geochemistry, 19. Tack, F. M. G., and Verloo, M. G. (1995). Chemical speciation and fraéctination in soil and sediment heavy-metal analysis - a review. International Journal of Environmental Analytical Chemistry, 59, 225-238. Tessier, A., Campbell, P. G. C., and Bisson, M. (1979). Sequential extraction procedure for the speciation of particulate trace-metals. Analytical Chemistry, 51. Van Oort, F., Jongmans, A. G., Lamy, I., Baize, D., and Chevallier, P. (2008). Impacts of long-term waste-water irrigation on the development of sandy Luvisols: consequences for metal pollutant distributions. European Journal of Soil Science, 59.

Effect of sediment size on bioleaching of heavy metals from contaminated sediments of Izmir Inner Bay.

PubMed

Guven, Duyusen E; Akinci, Gorkem

2013-09-01

The effect of sediment size on metals bioleaching from bay sediments was investigated by using fine (< 45 microm), medium (45-300 microm), and coarse (300-2000 microm) size fractions of a sediment sample contaminated with Cr, Cu, Pb, and Zn. Chemical speciation of the metals in bulk and size fractions of sediment were studied before and after bioleaching. Microbial activity was provided with mixed cultures of Acidithiobacillus thiooxidans and Acidithiobacillus ferrooxidans. The bioleaching process was carried out in flask experiments for 48 days, by using 5% (W/V) of solid concentration in suspension. Bioleaching was found to be efficient for the removal of selected heavy metals from every size fraction of sediments, where the experiments with the smaller particles resulted in the highest solubilization ratios. At the end of the experimental period, Cr, Cu, Pb and Zn were solubilized to the ratios of 68%, 88%, 72%, and 91% from the fine sediment, respectively. Higher removal efficiencies can be explained by the larger surface area provided by the smaller particles. The changes in the chemical forms of metals were determined and most of the metal releases were observed from the reducible and organic fractions independent from grain size. Higher concentrations were monitored in the residual fraction after bioleaching period, suggesting they are trapped in this fraction, and cannot be solubilized under natural conditions.

Bioleaching combined brine leaching of heavy metals from lead-zinc mine tailings: Transformations during the leaching process.

PubMed

Ye, Maoyou; Yan, Pingfang; Sun, Shuiyu; Han, Dajian; Xiao, Xiao; Zheng, Li; Huang, Shaosong; Chen, Yun; Zhuang, Shengwei

2017-02-01

During the process of bioleaching, lead (Pb) recovery is low. This low recovery is caused by a problem with the bioleaching technique. This research investigated the bioleaching combination of bioleaching with brine leaching to remove heavy metals from lead-zinc mine tailings. The impact of different parameters were studied, including the effects of initial pH (1.5-3.0) and solid concentration (5-20%) for bioleaching, and the effects of sodium chloride (NaCl) concentration (10-200 g/L) and temperature (25 and 50 °C) for brine leaching. Complementary characterization experiments (Sequential extraction, X-ray diffractometer (XRD), scanning electronic microscope (SEM)) were also conducted to explore the transformation of tailings during the leaching process. The results showed that bioleaching efficiency was significantly influenced by initial pH and solid concentration. Approximately 85.45% of iron (Fe), 4.12% of Pb, and 97.85% of zinc (Zn) were recovered through bioleaching in optimum conditions. Increasing the brine concentration and temperature promoted lead recovery. Lead was recovered from the bioleaching residues at a rate of 94.70% at 25 °C and at a rate of 99.46% at 50 °C when the NaCl concentration was 150 g/L. The study showed that bioleaching significantly changed the speciation of heavy metals and the formation and surface morphology of tailings. The metals were mainly bound in stable fractions after bioleaching. Copyright © 2016 Elsevier Ltd. All rights reserved.

Metal speciation of environmental samples using SPE and SFC-AED analysis

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

Mitchell, S.C.; Burford, M.D.; Robson, M.

1995-12-31

Due to growing public concern over heavy metals in the environment, soil, water and air particulate samples azre now routinely screened for their metal content. Conventional metal analysis typically involves acid digestion extraction and results in the generation of large aqueous and organic solvent waste. This harsh extraction process is usually used to obtain the total metal content of the sample, the extract being analysed by atomic emission or absorption spectroscoply techniques. A more selective method of metal extraction has been investigated which uses a supercritical fluid modified with a complexing agent. The relatively mild extraction method enables both organometallicmore » and inorganic metal species to be recovered intact. The various components from the supercritical fluid extract can be chromatographically separated using supercritical fluid chromatography (SFC) and positive identification of the metals achieved using atomic emission detection (AED). The aim of the study is to develop an analytical extraction procedure which enables a rapid, sensitive and quantitative analysis of metals in environmental samples, using just one extraction (eg SFE) and one analysis (eg SFC-AED) procedure.« less

Capillary electrophoresis application in metal speciation and complexation characterization

USDA-ARS?s Scientific Manuscript database

Capillary electrophoresis is amenable to the separation of metal ionic species and the characterization of metal-ligand interactions. This book chapter reviews and discusses three representative case studies in applications of CE technology in speciation and reactions of metal with organic molecules...

Temporal variability in Cu speciation, phytotoxicity, and soil microbial activity of Cu-polluted soils as affected by elevated temperature.

PubMed

Fu, Qing-Long; Weng, Nanyan; Fujii, Manabu; Zhou, Dong-Mei

2018-03-01

Global warming has obtained increasing attentions due to its multiple impacts on agro-ecosystem. However, limited efforts had been devoted to reveal the temporal variability of metal speciation and phytotoxicity of heavy metal-polluted soils affected by elevated temperature under the global warming scenario. In this study, effects of elevated temperature (15 °C, 25 °C, and 35 °C) on the physicochemical properties, microbial metabolic activities, and phytotoxicity of three Cu-polluted soils were investigated by a laboratory incubation study. Soil physicochemical properties were observed to be significantly altered by elevated temperature with the degree of temperature effect varying in soil types and incubation time. The Biolog and enzymatic tests demonstrated that soil microbial activities were mainly controlled and decreased with increasing incubation temperature. Moreover, plant assays confirmed that the phytotoxicity and Cu uptake by wheat roots were highly dependent on soil types but less affected by incubation temperature. Overall, the findings in this study have highlighted the importance of soil types to better understand the temperature-dependent alternation of soil properties, Cu speciation and bioavailability, as well as phytotoxicity of Cu-polluted soils under global warming scenario. The present study also suggests the necessary of investigating effects of soil types on the transport and accumulation of toxic elements in soil-crop systems under global warming scenario. Copyright © 2017 Elsevier Ltd. All rights reserved.

Characterisation of zinc in slags originated from a contaminated sediment by coupling /μ-PIXE, /μ-RBS, /μ-EXAFS and powder EXAFS spectroscopy

NASA Astrophysics Data System (ADS)

Isaure, M. P.; Laboudigue, A.; Manceau, A.; Sarret, G.; Tiffreau, C.; Trocellier, P.

2001-07-01

Depositing dredged sediments on soils is usual but it is a hazardous practice for the local environment when these sediments are polluted by heavy metals. This chemical hazard can be assessed by determining the speciation of metals. In this study, slags highly polluted with Zn and originated from a contaminated dredged sediment were investigated. Zn speciation was studied by laterally resolved techniques such as μ-particle induced X-ray emission (μ-PIXE), μ-Rutherford backscattering spectrometry (μ-RBS), μ-extended X-ray absorption fine structure (μ-EXAFS), and bulk analyses such as powder EXAFS spectroscopy. μ-PIXE and μ-RBS results showed that high concentrations of Zn were associated with S in localised areas at the surface of the slags while moderate amounts of Zn were mainly associated with Fe in the matrix. EXAFS results allowed to identify ZnS and Zn sorbed on ferrihydrite (5Fe 2O 3·9H 2O), proxy for iron oxy-hydroxides, as the main Zn-bearing phases. The occurrence of this Zn-iron oxy-hydroxide is interpreted as a mobilisation of Zn released from ZnS oxidation.

Speciation and Toxic Emissions from On road Vehicles, and Particulate Matter Emissions from Light-Duty Gasoline Vehicles in MOVES201X

EPA Science Inventory

Updated methane, non-methane organic gas, and volatile organic compound calculations based on speciation data. Updated speciation and toxic emission rates for new model year 2010 and later heavy-duty diesel engines. Updated particulate matter emission rates for 2004 and later mod...

CORRELATING METAL SPECIATION IN SOILS

EPA Science Inventory

Understanding bioavailability of metals from exposure to contaminated soils is a challenging aspect of environmental research. This presentation will examine three areas of research with respect to metal speciation in soils as it relates to bioavailability: 1) Pb immobilization a...

Augmenting granular activated carbon with natural clay for multicomponent sorption of heavy metals from aqueous solutions.

PubMed

Mu'azu, Nuhu Dalhat; Essa, Mohammed Hussain; Lukman, Salihu

2017-10-01

Multicomponent adsorption of Cd, Cr, Cu, Pb and Zn onto date palm pits based granular activated carbon (GAC) augmented with highly active natural clay at different proportion was investigated. The effects of the initial pH and the adsorbents mixed ratio on the removal selectivity sequence of the metals evaluated. Batch adsorption experiments were undertaken at initial pH 2, 6 and 12. At initial pH 2, both the percent removal and the metals adsorptive capacity decreased with increasing GAC to clay ratio (from 0 to 1) with the percentage removal of Cd, Zn and Cr ions dropping from 68, 81, 100% to 43, 57 and 70%, respectively. At both pH 6 and 12, the percentage removals and adsorption capacities of all the heavy metal ions are higher than at pH 2. Selectivity sequences for pH 2, 6 and 12 followed the order Pb > Cr > Cu > Zn > Cd; Pb > Cr > Cu > Cd > Zn and Cd > Cr > Cu > Pb > Zn, respectively. The adsorption trends were analyzed in relation to point of zero charge and ξ-potential and the metals ions speciation at different pH. These results will help better understand the feasibility of augmenting GAC with natural clay minerals during fixed bed column test which is more beneficial for practical industrial applications.

CORRELATING METAL SPECIATION IN SOILS TO RISK

EPA Science Inventory

Understanding bioavailability of metals from exposure to contaminated soils is a challenging aspect of environmental research. This presentation will examine three areas of research with respect to metal speciation in soils as it relates to bioavailability: 1) Pb immobilization a...

Phytoextraction of cadmium by Ipomoea aquatica (water spinach) in hydroponic solution: effects of cadmium speciation.

PubMed

Wang, Kai-Sung; Huang, Lung-Chiu; Lee, Hong-Shen; Chen, Pai-Ye; Chang, Shih-Hsien

2008-06-01

Phytoextraction is a promising technique to remediate heavy metals from contaminated wastewater. However, the interactions of multi-contaminants are not fully clear. This study employed cadmium, Triton X-100 (TX-100), and EDTA to investigate their interactions on phytotoxicity and Cd phytoextraction of Ipomoea aquatica (water spinach) in simulated wastewater. The Cd speciation was estimated by a chemical equilibrium model and MINEQL+. Statistic regression was applied to evaluate Cd speciation on Cd uptake in shoots and stems of I. aquatica. Results indicated that the root length was a more sensitive parameter than root weight and shoot weight. Root elongation was affected by Cd in the Cd-EDTA solution and TX-100 in the Cd-TX-100 solution. Both the root length and the root biomass were negatively correlated with the total soluble Cd ions. In contrast, Cd phytoextraction of I. aquatic was correlated with the aqueous Cd ions in the free and complex forms rather than in the chelating form. Additionally, the high Cd bioconcentration factors of I. aquatica (375-2227 l kg(-1) for roots, 45-144 l kg(-1) for shoots) imply that I. aquatica is a potential aquatic plant to remediate Cd-contaminated wastewater.

Quantitative Zn speciation in a contaminated dredged sediment by μ-PIXE, μ-SXRF, EXAFS spectroscopy and principal component analysis

NASA Astrophysics Data System (ADS)

Isaure, Marie-Pierre; Laboudigue, Agnès; Manceau, Alain; Sarret, Géraldine; Tiffreau, Christophe; Trocellier, Patrick; Lamble, Géraldine; Hazemann, Jean-Louis; Chateigner, Daniel

2002-05-01

Dredging and disposal of sediments onto agricultural soils is a common practice in industrial and urban areas that can be hazardous to the environment when the sediments contain heavy metals. This chemical hazard can be assessed by evaluating the mobility and speciation of metals after sediment deposition. In this study, the speciation of Zn in the coarse (500 to 2000 μm) and fine (<2 μm) fractions of a contaminated sediment dredged from a ship canal in northern France and deposited on an agricultural soil was determined by physical analytical techniques on raw and chemically treated samples. Zn partitioning between coexisting mineral phases and its chemical associations were first determined by micro-particle-induced X-ray emission and micro-synchrotron-based X-ray radiation fluorescence. Zn-containing mineral species were then identified by X-ray diffraction and powder and polarized extended X-ray absorption fine structure spectroscopy (EXAFS). The number, nature, and proportion of Zn species were obtained by a coupled principal component analysis (PCA) and least squares fitting (LSF) procedure, applied herein for the first time to qualitatively (number and nature of species) and quantitatively (relative proportion of species) speciate a metal in a natural system. The coarse fraction consists of slag grains originating from nearby Zn smelters. In this fraction, Zn is primarily present as sphalerite (ZnS) and to a lesser extent as willemite (Zn 2SiO 4), Zn-containing ferric (oxyhydr)oxides, and zincite (ZnO). In the fine fraction, ZnS and Zn-containing Fe (oxyhydr)oxides are the major forms, and Zn-containing phyllosilicate is the minor species. Weathering of ZnS, Zn 2SiO 4, and ZnO under oxidizing conditions after the sediment disposal accounts for the uptake of Zn by Fe (oxyhydr)oxides and phyllosilicates. Two geochemical processes can explain the retention of Zn by secondary minerals: uptake on preexisting minerals and precipitation with dissolved Fe and Si. The second process likely occurs because dissolved Zn and Si are supersaturated with respect to Zn phyllosilicate. EXAFS spectroscopy, in combination with PCA and LSF, is shown to be a meaningful approach to quantitatively determining the speciation of trace elements in sediments and soils.

Interaction of Thermus thermophilus, ArsC enzyme and gold nanoparticles naked-eye assays speciation between As(III) and As(V)

NASA Astrophysics Data System (ADS)

Politi, Jane; Spadavecchia, Jolanda; Fiorentino, Gabriella; Antonucci, Immacolata; Casale, Sandra; De Stefano, Luca

2015-10-01

The thermophilic bacterium Thermus thermophilus HB27 encodes chromosomal arsenate reductase (TtArsC), the enzyme responsible for resistance to the harmful effects of arsenic. We report on adsorption of TtArsC onto gold nanoparticles for naked-eye monitoring of biomolecular interaction between the enzyme and arsenic species. Synthesis of hybrid biological-metallic nanoparticles has been characterized by transmission electron microscopy (TEM), ultraviolet-visible (UV-vis), dynamic light scattering (DLS) and phase modulated infrared reflection absorption (PM-IRRAS) spectroscopies. Molecular interactions have been monitored by UV-vis and Fourier transform-surface plasmon resonance (FT-SPR). Due to the nanoparticles’ aggregation on exposure to metal salts, pentavalent and trivalent arsenic solutions can be clearly distinguished by naked-eye assay, even at 85 μM concentration. Moreover, the assay shows partial selectivity against other heavy metals.

An experimental and thermodynamic equilibrium investigation of the Pb, Zn, Cr, Cu, Mn and Ni partitioning during sewage sludge incineration.

PubMed

Liu, Jingyong; Fu, Jiewen; Ning, Xun'an; Sun, Shuiyu; Wang, Yujie; Xie, Wuming; Huang, Shaosong; Zhong, Sheng

2015-09-01

The effects of different chlorides and operational conditions on the distribution and speciation of six heavy metals (Pb, Zn, Cr, Cu, Mn and Ni) during sludge incineration were investigated using a simulated laboratory tubular-furnace reactor. A thermodynamic equilibrium investigation using the FactSage software was performed to compare the experimental results. The results indicate that the volatility of the target metals was enhanced as the chlorine concentration increased. Inorganic-Cl influenced the volatilization of heavy metals in the order of Pb>Zn>Cr>Cu>Mn>Ni. However, the effects of organic-Cl on the volatility of Mn, Pb and Cu were greater than the effects on Zn, Cr and Ni. With increasing combustion temperature, the presence of organic-Cl (PVC) and inorganic-Cl (NaCl) improved the transfer of Pb and Zn from bottom ash to fly ash or fuse gas. However, the presence of chloride had no obvious influence on Mn, Cu and Ni. Increased retention time could increase the volatilization rate of heavy metals; however, this effect was insignificant. During the incineration process, Pb readily formed PbSiO4 and remained in the bottom ash. Different Pb compounds, primarily the volatile PbCl2, were found in the gas phase after the addition of NaCl; the dominant Pb compounds in the gas phase after the addition of PVC were PbCl2, Pb(ClO4)2 and PbCl2O4. Copyright © 2015. Published by Elsevier B.V.

Pyrolysis of the mixture of MSWI fly ash and sewage sludge for co-disposal: Effect of ferrous/ferric sulfate additives.

PubMed

Hu, Yuyan; Yang, Fan; Chen, Fangfang; Feng, Yuheng; Chen, Dezhen; Dai, Xiaohu

2018-05-01

Co-pyrolysis with sewage sludge was proved to be an efficient pre-treatment for sanitary landfill of municipal solid waste incineration (MSWI) fly ash (FA). In this study, to improve the stabilization effect of heavy metals, mixed ferrous/ferric sulfate was added into the FA/SS mixture before pyrolysis. To examine the feasibility of the landfill of co-pyrolysis char, toxicity characteristic leaching procedure (HJ/T300) was conducted. In addition, physio-chemical characteristics of char were also tested to explain the stability of heavy metals, including the speciation, mineralogical composition and the morphological features of them. The results indicated that within the range that the obtained char could meet the standard for landfill (GB16889-2008), the appropriate addition of mixed ferrous/ferric sulfates benefit to raising the FA ratio in the FA/SS mixture. The maximum ratio of 67 wt% is achieved when the additive was 1.5 wt% of dried SS (based on iron element) and the pyrolysis temperature was 500 °C. Copyright © 2018 Elsevier Ltd. All rights reserved.

Mechanisms of lichen resistance to metallic pollution

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

Sarret, C.; Manceau, A.; Eybert-Berard, L.

1998-11-01

Some lichens have a unique ability to grow in heavily contaminated areas due to the development of adaptative mechanisms allowing a high tolerance to metals. Here the authors report on the chemical forms of Pb and Zn in the metal hyperaccumulator Diploschistes muscorum and of Pb in the metal tolerant lichen Xanthoria parietina. The speciation of Zn and Pb has been investigated by powder X-ray diffraction (XRD) and extended X-ray absorption fine structure (EXAFS) spectroscopy using the advanced third-generation synchrotron radiation source of the European synchrotron radiation facility (ESRF in Grenoble). This study reveals that in both lichens cells aremore » protected from toxicity by complexation of heavy metals, but the strategies differ: in D. muscorum, Pb and Zn are accumulated through an enhanced synthesis of oxalate, which precipitates toxic elements as insoluble salts, whereas in X. parietina, Pb is complexed to carboxylic groups of the fungal cell walls. The authors conclude that hyperaccumulation of metals results from a reactive mechanism of organic acid production, whereas metallo-tolerance is achieved by a passive complexation to existing functional groups.« less

Effects of freeze-thaw on characteristics of new KMP binder stabilized Zn- and Pb-contaminated soils.

PubMed

Wei, Ming-Li; Du, Yan-Jun; Reddy, Krishna R; Wu, Hao-Liang

2015-12-01

For viable and sustainable reuse of solidified/stabilized heavy metal-contaminated soils as roadway subgrade materials, long-term durability of these soils should be ensured. A new binder, KMP, has been developed for solidifying/stabilizing soils contaminated with high concentrations of heavy metals. However, the effects of long-term extreme weather conditions including freeze and thaw on the leachability and strength of the KMP stabilized contaminated soils have not been investigated. This study presents a systematic investigation on the impacts of freeze-thaw cycle on leachability, strength, and microstructural characteristics of the KMP stabilized soils spiked with Zn and Pb individually and together. For comparison purpose, Portland cement is also tested as a conventional binder. Several series of tests are conducted including the toxicity characteristic leaching procedure (TCLP), modified European Community Bureau of Reference (BCR) sequential extraction procedure, unconfined compression test (UCT), and mercury intrusion porosimetry (MIP). The results demonstrate that the freeze-thaw cycles have much less impact on the leachability and strength of the KMP stabilized soils as compared to the PC stabilized soils. After the freeze-thaw cycle tests, the KMP stabilized soils display much lower leachability, mass loss, and strength loss. These results are assessed based on the chemical speciation of Zn and Pb, and pore size distribution of the soils. Overall, this study demonstrates that the KMP stabilized heavy metal-contaminated soils perform well under the freeze-thaw conditions.

Biosensor for metal analysis and speciation

DOEpatents

Aiken, Abigail M.; Peyton, Brent M.; Apel, William A.; Petersen, James N.

2007-01-30

A biosensor for metal analysis and speciation is disclosed. The biosensor comprises an electron carrier immobilized to a surface of an electrode and a layer of an immobilized enzyme adjacent to the electrode. The immobilized enzyme comprises an enzyme having biological activity inhibited by a metal to be detected by the biosensor.

Speciation and precipitation of heavy metals in high-metal and high-acid mine waters from the Iberian Pyrite Belt (Portugal).

PubMed

Durães, Nuno; Bobos, Iuliu; da Silva, Eduardo Ferreira

2017-02-01

Acid mine waters (AMW) collected during high- and low-flow water conditions from the Lousal, Aljustrel, and São Domingos mining areas (Iberian Pyrite Belt) were physicochemically analyzed. Speciation calculation using PHREEQC code confirms the predominance of Me n+ and Me-SO 4 species in AMW samples. Higher concentration of sulfate species (Me-SO 4 ) than free ion species (Me n+ , i.e., Al, Fe, and Pb) were found, whereas opposite behavior is verified for Mg, Cu, and Zn. A high mobility of Zn than Cu and Pb was identified. The sulfate species distribution shows that Fe 3+ -SO 4 2- , SO 4 2- , HSO 4 - , Al-SO 4 , MgSO 4 0 , and CaSO 4 0 are the dominant species, in agreement with the simple and mixed metal sulfates and oxy-hydroxysulphates precipitated from AMW. The saturation indices (SI) of melanterite and epsomite show a positive correlation with Cu and Zn concentrations in AMW, which are frequently retained in simple metal sulfates. Lead is well correlated with jarosite and alunite (at least in very acid conditions) than with simple metal sulfates. The Pb for K substitution in jarosite occurs as increasing Pb concentration in solution. Lead mobility is also controlled by anglesite precipitation (a fairly insoluble sulfate), where a positive correlation was ascertained when the SI approaches equilibrium. The zeta potential of AMW decreased as pH increased due to colloidal particles aggregation, where water species change from SO 4 2- to OH - species during acid to alkaline conditions, respectively. The AMW samples were supersaturated in schwertmannite and goethite, confirmed by the Me n+ -SO 4 , Me n+ -Fe-O-OH, or Me n+ -S-O-Fe-O complexes identified by attenuated total reflectance infrared spectroscopy (ATR-IR). The ATR-IR spectrum of an AMW sample with pH 3.5 (sample L1) shows well-defined vibration plans attributed to SO 4 tetrahedron bonded with Fe-(oxy)hydroxides and the Me n+ sorbed by either SO 4 or Fe-(oxy)hydroxides. For samples with lower pH values (pH ~ 2.5-samples SD1 and SD4), the vibration plans attributed to Me n+ sorption are not evidenced, indicating its release in solution. The sorption of heavy metals on the first precipitated simple metal sulfates was ascertained by scanning electron microscopy coupled with X-ray spectrometry (SEM-EDX), where X-ray maps of Cu and Zn confirm a distribution of both metals in the melanterite structure.

[Study on composite stabilization of arsenic (As) contaminated soil].

PubMed

Wang, Hao; Pan, Li-xiang; Zhang, Xiang-yu; Li, Meng; Song, Bao-hua

2013-09-01

Since the contaminated soil may contain various kinds of heavy metals, use of single chemical reagent leads to poor remediation and high cost. In this study, soil containing As, Zn, Cd was sampled, and different reagents were selected to carry out the rapid stabilization of contaminated soil. The TCLP (toxicity characteristic leaching procedure) was used to evaluate the leachate toxicity of heavy metals and the results indicated that calcium-containing, sulphur-containing and iron-containing reagents had good performance in reducing the metal mobility. The stabilization efficiency of the six reagents tested ranked in the order of CaO > Na2S > organic sulfur > Chitosan > FeSO4 > (C2H5)2NCS2Na. Two types of reagents (six reagents) were combined based on the target properties of different reagents and the stabilization efficiency was evaluated and analyzed. The results indicated that the composite reagents had higher stabilization efficiency: the efficiency of 3% FeSO4 + 5% CaO was 81.7%, 97.2% and 68.2% for As, Cd and Zn, respectively, and the efficiency of 3% CaO + 5% organic sulfur was 76.6%, 95.7% and 93.8% for these three metals, respectively. Speciation analysis was carried out in this study and the results suggested that it was the change of metals from the exchangeable state to the reduction (for inorganic reagent) or oxidation state (for organic reagent) that caused the soil stabilization and the degree of change determined the stabilization efficiency.

Influence of Organic Matter - Mineral Interfacial Reactions on Metal(loid) Speciation and Bioaccessibility

NASA Astrophysics Data System (ADS)

Chorover, J.; Kong, S.; Root, R. A.; Thomas, A.

2015-12-01

Bioaccessibility of contaminant metals in geomedia is often measured on the basis of kinetic release to solution during in vitro reaction with biofluid simulants. We postulate that development of a predictive-mechanistic understanding of bioaccessibility requires knowledge of metal(loid) molecular speciation upon sample introduction, as well as its change over the course of the in vitro reaction. Our results - including data from batch, column, mesocosm and field studies pertaining to arsenic, lead, and zinc contaminated materials - indicate the strong influence of organic matter and associated biological activity on metal(loid) speciation in mine tailings and related model systems. Furthermore, presence/absence of organic matter during bioassays affects the kinetics of metal(loid) release into biofluid simulants through multiple mechanisms.

Assessment of heavy metal contamination in the sediments of Nansihu Lake Catchment, China.

PubMed

Liu, Enfeng; Shen, Ji; Yang, Liyuan; Zhang, Enlou; Meng, Xianghua; Wang, Jianjun

2010-02-01

At present, anthropogenic contribution of heavy metals far exceeds natural input in some aquatic sediment, but the proportions are difficult to differentiate due to the changes in sediment characters. In this paper, the metal (Al, Fe, K, Mg, Ca, Cr, Cu, Ni, and Zn) concentrations, grain size, and total organic carbon (TOC) content in the surface and core sediments of Nansihu Lake Catchment (the open lake and six inflow rivers) were determined. The chemical speciations of the metals (Al, Fe, Cr, Cu, Ni, and Zn) in the surface sediments were also analyzed. Approaches of factor analysis, normalized enrichment factor (EF) and the new non-residual fractions enrichment factor (K(NRF)) were used to differentiate the sources of the metals in the sediments, from detrital clastic debris or anthropogenic input, and to quantify the anthropogenic contamination. The results indicate that natural processes were more dominant in concentrating the metals in the surface and core sediments of the open lake. High concentration of Ca and deficiency of other metals in the upper layers of the sediment core were attributed to the input of carbonate minerals in the catchment with increasing human activities since 1980s. High TOC content magnified the deficiency of the metals. Nevertheless, the EF and K(NRF) both reveal moderate to significant anthropogenic contamination of Cr, Cu, Ni, and Zn in the surface sediments of Laoyun River and the estuary and Cr in the surface sediments of Baima River. The proportion of non-residual fractions (acid soluble, reducible, and oxidizable fractions) of Cr, Cu, Ni, and Zn in the contaminated sediments increased to 37-99% from the background levels less than 30%.

Small changes in Cu redox state and speciation generate large isotope fractionation during adsorption and incorporation of Cu by a phototrophic biofilm

NASA Astrophysics Data System (ADS)

Coutaud, Margot; Méheut, Merlin; Glatzel, Pieter; Pokrovski, Gleb S.; Viers, Jérôme; Rols, Jean-Luc; Pokrovsky, Oleg S.

2018-01-01

Despite the importance of phototrophic biofilms in metal cycling in freshwater systems, metal isotope fractionation linked to metal adsorption and uptake by biofilm remains very poorly constrained. Here, copper isotope fractionation by a mature phototrophic biofilm during Cu surface adsorption and incorporation was studied in batch reactor (BR) and open drip flow reactor (DFR) systems at ambient conditions. X-ray Absorption Spectroscopy (both Near Edge Structure, XANES, and Extended Fine Structure, EXAFS) at Cu K-edge of the biofilm after its interaction with Cu in BR experiments allowed characterizing the molecular structure of assimilated Cu and quantifying the degree of CuII to CuI reduction linked to Cu assimilation. For both BR and DFR experiments, Cu adsorption caused enrichment in heavy isotope at the surface of the biofilm relative to the aqueous solution, with an apparent enrichment factor for the adsorption process, ε65Cuads, of +1.1 ± 0.3‰. In contrast, the isotope enrichment factor during copper incorporation into the biofilm (ε65Cuinc) was highly variable, ranging from -0.6 to +0.8‰. This variability of the ε65Cuinc value was likely controlled by Cu cellular uptake via different transport pathways resulting in contrasting fractionation. Specifically, the CuII storage induced enrichment in heavy isotope, whereas the toxicity response of the biofilm to Cu exposure resulted in reduction of CuII to CuI, thus yielding the biofilm enrichment in light isotope. EXAFS analyses suggested that a major part of the Cu assimilated by the biofilm is bound to 5.1 ± 0.3 oxygen or nitrogen atoms, with a small proportion of Cu linked to sulfur atoms (NS < 0.6) of sulfhydryl groups. XANES analyses showed that the proportion of CuIIvs CuI, compared to the initial CuII/CuI ratio, decreased by 14% after the first hour of reaction and by 6% after 96 h of reaction. The value of ε65Cuinc of the biofilm exhibited a similar trend over time of exposure. Our study demonstrates the complexity of biological processes associated with live phototrophic biofilms, which produce large and contrasting isotope fractionations following rather small Cu redox and speciation changes during uptake, storage or release of the metal, i.e., favoring heavy isotopes during complexation with carboxylate ligands and light isotopes during reduction of CuII-O/N to CuI-sulfhydryl moieties.

Effect of sulphur concentration on bioleaching of heavy metals from contaminated dredged sediments.

PubMed

Fang, D; Zhao, L; Yang, Z Q; Shan, H X; Gao, Y; Yang, Q

2009-11-01

The sulphur-based bioleaching process using sulphur-oxidizing bacteria (SOB) has been demonstrated to be a feasible technology for removing heavy metals from contaminated sediments, but the excess sulphur application will lead to the re-acidification of bioleached sediments. The objective of the present study was to examine the effect of sulphur concentration on the bioleaching of heavy metals from contaminated sediments, with the ultimate purpose of minimizing the sulphur addition. The results showed that the inoculation of 7% of indigenous SOB, containing 3.6 x 10(8) colony forming units (CFU) mL(-1), and addition of elemental sulphur as a substrate (0.5 to 7.0 g L(-1)) resulted in a sharp decrease in sediment pH from an initial pH 8.0 to pH 1.4-2.4 and an increase in ORP (oxidation-reduction potential) from -10 mV to 500 mV within 10 days of bioleaching. Although the increase in sulphur concentration enhanced the rates of pH reduction and ORP elevation, the bioleaching process with the addition of 3.0 g L(-1) of sulphur was already sufficient to reach conditions of acidity (pH < 2.0) and ORP (500 mV) necessary for a satisfactory removal of metals, and, at day 10, 71.8% of Cu, 58.2% of Zn, and 25.3% of Cr were removed from the sediments. During the bioleaching process, Zn removal increased with a reduction in pH, whereas the removal of Cu and Cr increased not only with a reduction in pH but also with an increase in ORP. Results of sequential selective extraction indicated that the final levels of metal removals were dependent on their speciation distribution in the original sediments, and after bioleaching those unremoved metals in the bioleached sediments mainly existed in the residual fraction.

[Impact of acid mining drainage on the quality of superficial waters and sediments in the Marrakesh region, Morocco].

PubMed

El Gharmali, A; Rada, A; El Adnani, M; Tahlil, N; El Meray, M; Nejmeddine, A

2004-12-01

The aim of the present study is the evaluation of the effects of the acid drainage of three abandoned mining sites: SB-Othmane, Kettara and Draâ-sfar, on water and sediment quality of the Tensift River and its two temporary tributaries, the Kettara and El-Coudia Oueds. These mining sites located near Marrakesh contain mining residues abandoned for ten to twenty years. They are presently in an agricultural region of the Haouz district. In each site, these uncontrolled mining residues present a high level of metallic sulphide and generate, during rainy periods, leaching products which have physical and chemical characteristics of acid mine drainage (AMD). These percolates display an acidic pH ranging from 2.5 to 5.2, a high electric conductivity, large amounts of sulphate and heavy metals, especially under dissolved form (e.g. Cd: 17.34 mg l(-1); Fe: 1734 mg l(-1); Zn: 3935 mg l(-1)). Except for Pb, the free ionic form is the most abundant metallic form, as showed by calculations using the speciation GEOCHEM program. The analysis of water and sediments of the surrounding superficial aquatic ecosystems shows a modification of water chemical facies and an enrichment in heavy metals, mainly under the solid phase for Fe, Pb, Cu, Co, Cr and Ni, and under dissolved fraction for Cd and Zn. The dissolved fraction of these metals is dominated by the free ionic form, considered as available for organisms. Furthermore, sediments contain important quantities of heavy metals (Pb: 1450 microg g(-1), Zn: 1562 microg g(-1)) with an available fraction which is higher than 40% for the Cd and Zn. The abundance of trace elements (free ionic and available forms) in water and sediment presents a durable risk of their transfer to food chains.

Including the spatial variability of metal speciation in the effect factor in life cycle impact assessment: Limits of the equilibrium partitioning method.

PubMed

Tromson, Clara; Bulle, Cécile; Deschênes, Louise

2017-03-01

In life cycle assessment (LCA), the potential terrestrial ecotoxicity effect of metals, calculated as the effect factor (EF), is usually extrapolated from aquatic ecotoxicological data using the equilibrium partitioning method (EqP) as it is more readily available than terrestrial data. However, when following the AMI recommendations (i.e. with at least enough species that represents three different phyla), there are not enough terrestrial data for which soil properties or metal speciation during ecotoxicological testing are specified to account for the influence of soil property variations on metal speciation when using this approach. Alternatively, the TBLM (Terrestrial Biotic Ligand Model) has been used to determine an EF that accounts for speciation, but is not available for metals; hence it cannot be consistently applied to metals in an LCA context. This paper proposes an approach to include metal speciation by regionalizing the EqP method for Cu, Ni and Zn with a geochemical speciation model (the Windermere Humic Aqueous Model 7.0), for 5213 soils selected from the Harmonized World Soil Database. Results obtained by this approach (EF EqP regionalized ) are compared to the EFs calculated with the conventional EqP method, to the EFs based on available terrestrial data and to the EFs calculated with the TBLM (EF TBLM regionalized ) when available. The spatial variability contribution of the EF to the overall spatial variability of the characterization factor (CF) has been analyzed. It was found that the EFs EqP regionalized show a significant spatial variability. The EFs calculated with the two non-regionalized methods (EqP and terrestrial data) fall within the range of the EFs EqP regionalized . The EFs TBLM regionalized cover a larger range of values than the EFs EqP regionalized but the two methods are not correlated. This paper highlights the importance of including speciation into the terrestrial EF and shows that using the regionalized EqP approach is not an acceptable proxy for terrestrial ecotoxicological data even if it can be applied to all metals. Copyright © 2016. Published by Elsevier B.V.

Biodiesel and Cold Temperature Effects on Speciated Mobile Source Air Toxics from Modern Diesel Trucks

EPA Science Inventory

Speciated volatile organic compounds (VOCs) with a particular focus on mobile source air toxics (MSATs) were measured in diesel exhaust from three heavy-duty trucks equipped with modern aftertreatment technologies. Emissions testing was conducted on a temperature controlled chass...

Biodiesel and Cold Temperature Effect on Speciated Mobile Source Air Toxics from Modern Diesel Trucks

EPA Science Inventory

Speciated volatile organic compounds (VOCs) with a particular focus on mobile source air toxics (MSATs) were measured in diesel exhaust from three heavy-duty trucks equipped with modern aftertreatment technologies. Emissions testing was conducted on a temperature controlled chass...

Biodegradation and speciation of residual SS-ethylenediaminedisuccinic acid (EDDS) in soil solution left after soil washing.

PubMed

Tandy, Susan; Ammann, Adrian; Schulin, Rainer; Nowack, Bernd

2006-07-01

This paper aims to investigate the degradation and speciation of EDDS-complexes (SS-ethylenediaminedisuccinic acid) in soil following soil washing. The changes in soil solution metal and EDDS concentrations were investigated for three polluted soils. EDDS was degraded after a lag phase of 7-11 days with a half-life of 4.18-5.60 days. No influence of EDDS-speciation on the reaction was observed. The decrease in EDDS resulted in a corresponding decrease in solubilized metals. Changes in EDDS speciation can be related to (1) initial composition of the soil, (2) temporarily anoxic conditions in the soil slurry after soil washing, (3) exchange of EDDS complexes with Cu even in soils without elevated Cu and (4) formation of NiEDDS. Dissolved organic matter is important for metal speciation at low EDDS concentrations. Our results show that even in polluted soils EDDS is degraded from a level of several hundred micromoles to below 1 microM within 50 days.

Sources and fates of heavy metals in a mining-impacted stream: Temporal variability and the role of iron oxides

PubMed Central

Schaider, Laurel A.; Senn, David B.; Estes, Emily R.; Brabander, Daniel J.; Shine, James P.

2014-01-01

Heavy metal contamination of surface waters at mining sites often involves complex interactions of multiple sources and varying biogeochemical conditions. We compared surface and subsurface metal loading from mine waste pile runoff and mine drainage discharge and characterized the influence of iron oxides on metal fate along a 0.9-km stretch of Tar Creek (Oklahoma, USA), which drains an abandoned Zn/Pb mining area. The importance of each source varied by metal: mine waste pile runoff contributed 70% of Cd, while mine drainage contributed 90% of Pb, and both sources contributed similarly to Zn loading. Subsurface inputs accounted for 40% of flow and 40-70% of metal loading along this stretch. Streambed iron oxide aggregate material contained highly elevated Zn (up to 27,000 μg g−1), Pb (up to 550 μg g−1) and Cd (up to 200 μg g−1) and was characterized as a heterogeneous mixture of iron oxides, fine-grain mine waste, and organic material. Sequential extractions confirmed preferential sequestration of Pb by iron oxides, as well as substantial concentrations of Zn and Cd in iron oxide fractions, with additional accumulation of Zn, Pb, and Cd during downstream transport. Comparisons with historical data show that while metal concentrations in mine drainage have decreased by more than an order of magnitude in recent decades, the chemical composition of mine waste pile runoff has remained relatively constant, indicating less attenuation and increased relative importance of pile runoff. These results highlight the importance of monitoring temporal changes at contaminated sites associated with evolving speciation and simultaneously addressing surface and subsurface contamination from both mine waste piles and mine drainage. PMID:24867708

Characterizing Zinc Speciation in Soils from a Smelter-Affected Boreal Forest Ecosystem.

PubMed

Hamilton, Jordan G; Farrell, Richard E; Chen, Ning; Feng, Renfei; Reid, Joel; Peak, Derek

2016-03-01

HudBay Minerals, Inc., has mined and/or processed Zn and Cu ore in Flin Flon, MB, Canada, since the 1930s. The boreal forest ecosystem and soil surrounding these facilities have been severely impacted by mixed metal contamination and HSO deposition. Zinc is one of the most prevalent smelter-derived contaminants and has been identified as a key factor that may be limiting revegetation. Metal toxicity is related to both total concentrations and speciation; therefore, X-ray absorption spectroscopy and X-ray fluorescence mapping were used to characterize Zn speciation in soils throughout the most heavily contaminated areas of the landscape. Zinc speciation was linked to two distinct soil types. Group I soils consist of exposed soils in weathered positions of bedrock outcrops with Zn present primarily as franklinite, a (ZnFeO) spinel mineral. Group II soils are stabilized by an invasive metal-tolerant grass species, with Zn found as a mixture of octahedral (Fe oxides) and tetrahedral Mn oxides) adsorption complexes with a franklinite component. Soil erosion influences Zn speciation through the redistribution of Zn and soil particulates from Group I landscape positions to Group II soils. Despite Group II soils having the highest concentrations of CaCl-extractable Zn, they support metal-tolerant plant growth. The metal-tolerant plants are probably preferentially colonizing these areas due to better soil and nutrient conditions as a result of soil deposition from upslope Group I areas. Zinc concentration and speciation appears to not influence the colonization by metal-tolerant grasses, but the overall soil properties and erosion effects prevent the revegetation by native boreal forest species. Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.

Nickel speciation in several serpentine (ultramafic) topsoils via bulk synchrotron-based techniques

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

Siebecker, Matthew G.; Chaney, Rufus L.; Sparks, Donald L.

2017-07-01

Serpentine soils have elevated concentrations of trace metals including nickel, cobalt, and chromium compared to non-serpentine soils. Identifying the nickel bearing minerals allows for prediction of potential mobility of nickel. Synchrotron-based techniques can identify the solid-phase chemical forms of nickel with minimal sample treatment. Element concentrations are known to vary among soil particle sizes in serpentine soils. Sonication is a useful method to physically disperse sand, silt and clay particles in soils. Synchrotron-based techniques and sonication were employed to identify nickel species in discrete particle size fractions in several serpentine (ultramafic) topsoils to better understand solid-phase nickel geochemistry. Nickel commonlymore » resided in primary serpentine parent material such as layered-phyllosilicate and chain-inosilicate minerals and was associated with iron oxides. In the clay fractions, nickel was associated with iron oxides and primary serpentine minerals, such as lizardite. Linear combination fitting (LCF) was used to characterize nickel species. Total metal concentration did not correlate with nickel speciation and is not an indicator of the major nickel species in the soil. Differences in soil texture were related to different nickel speciation for several particle size fractionated samples. A discussion on LCF illustrates the importance of choosing standards based not only on statistical methods such as Target Transformation but also on sample mineralogy and particle size. Results from the F-test (Hamilton test), which is an underutilized tool in the literature for LCF in soils, highlight its usefulness to determine the appropriate number of standards to for LCF. EXAFS shell fitting illustrates that destructive interference commonly found for light and heavy elements in layered double hydroxides and in phyllosilicates also can occur in inosilicate minerals, causing similar structural features and leading to false positive results in LCF.« less

Dissolved sulfides in the oxic water column of San Francisco Bay, California

USGS Publications Warehouse

Kuwabara, J.S.; Luther, G.W.

1993-01-01

Trace contaminants enter major estuaries such as San Francisco Bay from a variety of point and nonpoint sources and may then be repartitioned between solid and aqueous phases or altered in chemical speciation. Chemical speciation affects the bioavailability of metals as well as organic ligands to planktonic and benthic organisms, and the partitioning of these solutes between phases. Our previous, work in south San Francisco Bay indicated that sulfide complexation with metals may be of particular importance because of the thermodynamic stability of these complexes. Although the water column of the bay is consistently well-oxygenated and typically unstratified with respect to dissolved oxygen, the kinetics of sulfide oxidation could exert at least transient controls on metal speciation. Our initial data on dissolved sulfides in the main channel of both the northern and southern components of the bay consistently indicate submicromolar concenrations (from <1 nM to 162 nM), as one would expect in an oxidizing environment. However, chemical speciation calculations over the range of observed sulfide concentrations indicate that these trace concentrations in the bay water column can markedly affect chemical speciation of ecologically significant trace metals such as cadmium, copper, and zinc.

Utilization of steel, pulp and paper industry solid residues in forest soil amendment: relevant physicochemical properties and heavy metal availability.

PubMed

Mäkelä, Mikko; Watkins, Gary; Pöykiö, Risto; Nurmesniemi, Hannu; Dahl, Olli

2012-03-15

Industrial residue application to soil was investigated by integrating granulated blast furnace or converter steel slag with residues from the pulp and paper industry in various formulations. Specimen analysis included relevant physicochemical properties, total element concentrations (HCl+HNO3 digestion, USEPA 3051) and chemical speciation of chosen heavy metals (CH3COOH, NH2OH·HCl and H2O2+H2O2+CH3COONH4, the BCR method). Produced matrices showed liming effects comparable to commercial ground limestone and included significant quantities of soluble vital nutrients. The use of converter steel slag, however, led to significant increases in the total concentrations of Cr and V. Subsequently, total Cr was attested to occur as Cr(III) by Na2CO3+NaOH digestion followed by IC UV/VIS-PCR (USEPA 3060A). Additionally, 80.6% of the total concentration of Cr (370 mg kg(-1), d.w.) occurred in the residual fraction. However, 46.0% of the total concentration of V (2470 mg kg(-1), d.w.) occurred in the easily reduced fraction indicating potential bioavailability. Copyright © 2011 Elsevier B.V. All rights reserved.

Controls on accumulation and soil solution partitioning of heavy metals across upland sites in United Kingdom (UK).

PubMed

Zia, Afia; van den Berg, Leon; Ahmad, Muhammad Nauman; Riaz, Muhammad; Zia, Dania; Ashmore, Mike

2018-05-31

A significant body of knowledge suggests that soil solution pH and dissolved organic carbon (DOC) strongly influence metal concentrations and speciation in porewater, however, these effects vary between different metals. This study investigated the factors influencing soil and soil solution concentrations of copper (Cu), lead (Pb), nickel (Ni) and zinc (Zn) under field conditions in upland soils from UK having a wide range of pH, DOC and organic matter contents. The study primarily focussed on predicting soil and soil solution metal concentrations from the data on total soil metal concentrations (HNO 3 extracts) and soil and soil solution properties (pH, DOC and organic matter content). We tested the multiple regression models proposed by Tipping et al. (2003) to predict heavy metal concentrations in soil solutions and the results indicated a better fit (higher R 2 values) in both studies for Pb compared to the Zn and Cu concentrations. Both studies observed consistent negative relationships of metals with pH and loss on ignition (LOI) suggesting an increase in soil solution metal concentrations with increasing acidity. The positive relationship between Pb concentrations in porewater and HNO 3 extracts was similar for both studies, however, similar relationships were not found for the Zn and Cu concentrations because of the negative coefficients for these metals in our study. The results of this study conclude that the predictive equations of Tipping et al. (2003) may not be applicable to the field sites where the range of DOC and metal concentrations is much lower than their study. Our study also suggests that the extent to which metals are partitioned into soil solution is lower in soils with a higher organic matter contents due to binding of these metals to soil organic matter. Copyright © 2018 Elsevier Ltd. All rights reserved.

Adding to the Mercury Speciation Toolbox

NASA Astrophysics Data System (ADS)

Fitts, J. P.; Northrup, P. A.; Chidambaram, D.; Kalb, P. D.

2007-12-01

Mercury was used to separate lithium-6 isotope for weapons production at the Y-12 Plant in Oak Ridge, TN in the 1950s and 1960s. A large portion of the waste Hg entered the environment and continues to move throughout the sub-surface and surface waters in the area. Environmental management of Hg contamination within this complex hydrologic system, where Hg speciation and the mobile fraction have been found to vary widely, will require ongoing characterization and predictive modeling of Hg speciation. State-of-the-art spectroscopic tools that can directly probe Hg speciation in preserved aqueous and sediment samples with greater sensitivity, however, are required to determine rates and mechanisms of biogeochemical reactions. We will present the first results demonstrating the use of x-ray absorption spectroscopy (XAS) at the Hg M5 edge (2295 eV) to fingerprint Hg species. Heavy-metal M5 absorption edges can have very sharp features due to local electron transitions, and therefore, we are developing this edge as a tool for quantitative measurement of Hg species. In addition, sulfur speciation using the sulfur K absorption edge, which is at a similar energy (2472 eV), can be measured in the same scan as the Hg M5 edge. Potentially important organic and inorganic sulfur species (sulfide, disulfide, elemental sulfur, sulfite and sulfate) are readily differentiated, and thereby, provides an independent method for monitoring the redox state of the system along with changes in S-Hg bonding. We will also present x-ray microprobe 2-D concentration maps of Hg and other elements at the grain and pore scales to identify its microscopic distribution and chemical associations. When used in combination with established sequential extraction and direct spectroscopic methods, the addition of XAS at the Hg M5 edge should provide a significant advancement in the determination of Hg speciation in complex biogeochemical environments.

Leaching assessments of toxic metals in waste plasma display panel glass.

PubMed

Chen, Mengjun; Jiang, Pengfei; Chen, Haiyan; Ogunseitan, Oladele A; Li, Yungui

2015-06-01

The plasma display panel (PDP) is rapidly becoming obsolete, contributing in large amounts to the electronic waste stream. In order to assess the potential for environmental pollution due to hazardous metals leached from PDP glass, standardized leaching procedures, chemical speciation assessments, and bioavailability tests were conducted. According to the Toxicity Characteristic Leaching Procedure (TCLP), arsenic in back glass was present at 4.46 ± 0.22 mg/L, close to its regulation limit of 5 mg/L. Zn is not available in the TCLP, but its TCLP leaching concentration in back glass is 102.96 ± 5.34 mg/L. This is because more than 90% of Zn is in the soluble and exchangeable and carbonate fraction. We did not detect significant levels of Ag, Ba, or Cu in the TCLP leachate, and the main fraction of Ag and Ba is residual, more than 95%, while the fraction distribution of Cu changes SEP by SEP. Ethylenediamine tetraacetic acid (EDTA)- and diethylenetriamine pentaacetic acid (DTPA)-extractable Ag, As, Ba, Cu, Zn, and Ni indicate a lower biohazards potential. These results show that, according to the EPA regulations, PDP glass may not be classified as hazardous waste because none of the metals exceeded their thresholds in PDP leachate. However, the concentrations of As and Zn should be lowered in the manufacturing process and finished product to avoid potential pollution problems. The plasma display panel is rapidly becoming obsolete because of the liquid crystal display. In this study, the leachability of heavy metals contained in the waste plasma display panel glass was first examined by standardized leaching tests, typical chemical speciation assessments, and bioavailability tests, providing fundamental data for waste PDP glass recovery, recycling, and reuse.

Heavy metals alter the electrokinetic properties of bacteria, yeasts, and clay minerals.

PubMed Central

Collins, Y E; Stotzky, G

1992-01-01

The electrokinetic patterns of four bacterial species (Bacillus subtilis, Bacillus megaterium, Pseudomonas aeruginosa, and Agrobacterium radiobacter), two yeasts (Saccharomyces cerevisiae and Candida albicans), and two clay minerals (montmorillonite and kaolinite) in the presence of the chloride salts of the heavy metals, Cd, Cr, Cu, Hg, Ni, Pb, and Zn, and of Na and Mg were determined by microelectrophoresis. The cells and kaolinite were net negatively charged at pH values above their isoelectric points (pI) in the presence of Na, Mg, Hg, and Pb at an ionic strength (mu) of 3 x 10(-4); montmorillonite has no pI and was net negatively charged at all pH values in the presence of these metals. However, the charge of some bacteria, S. cerevisiae, and kaolinite changed to a net positive charge (charge reversal) in the presence of Cd, Cr, Cu, Ni, and Zn at pH values above 5.0 (the pH at which charge reversal occurred differed with the metal) and then, at higher pH values, again became negative. The charge of the bacteria and S. cerevisiae also reversed in solutions of Cu and Ni with a mu of greater than 3 x 10(-4), whereas there was no reversal in solutions with a mu of less than 3 x 10(-4). The clays became net positively charged when the mu of Cu was greater than 3 x 10(-4) and that of Ni was greater than 1.5 x 10(-4). The charge of the cells and clays also reversed in solutions containing both Mg and Ni or both Cu and Ni (except montmorillonite) but not in solutions containing both Mg and Cu (except kaolinite) (mu = 3 x 10(-4)). The pIs of the cells in the presence of the heavy metals were at either higher or lower pH values than in the presence of Na and Mg. Exposure of the cells to the various metals at pH values from 2 to 9 for the short times (ca. 10 min) required to measure the electrophoretic mobility did not affect their viability. The specific adsorption on the cells and clays of the hydrolyzed species of some of the heavy metals that formed at higher pH values was probably responsible for the charge reversal. These results suggest that the toxicity of some heavy metals to microorganisms varies with pH because the hydrolyzed speciation forms of these metals, which occur at higher pH values, bind on the cell surface and alter the net charge of the cell.(ABSTRACT TRUNCATED AT 400 WORDS) PMID:1622229

Metal speciation in salt marsh sediments: Influence of halophyte vegetation in salt marshes with different morphology

NASA Astrophysics Data System (ADS)

Pedro, Sílvia; Duarte, Bernardo; Raposo de Almeida, Pedro; Caçador, Isabel

2015-12-01

Salt marshes provide environmental conditions that are known to affect metal speciation in sediments. The elevational gradient along the marsh and consequent differential flooding are some of the major factors influencing halophytic species distribution and coverage due to their differential tolerance to salinity and submersion. Different species, in turn, also have distinct influences on the sediment's metal speciation, and its metal accumulation abilities. The present work aimed to evaluate how different halophyte species in two different salt marshes could influence metal partitioning in the sediment at root depth and how that could differ from bare sediments. Metal speciation in sediments around the roots (rhizosediments) of Halimione portulacoides, Sarcocornia fruticosa and Spartina maritima was determined by sequentially extracting operationally defined fractions with solutions of increasing strength and acidity. Rosário salt marsh generally showed higher concentrations of all metals in the rhizosediments. Metal partitioning was primarily related to the type of metal, with the elements' chemistry overriding the environment's influence on fractionation schemes. The most mobile elements were Cd and Zn, with greater availability being found in non-vegetated sediments. Immobilization in rhizosediments was predominantly influenced by the presence of Fe and Mn oxides, as well as organic complexes. In the more mature of both salt marshes, the differences between vegetated and non-vegetated sediments were more evident regarding S. fruticosa, while in the younger system all halophytes presented significantly different metal partitioning when compared to that of mudflats.

Distribution and speciation of metals (Cu, Zn, Cd, and Pb) in agricultural and non-agricultural soils near a stream upriver from the Pearl River, China.

PubMed

Yang, Silin; Zhou, Dequn; Yu, Huayong; Wei, Rong; Pan, Bo

2013-06-01

The distribution and chemical speciation of typical metals (Cu, Zn, Cd and Pb) in agricultural and non-agricultural soils were investigated in the area of Nanpan River, upstream of the Pearl River. The investigated four metals showed higher concentrations in agricultural soils than in non-agricultural soils, and the site located in factory district contained metals much higher than the other sampling sites. These observations suggested that human activities, such as water irrigation, fertilizer and pesticide applications might have a major impact on the distribution of metals. Metal speciation analysis presented that Cu, Zn and Cd were dominated by the residual fraction, while Pb was dominated by the reducible fraction. Because of the low mobility of the metals in the investigated area, no remarkable difference could be observed between upstream and downstream separated by the factory site. Copyright © 2013 Elsevier Ltd. All rights reserved.

TEMPORAL VARIABILITY IN PHYSICAL SPECIATION OF METALS DURING A WINTER RAIN-ON-SNOW EVENT

EPA Science Inventory

Particulate matter in urban rivers transports a significant fraction of pollutants, changes rapidly during storm events and is difficult to characterize. In this study, the physical speciation of trace metals and organic carbon in an urban river and upstream headwaters site in To...

Synthetic humic substances and their use for remediation of contaminated environments

NASA Astrophysics Data System (ADS)

Dudare, Diana; Klavins, Maris

2014-05-01

Soils are increasingly subjected to different chemical stresses, because of increasing industrialization process and other factors. Different anthropogenic compounds (organic or inorganic in nature) upon entering the soil, may not only influence its productivity potential, but may also affect the quality of groundwater and food chain. Consequently, soils of different environments contain a complex mixture of contaminants, such as oil products, metals, organic solvents, acids, bases and radionuclides. Thereby greater focus should be paid to risk assessment and evaluation of remedial techniques in order to restore the quality of the soil and groundwater. The treatment technologies presently used to remove contaminants are physical, chemical and biological technologies. Many functional groups in the structure of humic substances determine their ability to interact with metal ions forming stable complexes and influencing speciation of metal ions in the environment, as well mobility, behaviour and speciation forms in the environment. Humic substances are suggested for use in the remediation of environments contaminated with metals, owing to complex forming properties. Several efforts have been undertaken with respect to synthesize humic substances for their structural studies. At the same time the real number of methods suggested for synthesis of humic substances is highly limited and their synthesis in general has been used mostly for their structural analysis. The present study deals with development of approaches for synthesis of humic substances with increased complex forming ability in respect to metal ions. Industrially produced humic substances (TEHUM) were used for comparison and after their modification their properties were analyzed for their elemental composition; functional group content changes in spectral characteristics. Synthetic humic substances showed significant differences in the number of functional groups and in ability to interact with the metal ions, which were reflected in their complexation properties towards metal ions. FTIR spectra gave evidence of the presence of metal ions, strongly bound and protected in inner sphere complexes. Considering a large scale of production of humic substances, the obtained synthetic humic substances with modified properties are perspective and sustainable areas of use. The obtained results of this study showed that synthetic humic substances can be used for remediation of environments contaminated with heavy metal ions.

Effects of artificial sweeteners on metal bioconcentration and toxicity on a green algae Scenedesmus obliquus.

PubMed

Hu, Hongwei; Deng, Yuanyuan; Fan, Yunfei; Zhang, Pengfei; Sun, Hongwen; Gan, Zhiwei; Zhu, Hongkai; Yao, Yiming

2016-05-01

The ecotoxicity of heavy metals depends much on their speciation, which is influenced by other co-existing substances having chelating capacity. In the present study, the toxic effects of Cd(2+) and Cu(2+) on a green algae Scenedesmus obliquus were examined in the presence of two artificial sweeteners (ASs), acesulfame (ACE) and sucralose (SUC) by comparing the cell specific growth rate μ and pulse-amplitude-modulated (PAM) parameters (maximal photosystem II photochemical efficiency Fv/Fm, actual photochemical efficiency Yield, and non-photochemical quenching NPQ) of the algae over a 96-h period. Simultaneously, the bioconcentration of the metals by the algal cells in the presence of the ASs was measured. The presence of ACE enhanced the growth of S. obliquus and promoted the bioconcentration of Cd(2+) in S. obliquus, while the impacts of SUC were not significant. Meanwhile, EC50 values of Cd(2+) on the growth of S. obliquus increased from 0.42 mg/L to 0.54 mg/L and 0.48 mg/L with the addition of 1.0 mg/L ACE and SUC, respectively. As for Cu(2+), EC50 values increased from 0.13 mg/L to 0.17 mg/L and 0.15 mg/L with the addition of 1.0 mg/L ACE and SUC, respectively. In summary, the two ASs reduced the toxicity of the metals on the algae, with ACE showing greater effect than SUC. Although not as sensitive as the cell specific growth rate, PAM parameters could disclose the mechanisms involved in metal toxicity at subcellular levels. This study provides the first evidence for the possible impact of ASs on the ecotoxicity of heavy metals. Copyright © 2016 Elsevier Ltd. All rights reserved.

Application of chemometric analysis and self Organizing Map-Artificial Neural Network as source receptor modeling for metal speciation in river sediment.

PubMed

Pandey, Mayank; Pandey, Ashutosh Kumar; Mishra, Ashutosh; Tripathi, B D

2015-09-01

Present study deals with the river Ganga water quality and its impact on metal speciation in its sediments. Concentration of physico-chemical parameters was highest in summer season followed by winter and lowest in rainy season. Metal speciation study in river sediments revealed that exchangeable, reducible and oxidizable fractions were dominant in all the studied metals (Cr, Ni, Cu, Zn, Cd, Pb) except Mn and Fe. High pollution load index (1.64-3.89) recommends urgent need of mitigation measures. Self-organizing Map-Artificial Neural Network (SOM-ANN) was applied to the data set for the prediction of major point sources of pollution in the river Ganga. Copyright © 2015 Elsevier Ltd. All rights reserved.

The mutual influence of speciation and combination of Cu and Pb on the photodegradation of dimethyl o-phthalate.

PubMed

Jiang, Xinshu; Wang, Zhe; Zhang, Yiyue; Wang, Fei; Zhu, Mijia; Yao, Jun

2016-12-01

Specific industrial application of dimethyl o-phthalate (DMP) in ore flotation has led to DMP-heavy metals combined pollution, which causes the abiotic degradation of DMP in the environment more complex. This study focused on the effect of Cu and Pb on photodegradation of DMP. The major mechanism of inhibiting effect of Cu and Pb on degradation of DMP involved their speciation and combination. It was found that the Cu (5 mg/L, I = 95.4%) and Pb (5 mg/L, I = 100%) could inhibit the photodegradation of DMP. The main species that inhibit the DMP degradation were Cu(OH) + and Pb(OH) + , respectively. The intensity of the UV-Vis absorbance of DMP was obviously related to the concentration of Cu 2+ (R 2  = 0.8655) or Pb 2+ (R 2  = 0.9019) ions. Fluorescence quenching effect of Cu 2+ (R 2  > 0.9946), Pb 2+ (R 2  > 0.6879) on DMP is strongly correlated with the concentration of ions. And the equilibrium membrane dialysis experiment has also verified the combination of DMP and Cu, Pb. These results are useful to understand the effect mechanism of metal species on the photodegradation of organic chemicals. Copyright © 2016 Elsevier Ltd. All rights reserved.

Subcellular Distribution and Chemical Forms of Pb in Corn: Strategies Underlying Tolerance in Pb Stress.

PubMed

Sun, Jianling; Luo, Liqiang

2018-06-22

Studying the accumulation position and forms of heavy metals (HMs) in organisms and cells is helpful to understand the transport process and detoxification mechanism. As typical HMs, lead (Pb) subcellular content, localization, and speciation of corn subcellular fractions were studied by a series of technologies, including transmission electron microscopy, inductively coupled plasma mass spectrometry, and X-ray absorption near edge structure. The results revealed that the electrodense granules of Pb were localized in the cell wall, intercellular space, and plasma membranes. About 71% Pb was localized at the cell wall and soluble fraction. In cell walls, the total amount of pyromorphite and Pb carbonate was about 80% and the remaining was Pb stearate. In the nuclear and chloroplast fraction, which demonstrated significant changes, major speciations were Pb sulfide (72%), basic Pb carbonate (16%), and Pb stearate (12%). Pb is blocked by cell walls as pyromorphite and Pb carbonate sediments and compartmentalized by vacuoles, which both play an inportant role in cell detoxification. Besides, sulfur-containing compounds form inside the cells.

Cold Temperature and Biodiesel Fuel Effects on Speciated Emissions of Volatile Organic Compounds from Diesel Trucks

EPA Science Inventory

Speciated volatile organic compounds (VOCs) were measured in diesel exhaust from three medium heavy-duty trucks equipped with modern aftertreatment technologies. Emissions testing was conducted on a chassis dynamometer at two ambient temperatures (-6.7°C and 21.7°C) operating on ...

Influence of sulfhydryl sites on metal binding by bacteria

NASA Astrophysics Data System (ADS)

Nell, Ryan M.; Fein, Jeremy B.

2017-02-01

The role of sulfhydryl sites within bacterial cell envelopes is still unknown, but the sites may control the fate and bioavailability of metals. Organic sulfhydryl compounds are important complexing ligands in aqueous systems and they can influence metal speciation in natural waters. Though representing only approximately 5-10% of the total available binding sites on bacterial surfaces, sulfhydryl sites exhibit high binding affinities for some metals. Due to the potential importance of bacterial sulfhydryl sites in natural systems, metal-bacterial sulfhydryl site binding constants must be determined in order to construct accurate models of the fate and distribution of metals in these systems. To date, only Cd-sulfhydryl binding has been quantified. In this study, the thermodynamic stabilities of Mn-, Co-, Ni-, Zn-, Sr- and Pb-sulfhydryl bacterial cell envelope complexes were determined for the bacterial species Shewanella oneidensis MR-1. Metal adsorption experiments were conducted as a function of both pH, ranging from 5.0 to 7.0, and metal loading, from 0.5 to 40.0 μmol/g (wet weight) bacteria, in batch experiments in order to determine if metal-sulfhydryl binding occurs. Initially, the data were used to calculate the value of the stability constants for the important metal-sulfhydryl bacterial complexes for each metal-loading condition studied, assuming a single binding reaction for the dominant metal-binding site type under the pH conditions of the experiments. For most of the metals that we studied, these calculated stability constant values increased significantly with decreasing metal loading, strongly suggesting that our initial assumption was not valid and that more than one type of binding occurs at the assumed binding site. We then modeled each dataset with two distinct site types with identical acidity constants: one site with a high metal-site stability constant value, which we take to represent metal-sulfhydryl binding and which dominates under low metal loading conditions, and another more abundant site that we term non-sulfhydryl sites that becomes important at high metal loadings. The resulting calculated stability constants do not vary significantly as a function of metal loading and yield reasonable fits to the observed adsorption behaviors as a function of both pH and metal loading. We use the results to calculate the speciation of metals bound by the bacterial envelope in realistic bacteria-bearing, heavy metal contaminated systems in order to demonstrate the potential importance of metal-sulfhydryl binding in the budget of bacterially-adsorbed metals under low metal-loading conditions.

X-ray Microprobe Investigations of Elemental Distributions and Concentrations at Mineral-Microbe Interfaces

NASA Astrophysics Data System (ADS)

Kemner, K. M.; Kelly, S. D.; O'Loughlin, E. J.; Lai, B.; Maser, J.; Cai, Z.; Londer, Y.; Schiffer, M.; Nealson, K.

2003-12-01

Understanding the fate of heavy-metal contaminants in the environment is of fundamental importance in the development and evaluation of effective remediation and sequestration strategies. Bacteria and the extracellular material associated with them are thought to play a key role in determining a contaminant's speciation and thus its mobility in the environment. Additionally, the metabolism and surface properties of bacteria can be quite different depending upon whether the bacteria exhibit a planktonic (free-floating) or biofilm (surface adhered) habit. The microenvironment at and adjacent to actively metabolizing cells also can be significantly different from the bulk environment. Thus, to understand the microscopic physical, geological, chemical, and biological interfaces that determine a contaminant's macroscopic fate, the spatial distribution and chemical speciation of contaminants and elements that are key to biological processes must be characterized at micron and submicron lengthscales for bacteria in both planktonic and adhered states. Hard x-ray microimaging is a powerful technique for the element-specific investigation of complex environmental samples at the needed micron and submicron resolution. An important advantage of these techniques results from the large penetration depth of hard x-rays in water. This advantage minimizes the requirements for sample preparation and allows the detailed study of hydrated samples. The objectives of the studies to be presented are (1) to determine the spatial distribution, concentration, and chemical speciation of metals at, in, and near bacteria and bacteria-geosurface interfaces, (2) to use this information to identify the metabolic processes occurring within the microbes, and (3) to identify the interactions occurring near these interfaces among the metals, mineral surfaces, and bacteria under a variety of conditions. We have used x-ray fluorescence microscopy to investigate the spatial distribution of 3d elements in Pseudomonas fluorescens cells in both planktonic and surface-adhered states. We have used x-ray fluorescence spectromicroscopy to investigate the chemical speciation and distribution of Cr that was introduced to these cells as Cr(VI). Additionally, we have used these techniques to identify the distribution of an over expressed cytochrome c7 in individual E. coli. Finally, we have used x-ray fluorescence microscopy to investigate Shewanella oneidensis MR-1 cells adhered to iron oxyhydroxide thin films. The zone plate used in these microscopy experiments produced a focused beam with a cross section (and hence spatial resolution) of 100-300 nanometers. Results from x-ray fluorescence imaging experiments indicate that the distribution of P, S, Cl, Ca, Fe, Ni, Cu, and Zn can define the location of the microbe. Additionally, quantitative elemental analysis of individual microbes identified significant changes in concentration of 3d transition elements depending on the age of the culture and the type of electron acceptor presented to the microbes. These results and a discussion of the use of this technique for identifying metabolic states of individual microbes within communities and the chemical speciation of metal contaminants at the mineral-microbe interface will be presented.

Influence of population density on the concentration and speciation of metals in the soil and street dust from urban areas.

PubMed

Acosta, J A; Gabarrón, M; Faz, A; Martínez-Martínez, S; Zornoza, R; Arocena, J M

2015-09-01

Street dust and soil from high, medium and low populated cities and natural area were analysed for selected physical-chemical properties, total and chemical speciation of Zn, Pb, Cu, Cr, Cd, Co, Ni to understand the influence of human activities on metal accumulation and mobility in the environment. The pH, salinity, carbonates and organic carbon contents were similar between soil and dust from the same city. Population density increases dust/soil salinity but has no influence on metals concentrations in soils. Increases in metal concentrations with population density were observed in dusts. Cu, Zn, Pb, Cr can be mobilized more easily from dust compared to the soil. In addition, population density increase the percentage of Pb and Zn associated to reducible and carbonate phase in the dust. The behaviour of metals except Cd in soil is mainly affected by physico-chemical properties, while total metal influenced the speciation except Cr and Ni in dusts. Copyright © 2015 Elsevier Ltd. All rights reserved.

Sorbent control of trace metals in sewage sludge combustion and incineration

NASA Astrophysics Data System (ADS)

Naruse, I.; Yao, H.; Mkilaha, I. S. N.

2003-05-01

Coal and wastes combustion have become an important issue not only in terms of energy generation but also environmental conservation. The need for alternative fuels and wastes management has made the two energy sources of importance. However, the utilization of the two is faced with problems of impurity trace metals in the fuel. These metals usually speciate during combustion or incineration leading to generation of fumes and subsequently particles. This paper reports on the study aimed at understanding the speciation of trace metals and their emission from combustion systems as particulates. Experiments carried out using a down-flow furnace and theoretical study carried out using lead, chromium and cadmium as basic metals had shown that their speciation and subsequent emission is controlled by both chemical composition and physical properties of the fuel. The physical and chemical and physical properties of the fuel and their respective compounds and the operating conditions of the incineration and combustion system control the enrichment of the particles with trace metals.

EPA’s SPECIATE 4.4 Database - Development and Uses

EPA Science Inventory

SPECIATE is the EPA's repository of TOG, PM, and Other Gases speciation profiles of air pollution sources. It includes weight fractions of both organic species and PM and provides data in consistent units. Species include metals, ions, elements, and organic and inorganic compound...

Chemistry of Marine Ligands and Siderophores

PubMed Central

Vraspir, Julia M.; Butler, Alison

2011-01-01

Marine microorganisms are presented with unique challenges to obtain essential metal ions required to survive and thrive in the ocean. The production of organic ligands to complex transition metal ions is one strategy to both facilitate uptake of specific metals, such as iron, and to mitigate the potential toxic effects of other metal ions, such as copper. A number of important trace metal ions are complexed by organic ligands in seawater, including iron, cobalt, nickel, copper, zinc, and cadmium, thus defining the speciation of these metal ions in the ocean. In the case of iron, siderophores have been identified and structurally characterized. Siderophores are low molecular weight iron-binding ligands produced by marine bacteria. Although progress has been made toward the identity of in situ iron-binding ligands, few compounds have been identified that coordinate the other trace metals. Deciphering the chemical structures and production stimuli of naturally produced organic ligands and the organisms they come from is fundamental to understanding metal speciation and bioavailability. The current evidence for marine ligands, with an emphasis on siderophores, and discussion of the importance and implications of metal-binding ligands in controlling metal speciation and cycling within the world’s oceans are presented. PMID:21141029

Albatross as Sentinels of Heavy Metal Pollution: Local and Global Factors

NASA Astrophysics Data System (ADS)

Sentman, W.; Edwards, S. V.; Vo, A. E.; Bank, M. S.

2012-12-01

Heavy metal pollution in the Pacific Ocean has garnered significant attention in recent years, especially with regard to rising mercury emissions from Asia. Uncertainty exists over the extent to which mercury in biota may have resulted from increases in anthropogenic emissions over time. Albatrosses, including those inhabiting the North Pacific, are wide-ranging, long-lived, keystone, avian predators. Consequently, they serve as ideal sentinel species for investigating the effects of historical and contemporary pollution as well as local and global factors related to heavy metal bioaccumulation, exposure, and ecotoxicological risk. To date, high levels of mercury and lead have been documented in albatross species throughout the Pacific. To address biotic exposure to these multiple stressors, here we synthesize and conduct meta-analyses of total mercury, methylmercury, and lead exposure data in Black-footed albatross (Phoebastria nigripes) and Laysan albatross (Phoebastria immutabilis). Our approach uses data from the field and literature and for methyl mercury uses museum feathers spanning the past 130 years for Black-Footed albatross. We discuss the use and application of stable isotopes (δ15N and δ13C) as a way to control for temporal changes in trophic structure and diet and the importance of conducting speciation analyses, for mercury, to account for curator mediated inorganic mercury in older specimens. Our data showed higher levels of inorganic mercury in older specimens of Black-Footed albatross as well as two non-pelagic species (control samples) lacking historical sources of bioavailable mercury exposure, which suggests that studies on bioaccumulation should measure methylmercury rather than total mercury when utilizing museum collections. Additionally, at the local scale, previous research has reported that lead paint exposure from buildings was also an important environmental stressor for Laysan albatross, suggesting that albatross species face heavy metal exposure threats at both local (lead) and global scales (mercury). Specific types of plastic pollution entering marine environments have been documented to contain heavy metals at levels, which if bio-available, may present a non-localized source of lead exposure in albatross species known to ingest (and regurgitate to their young) large amounts of marine plastic. Changes in methylmercury levels, in Black-Footed albatross, were consistent with historical global and recent regional increases observed among published estimates and proxies of anthropogenic mercury emissions. Heavy metal toxicity along with other stressors may undermine current and future reproductive outcomes in these seabird species. Collectively, our findings, and review of the literature, suggest that albatrosses in this region can be considered to be an effective marine flagship species and raising the profile of these organisms likely would successfully support broader biodiversity conservation efforts in the North Pacific.

Seasonal trends, chemical speciation and source apportionment of fine PM in Tehran

NASA Astrophysics Data System (ADS)

Arhami, Mohammad; Hosseini, Vahid; Zare Shahne, Maryam; Bigdeli, Mostafa; Lai, Alexandra; Schauer, James J.

2017-03-01

Frequent air pollution episodes have been reported for Tehran, Iran, mainly because of critically high levels of fine particulate matter (PM2.5). The composition and sources of these particles are poorly known, so this study aims to identify the major components and heavy metals in PM2.5 along with their seasonal trends and associated sources. 24-hour PM2.5 samples were collected at a main residential station every 6 days for a full year from February 2014 to February 2015. The samples were analyzed for ions, organic carbon (including water-soluble and insoluble portions), elemental carbon (EC), and all detectable elements. The dominant mass components, which were determined by means of chemical mass closure, were organic matter (35%), dust (25%), non-sea salt sulfate (11%), EC (9%), ammonium (5%), and nitrate (2%). Organic matter and EC together comprised 44% of fine PM on average (increased to >70% in the colder season), which reflects the significance of anthropogenic urban sources (i.e. vehicles). The contributions of different components varied considerably throughout the year, particularly the dust component that varied from 7% in the cold season to 56% in the hot and dry season. Principal component analyses were applied, resulting in 5 major source factors that explained 85% of the variance in fine PM. Factor 1, representing soil dust, explained 53%; Factor 2 denotes heavy metals mainly found in industrial sources and accounted for 18%; and rest of factors, mainly representing combustion sources, explained 14% of the variation. The levels of major heavy metals were further evaluated, and their trends showed considerable increases during cold seasons. The results of this study provide useful insight to fine PM in Tehran, which could help in identifying their health effects and sources, and also adopting effective control strategies.

Strategies to predict metal mobility in surficial mining environments

USGS Publications Warehouse

Smith, Kathleen S.

2007-01-01

This report presents some strategies to predict metal mobility at mining sites. These strategies are based on chemical, physical, and geochemical information about metals and their interactions with the environment. An overview of conceptual models, metal sources, and relative mobility of metals under different geochemical conditions is presented, followed by a discussion of some important physical and chemical properties of metals that affect their mobility, bioavailability, and toxicity. The physical and chemical properties lead into a discussion of the importance of the chemical speciation of metals. Finally, environmental and geochemical processes and geochemical barriers that affect metal speciation are discussed. Some additional concepts and applications are briefly presented at the end of this report.

Metal Transport, Heavy Metal Speciation and Microbial Fixation Through Fluvial Subenvironments, Lower Coeur D'Alene River Valley, Idaho

NASA Astrophysics Data System (ADS)

Hooper, R. L.; Mahoney, J. B.

2001-12-01

The lower Coeur d'Alene River Valley of northern Idaho is the site of extensive lead and zinc contamination resulting from both direct riverine tailings disposal and flood remobilization of contaminated sediments derived from the Coeur d'Alene mining district upstream. Variations in the hydrologic regime, redox conditions, porosity/permeability, organic content and microbial activity results in complicated metal transport pathways. Documentation of these pathways is a prerequisite to effective remediation, and requires accurate analysis of lateral and vertical variations. An analytical approach combining sequential extraction, electron microscopy, and microanalysis provides a comprehensive assessment of particulate speciation in this complex hydrologic system. Rigorously controlled sample preparation and a new sequential extraction protocol provide unprecedented insight into the role of metal sequestration in fluvial subenvironments. Four subenvironments were investigated: bedload, overbank (levee), marsh, and lacustrine. Periodic floods remobilize primary ore minerals and secondary minerals from upstream tailings (primarily oxyhydroxides, sulfides and carbonates). The bedload in the lower valley is a reducing environment and acts as a sink for detrital carbonates and sulfides moving downstream. In addition, authigenic/biogenic Fe, Pb and Zn sulfides and phosphates are common in bedload sediments near the sediment/water interface. Flood redistribution of oxide, sulfide and carbonate phases results in periodic contaminant recharge generating a complex system of metal dissolution, mobilization, migration and precipitation. In levee environments, authigenic sulfides from flood scouring are quickly oxidized resulting in development of oxide coated grain surfaces. Stability of detrital minerals on the levee is variable depending on sediment permeability, grain size and mineralogy resulting in a complex stratigraphy of oxide zones mottled with zones dominated by detrital and authigenic carbonate and sulfide phases. Marshes subjected to periodic subaerial exposure/flooding are even more complex and dominated by authigenic and biogenic mineralization. Lacustrine environments are dominated by nanocrystalline inorganic and biogenic sulfide minerals in the upper third of the contaminated sediment column with increasing amounts of silt sized detrital sulfides (especially sphalerite) closer to the premining surface. In pH-neutral subenvironments within the wetlands and lateral lakes of the lower Coeur d'Alene River Valley, microbial fixation plays a critical role in sequestering metals. Complex metal oxyhydroxide phases provided via flood recharge to river edge, marsh and lacustrine environments rapidly dissolve upon encountering anoxic conditions. Microbial activity is extremely effective in removing heavy metals from the water column, producing a nanocrystalline biofilm substrate characterized by ZnS (sphalerite) and non-stoichiometric PbS, FeS, and mixed metal sulfides. These solid phases are inherently unstable, and the sequestered metals become readily available through changes in redox or pH conditions, particularly dam-controlled annual fluctuations in base level, or during removal by bottom-feeding aquatic water fowl. The recognition of the inherent complexity and instability of microbially produced sulfidic material in a pH-neutral environment has important implications for remediation efforts utilizing wetland filtration methods.

Volcanic gas composition, metal dispersion and deposition during explosive volcanic eruptions on the Moon

NASA Astrophysics Data System (ADS)

Renggli, C. J.; King, P. L.; Henley, R. W.; Norman, M. D.

2017-06-01

The transport of metals in volcanic gases on the Moon differs greatly from their transport on the Earth because metal speciation depends largely on gas composition, temperature, pressure and oxidation state. We present a new thermochemical model for the major and trace element composition of lunar volcanic gas during pyroclastic eruptions of picritic magmas calculated at 200-1500 °C and over 10-9-103 bar. Using published volatile component concentrations in picritic lunar glasses, we have calculated the speciation of major elements (H, O, C, Cl, S and F) in the coexisting volcanic gas as the eruption proceeds. The most abundant gases are CO, H2, H2S, COS and S2, with a transition from predominantly triatomic gases to diatomic gases with increasing temperatures and decreasing pressures. Hydrogen occurs as H2, H2S, H2S2, HCl, and HF, with H2 making up 0.5-0.8 mol fractions of the total H. Water (H2O) concentrations are at trace levels, which implies that H-species other than H2O need to be considered in lunar melts and estimates of the bulk lunar composition. The Cl and S contents of the gas control metal chloride gas species, and sulfide gas and precipitated solid species. We calculate the speciation of trace metals (Zn, Ga, Cu, Pb, Ni, Fe) in the gas phase, and also the pressure and temperature conditions at which solids form from the gas. During initial stages of the eruption, elemental gases are the dominant metal species. As the gas loses heat, chloride and sulfide species become more abundant. Our chemical speciation model is applied to a lunar pyroclastic eruption model with isentropic gas decompression. The relative abundances of the deposited metal-bearing solids with distance from the vent are predicted for slow cooling rates (<5 °C/s). Close to a volcanic vent we predict native metals are deposited, whereas metal sulfides dominate with increasing distance from the vent. Finally, the lunar gas speciation model is compared with the speciation of a H2O-, CO2- and Cl-rich volcanic gas from Erta Ale volcano (Ethiopia) as an analogy for more oxidized planetary eruptions. In the terrestrial Cl-rich gas the metals are predominantly transported as chlorides, as opposed to metallic vapors and sulfides in the lunar gas. Due to the presence of Cl-species, metal transport is more efficient in the volcanic gas from Erta Ale compared to the Moon.

Molecular Environmental Science: An Assessment of Research Accomplishments, Available Synchrotron Radiation Facilities, and Needs

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

Brown, G

2004-02-05

Synchrotron-based techniques are fundamental to research in ''Molecular Environmental Science'' (MES), an emerging field that involves molecular-level studies of chemical and biological processes affecting the speciation, properties, and behavior of contaminants, pollutants, and nutrients in the ecosphere. These techniques enable the study of aqueous solute complexes, poorly crystalline materials, solid-liquid interfaces, mineral-aqueous solution interactions, microbial biofilm-heavy metal interactions, heavy metal-plant interactions, complex material microstructures, and nanomaterials, all of which are important components or processes in the environment. Basic understanding of environmental materials and processes at the molecular scale is essential for risk assessment and management, and reduction of environmental pollutantsmore » at field, landscape, and global scales. One of the main purposes of this report is to illustrate the role of synchrotron radiation (SR)-based studies in environmental science and related fields and their impact on environmental problems of importance to society. A major driving force for MES research is the need to characterize, treat, and/or dispose of vast quantities of contaminated materials, including groundwater, sediments, and soils, and to process wastes, at an estimated cost exceeding 150 billion dollars through 2070. A major component of this problem derives from high-level nuclear waste. Other significant components come from mining and industrial wastes, atmospheric pollutants derived from fossil fuel consumption, agricultural pesticides and fertilizers, and the pollution problems associated with animal waste run-off, all of which have major impacts on human health and welfare. Addressing these problems requires the development of new characterization and processing technologies--efforts that require information on the chemical speciation of heavy metals, radionuclides, and xenobiotic organic compounds and their reactions with environmental materials. To achieve this goal, both fundamental and targeted studies of complex environmental systems at a molecular level are needed, and examples of both types of studies are presented herein. These examples illustrate the fact that MES SR studies have led to a revolution in our understanding of the fundamental physical and chemical aspects of natural systems. The MES SR user community has continued to experience strong growth at U.S. SR laboratories, with MES researchers comprising up to 15% of the total user base. Further growth and development of the MES community is being hindered by insufficient resources, including support personnel, materials preparation facilities, and available beam time at U.S. SR laboratories. ''EnviroSync'' recommends the following actions, in cooperation with U.S. SR laboratory directors, to meet the MES community's needs.« less

The influence of metal speciation in combustion waste on the efficiency of Cu, Pb, Zn, Cd, Ni and Cr bioleaching in a mixed culture of sulfur-oxidizing and biosurfactant-producing bacteria.

PubMed

Karwowska, Ewa; Wojtkowska, Małgorzata; Andrzejewska, Dorota

2015-12-15

Metal leachability from ash and combustion slag is related to the physico-chemical properties, including their speciation in the waste. Metals speciation is an important factor that influences the efficiency of metal bioleaching from combustion wastes in a mixed culture of acidophilic and biosurfactant-producing bacteria. It was observed that individual metals tended to occur in different fractions, which reflects their susceptibility to bioleaching. Cr and Ni were readily removed from wastes when present with a high fraction bound to carbonates. Cd and Pb where not effectively bioleached when present in high amounts in a fraction bound to organic matter. The best bioleaching results were obtained for power plant slag, which had a high metal content in the exchangeable, bound to carbonates and bound to Fe and Mg oxides fractions- the metal recovery percentage for Zn, Cu and Ni from this waste exceeded 90%. Copyright © 2015 Elsevier B.V. All rights reserved.

Metal-organic complexes in geochemical processes: temperature dependence of the standard thermodynamic properties of aqueous complexes between metal cations and dicarboxylate ligands

NASA Astrophysics Data System (ADS)

Prapaipong, Panjai; Shock, Everett L.; Koretsky, Carla M.

1999-10-01

By combining results from regression and correlation methods, standard state thermodynamic properties for aqueous complexes between metal cations and divalent organic acid ligands (oxalate, malonate, succinate, glutarate, and adipate) are evaluated and applied to geochemical processes. Regression of experimental standard-state equilibrium constants with the revised Helgeson-Kirkham-Flowers (HKF) equation of state yields standard partial molal entropies (S¯°) of aqueous metal-organic complexes, which allow determination of thermodynamic properties of the complexes at elevated temperatures. In cases where S¯° is not available from either regression or calorimetric measurement, the values of S¯° can be estimated from a linear correlation between standard partial molal entropies of association (ΔS¯°r) and standard partial molal entropies of aqueous cations (S¯°M). The correlation is independent of cation charge, which makes it possible to predict S¯° for complexes between divalent organic acids and numerous metal cations. Similarly, correlations between standard Gibbs free energies of association of metal-organic complexes (ΔḠ°r) and Gibbs free energies of formation (ΔḠ°f) for divalent metal cations allow estimates of standard-state equilibrium constants where experimental data are not available. These correlations are found to be a function of ligand structure and cation charge. Predicted equilibrium constants for dicarboxylate complexes of numerous cations were included with those for inorganic and other organic complexes to study the effects of dicarboxylate complexes on the speciation of metals and organic acids in oil-field brines. Relatively low concentrations of oxalic and malonic acids affect the speciation of cations more than similar concentrations of succinic, glutaric, and adipic acids. However, the extent to which metal-dicarboxylate complexes contribute to the speciation of dissolved metals depends on the type of dicarboxylic acid ligand; relative concentration of inorganic, mono-, and dicarboxylate ligands; and the type of metal cation. As an example, in the same solution, dicarboxylic acids have a greater influence on the speciation of Fe+2 and Mg+2 than on the speciation of Zn+2 and Mn+2.

Modeling metal binding to soils: the role of natural organic matter.

PubMed

Gustafsson, Jon Petter; Pechová, Pavlina; Berggren, Dan

2003-06-15

The use of mechanistically based models to simulate the solution concentrations of heavy metals in soils is complicated by the presence of different sorbents that may bind metals. In this study, the binding of Zn, Pb, Cu, and Cd by 14 different Swedish soil samples was investigated. For 10 of the soils, it was found that the Stockholm Humic Model (SHM) was able to describe the acid-base characteristics, when using the concentrations of "active" humic substances and Al as fitting parameters. Two additional soils could be modeled when ion exchange to clay was also considered, using a component additivity approach. For dissolved Zn, Cd, Ca, and Mg reasonable model fits were produced when the metal-humic complexation parameters were identical for the 12 soils modeled. However, poor fits were obtained for Pb and Cu in Aquept B horizons. In two of the soil suspensions, the Lund A and Romfartuna Bhs, the calculated speciation agreed well with results obtained by using cation-exchange membranes. The results suggest that organic matter is an important sorbent for metals in many surface horizons of soils in temperate and boreal climates, and the necessity of properly accounting for the competition from Al in simulations of dissolved metal concentrations is stressed.

Heavy metal (Cu, Zn, Cd and Pb) partitioning and bioaccessibility in uncontaminated and long-term contaminated soils.

PubMed

Lamb, Dane T; Ming, Hui; Megharaj, Mallavarapu; Naidu, Ravi

2009-11-15

We investigated the pore-water content and speciation of copper (Cu), zinc (Zn), cadmium (Cd) and lead (Pb) in a range of uncontaminated and long-term contaminated soils in order to establish their potential bioaccessibility to soil biota, plants and humans. Among the samples, soil pH (0.01 M CaCl(2)) ranged from 4.9 to 8.2. The total metal content of the uncontaminated soils ranged from 3.8 to 93.8 mg Cu kg(-1), 10.3 to 95 mg kg(-1) Zn, 0.1 to 1.8 mg Cd kg(-1) and 5.2 to 183 mg kg(-1) Pb, while metal content in the contaminated soils ranged from 104 to 6841 mg Cu kg(-1), 312 to 39,000 mg kg(-1) Zn, 6 to 302 mg Cd kg(-1) and 609 to 12,000 mg kg(-1) Pb. Our analysis of pore-water found the Cu concentrations to be much higher in contaminated soils than in uncontaminated soils, with the distribution coefficients (K(d)) correlating significantly with the log of dissolved organic carbon concentrations. Despite the high total metal content of the contaminated soil, Zn, Cd and Pb were not generally found at elevated levels in the pore-water with the exception of a single contaminated soil. A long period of ageing and soil weathering may have led to a substantial reduction in heavy metal concentrations in the pore-water of contaminated soils. On the other hand, Pb bioaccessibility was found to be comparatively high in Pb contaminated soils, where it tended to exceed the total Pb values by more than 80%. We conclude that, despite the extensive ageing of some contaminated soils, the bioaccessibility of Pb remains relatively high.

[Effect of different soil types on the remediation of copper-pyrene compound contaminated soils by EK-oxidation process].

PubMed

Fan, Guang-Ping; Cang, Long; Zhou, Dong-Mei; Zhou, Li-Xiang

2011-11-01

The effect of different soil types (red soil,yellow-brown soil and black soil) on the electrokinetic (EK)-oxidation remediation of heavy metals-organic pollutant contaminated soil was studied in laboratory-scale experiments. Copper and pyrene were chosen as model pollutant, and 12% H2O2, 10% hydroxypropyl-beta-cyclodextrin and 0.01 mol x L(-1) NaNO3 solution were added into the anode and cathode cell. The applied voltage was 1 V x cm(-1). After 15 days of EK remediation, the removal rate of pyrene and copper in red soil, yellow-brown soil and black soil were 38.5%, 46.8%, 51.3% for pyrene and 85.0%, 22.6%, 24.1% for Cu, respectively. The high pH of black soil produced high electroosmotic flow and increased the exposure of oxidants and pollutants, meanwhile the low clay content was also conducive to the desorption of pyrene. The low pH and organic matter of red soil affected the chemical species distribution of Cu and increased its removal rate. It is concluded that soil pH, clay content and heavy metal speciation in soil are the dominant factors affecting the migration and removal efficiency of pollutants.

Characterization and environmental risk assessment of heavy metals found in fly ashes from waste filter bags obtained from a Chinese steel plant.

PubMed

Zhou, Yun; Ning, Xun-an; Liao, Xikai; Lin, Meiqing; Liu, Jingyong; Wang, Jianghui

2013-09-01

The environmental risk of exposure to six heavy metals (Cu, Pb, Zn, Cr, Ni, and Cd) found in fly ashes from waste filter bags obtained from a steel plant was estimated based on the mineralogical compositions, total concentrations and speciation of the metals in the fly ashes. The results indicated that the fly ashes mainly consisted of hematite, magnetite, cyanite, spinel, coesite and amorphous materials. The concentrations of Zn and Pb were much higher than that of other materials. After Zn and Pb, Ni was present in the highest concentration, followed by Cu, Cr and Cd. Each heavy metal was distributed differently in fly ashes. The levels of Zn, Cd and Pb in the active fraction were very high, and ranged from 64.83 to 81.96%, 34.48 to 82.4% and 6.92 to 79.65% respectively, while Cu, Cr and Ni were mainly present in the residual fraction. The risk assessment code (RAC) values of fly ashes showed that the Zn and Cd present in the H3 sample presented a very high risk, with RAC values greater than 50%. The Cu present in the H3 sample, Cd in the H2 sample and Zn in the H4 and H5 samples presented a high risk. The Pb present in the H2 sample, Cd in the H4 sample, Ni in the H1 and H5 samples, and Zn in the H1 sample presented a medium risk. A low risk was presented by the Cu present in the H1, H2, H4 and H5 samples, the Pb in the H1, H3 and H5 samples, the Cd in the H1 and H5 samples, and the Ni in the H2 sample. No risk was presented by Cr in any sample. Copyright © 2013 Elsevier Inc. All rights reserved.

Assessment of electrokinetic removal of heavy metals from soils by sequential extraction analysis.

PubMed

Reddy, K R; Xu, C Y; Chinthamreddy, S

2001-06-29

Electrokinetic remediation of metal-contaminated soils is strongly affected by soil-type and chemical species of contaminants. This paper investigates the speciation and extent of migration of heavy metals in soils during electrokinetic remediation. Laboratory electrokinetic experiments were conducted using two diverse soils, kaolin and glacial till, contaminated with chromium as either Cr(III) or Cr(VI). Initial total chromium concentrations were maintained at 1000mg/kg. In addition, Ni(II) and Cd(II) were used in concentrations of 500 and 250mg/kg, respectively. The contaminated soils were subjected to a voltage gradient of 1 VDC/cm for over 200h. The extent of migration of contaminants after the electric potential application was determined. Sequential extractions were performed on the contaminated soils before and after electrokinetic treatment to provide an understanding of the distribution of the contaminants in the soils. The initial speciation of contaminants was found to depend on the soil composition as well as the type and amounts of different contaminants present. When the initial form of chromium was Cr(III), exchangeable and soluble fractions of Cr, Ni, and Cd ranged from 10 to 65% in kaolin; however, these fractions ranged from 0 to 4% in glacial till. When the initial form of chromium was Cr(VI), the exchangeable and soluble fractions of Cr, Ni and Cd ranged from 66 to 80% in kaolin. In glacial till, however, the exchangeable and soluble fraction for Cr was 38% and Ni and Cd fractions were 2 and 10%, respectively. The remainder of the contaminants existed as the complex and precipitate fractions. During electrokinetic remediation, Cr(VI) migrated towards the anode, whereas Cr(III), Ni(II) and Cd(II) migrated towards the cathode. The speciation of contaminants after electrokinetic treatment showed that significant change in exchangeable and soluble fractions occurred. In kaolin, exchangeable and soluble Cr(III), Ni(II), and Cd(II) decreased near the anode and increased near the cathode, whereas exchangeable and soluble Cr(VI) decreased near the cathode and increased near the anode. In glacial till, exchangeable and soluble Cr(III), Ni(II), and Cd(II) were low even before electrokinetic treatment and no significant changes were observed after the electrokinetic treatment. However, significant exchangeable and soluble Cr(VI) that was present in glacial till prior to electrokinetic treatment decreased to non-detectable levels near the cathode and increased significantly near the anode. In both kaolin and glacial till, low migration rates occurred as a result of contaminants existing as immobile complexes and precipitates. The overall contaminant removal efficiency was very low (less than 20%) in all tests.

Radical change of Zn speciation in pig slurry amended soil: Key role of nano-sized sulfide particles.

PubMed

Formentini, Thiago Augusto; Legros, Samuel; Fernandes, Cristovão Vicente Scapulatempo; Pinheiro, Adilson; Le Bars, Maureen; Levard, Clément; Mallmann, Fábio Joel Kochem; da Veiga, Milton; Doelsch, Emmanuel

2017-03-01

Spreading livestock manure as fertilizer on farmlands is a widespread practice. It represents the major source of heavy metal(loid)s (HM) input in agricultural soils. Since zinc (Zn) is present at high concentrations in manure, it poses special environmental concerns related to phytotoxicity, groundwater contamination, and introduction in the food chain. Therefore, investigations on the fate and behavior of manure-borne Zn, when it enters the soil environment, are necessary to predict the environmental effects. Nevertheless, long-term field studies assessing Zn speciation in the organic waste matrix, as well as within the soil after manure application, are lacking. This study was designed to fill this gap. Using SEM-EDS and XAS analysis, we reported the following new results: (i) ZnS made up 100% of the Zn speciation in the pig slurry (the highest proportion of ZnS ever observed in organic waste); and (ii) ZnS aggregates were about 1-μm diameter (the smallest particle size ever reported in pig slurry). Moreover, the pig slurry containing ZnS was spread on the soil over an 11-year period, totaling 22 applications, and the resulting Zn speciation within the amended soil was analyzed. Surprisingly, ZnS, i.e. the only species responsible for a nearly 2-fold increase in the Zn concentration within the amended soil, was not detected in this soil. Based on SEM-EDS and XAS observations, we put forward the hypothesis that Zn in the pig slurry consisted of nano-sized ZnS crystallites that further aggregated. The low stability of ZnS nanoparticles within oxic and complex environments such as the studied soil was the key explanation for the radical change in pig slurry-borne Zn speciation after long-term amendments. Copyright © 2016 Elsevier Ltd. All rights reserved.

[Distribution and speciation of Pb in Arabidopsis thaliana shoot and rhizosphere soil by in situ synchrotron radiation micro X-ray fluorescence and X-ray absorption near edge structure].

PubMed

Shen, Ya-Ting

2014-03-01

In order to investigate plant reacting mechanism with heavy metal stress in organ and tissue level, synchrotron radiation micro X-ray fluorescence (micro-SRXRF) was used to determine element distribution characteristics of K, Ca, Mn, Fe, Cu, Zn, Pb in an Arabidopsis thaliana seedling grown in tailing dam soil taken from a lead-zinc mine exploration area. The results showed a regular distribution characters of K, Ca, Fe, Cu and Zn, while Pb appeared not only in root, but also in a leaf bud which was beyond previously understanding that Pb mainly appeared in plant root. Pb competed with Mn in the distribution of the whole seedling. Pb may cause the increase of oxidative stress in root and leaf bud, and restrict Mn absorption and utilization which explained the phenomenon of seedling death in this tailing damp soil. Speciation of Pb in Arabidopsis thaliana and tailing damp rhizosphere soil were also presented after using PbL3 micro X-ray absorption near edge structure (micro-XANES). By comparison of PbL3 XANES peak shape and peak position between standard samples and rhizosphere soil sample, it was demonstrated that the tailing damp soil was mainly formed by amorphous forms like PbO (64.2%), Pb (OH)2 (28.8%) and Pb3O4 (6.3%) rather than mineral or organic Pb speciations. The low plant bioavailability of Pb demonstrated a further research focusing on Pb absorption and speciation conversion is needed, especially the role of dissolve organic matter in soil which may enhance Pb bioavailability.

Bio-metals imaging and speciation in cells using proton and synchrotron radiation X-ray microspectroscopy

PubMed Central

Ortega, Richard; Devès, Guillaume; Carmona, Asunción

2009-01-01

The direct detection of biologically relevant metals in single cells and of their speciation is a challenging task that requires sophisticated analytical developments. The aim of this article is to present the recent achievements in the field of cellular chemical element imaging, and direct speciation analysis, using proton and synchrotron radiation X-ray micro- and nano-analysis. The recent improvements in focusing optics for MeV-accelerated particles and keV X-rays allow application to chemical element analysis in subcellular compartments. The imaging and quantification of trace elements in single cells can be obtained using particle-induced X-ray emission (PIXE). The combination of PIXE with backscattering spectrometry and scanning transmission ion microscopy provides a high accuracy in elemental quantification of cellular organelles. On the other hand, synchrotron radiation X-ray fluorescence provides chemical element imaging with less than 100 nm spatial resolution. Moreover, synchrotron radiation offers the unique capability of spatially resolved chemical speciation using micro-X-ray absorption spectroscopy. The potential of these methods in biomedical investigations will be illustrated with examples of application in the fields of cellular toxicology, and pharmacology, bio-metals and metal-based nano-particles. PMID:19605403

Effect of H+ ion activity and Ca2+ on the toxicity of metals in the environment.

PubMed Central

Hutchinson, T C; Collins, F W

1978-01-01

The role of acidity in determining and restricting plant distribution and performance is discussed. In soils especially, a key effect of H+ ion concentration is on the solubility of potentially toxic heavy metals such as aluminum, managenese, zinc, iron, copper, and nickel. Al has been reported from many studies since the 1920's as the key determining toxic factor in acid soils. Some acid-tolerant species have been shown to be especially tolerant of Al, and mechanisms of tolerance have been suggested. Mn is also a commonly toxic factor at soil pH less than 5.0. Calcium has been shown to alleviate Mn toxicity. Low pH soils are also generally low in Ca, K, Na, and P; all essential major elements for plant growth. In lakes and marine situations acidic waters are uncommon as the waters are buffered. Calcium is again ameliorative of metal toxicities. The pH, redox, and valency state are critical in determining nutrient availability and metal speciation. Recent increases in the H+ ion content of precipitation have caused increased acidities of freshwater lakes in Scandinavia and eastern North America, which have depleted biota, including fish populations. PMID:31277

Metals, Health and the Environment – Emergence of Correlations Between Speciation and Effects

PubMed Central

Williams, David R.

2004-01-01

Over the last half-century both the identification of the causes of diseases and the use of inorganic compounds to treat such conditions have been considerably enlightened through our emerging capabilities to identify the pivotal chemical species involved. The ‘duty of care’ placed upon scientists to protect the environment from manufactured chemicals and to limit their effects upon humans therefrom is best realised from a speciation knowledge database. This paper discusses categorising chemicals in terms of their persistence, bioaccumulation, and toxicities and uses speciation information to optimise desirable effects of chemicals in several applications such as the manufacture of pulp for paper and in the foliar nutrition of crops. Simultaneously, the chemical wasting side effects of industrial overdosing is easily avoided if speciation approaches are used. The move towards new environmentally friendly ligand agents is described and methods of finding substitute agents (often combinations of two or more chemicals) to replace nonbiodegradable EDTA. The geosphere migration of metals through the environment is discussed in terms of speciation. Future objectives discussed include improved means of communicating speciation-based recommendations to decision makers. PMID:18365083

Bioavailability of cadmium adsorbed on various oxides minerals to wetland plant species Phragmites australis.

PubMed

Wang, He; Jia, Yongfeng; Wang, Shaofeng; Zhu, Huijie; Wu, Xing

2009-08-15

The bioavailability of heavy metals strongly depends on their speciation in the environment. The effect of different chemical speciations of cadmium ions (i.e. adsorbed on different oxide minerals) on its bioavailability to wetland plant Phragmites australis was studied. Goethite, magnetite, gibbsite, alumina, and manganese oxide were chosen as representatives of metal (hydr)oxides commonly present in sediment. The cultivar system with Hoagland solution as nutrition supply, and single metal oxide with adsorbed Cd as contaminant was applied to study Cd accumulation by P. australis. The bioaccumulation degree in root after the 45-day treatment followed the order: Al(OH)(3)>Al(2)O(3)>Fe(3)O(4)>MnO(2)>FeOOH. The concentration of Cd in stem and leaf followed a similar order although it was considerably lower than that in root. Low-molecular-weight organic acids (LMWOAs), acetic acid, malic acid and citric acid were used to evaluate the desorbability of Cd from different oxides, which can be indicative of Cd-oxide bonding strength and Cd bioavailability. Desorption of Cd by acetic acid and malic acid followed the order: Al(OH)(3)>Fe(3)O(4)>Al(2)O(3)>FeOOH>MnO(2), while by citric acid: Al(OH)(3)> or =Al(2)O(3)>Fe(3)O(4)>FeOOH>MnO(2). This was consistent with the Cd accumulation degree in the plant. Cd adsorbed on Al(OH)(3) was the most easily desorbable species and most bioavailable to P. australis among the oxide minerals, whereas MnO(2) adsorbed Cd was least desorbable by LMWOAs hence constituted the least bioavailable Cd species adsorbed on the oxide minerals.

Partitioning of Dissolved Metals (Fe, Mn, Cu, Cd, Zn, Ni, and Pb) into Soluble and Colloidal Fractions in Continental Shelf and Offshore Waters, Northern California

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.

Multi-scale analysis of the occurrence of Pb, Cr and Mn in the NIST standards: Urban dust (SRM 1649a) and indoor dust (SRM 2584)

NASA Astrophysics Data System (ADS)

Jiang, Mingyu; Nakamatsu, Yuki; Jensen, Keld A.; Utsunomiya, Satoshi

2014-01-01

Adverse health effects of ambient particulate matters are closely related to the speciation of the constituting organic matters and toxic metals. To determine multi-parameters of the metal speciation in urban and indoor dusts, we have performed systematic bulk- to nano-scale (“multi-scale”) analysis on the speciation of Pb, Mn, and Cr in two National Institute of Standards and Technology (NIST) standard reference materials (SRMs): urban dust (SRM 1649a) and indoor dust (SRM 2584), utilizing X-ray absorption near-edge structure, powder X-ray diffraction analysis, electron microprobe analysis, scanning electron microscopy, and transmission electron microscopy. Major crystalline phases are quartz, gypsum, kaolinite, and muscovite in SRM 1649a, while quartz, gypsum, calcite, and possibly muscovite (or chabazite) in SRM 2584. A number of Pb sulfate nanoparticles (50-200 nm) occur in SRM 1649a, whereas micron-sized Pb carbonate is present containing various concentrations of Zn and Ti in the complex texture in SRM 2584. Relatively soluble Mn(II) sulfate is the bulk-averaged Mn speciation in SRM 1649a, although discrete Mn sulfate particles are not characterized by individual particle analysis, implying the diluted Mn distribution within other sulfate. In SRM 2584, Mn speciation includes a mixture of oxides and carbonates, and trace Mn in chromite. Chromite (FeCr2O4) is the major Cr speciation in SRM1694a, while unidentified Cr(III) phases with minor chromite and Pb chromate are present in SRM 2584, among which the Pb chromate is composed of Cr(VI). A significant number of the metal-bearing particles are distributed to the submicron-size fraction in the urban dust, SRM 1649a, suggesting that these metal nanoparticles can potentially penetrate into the deep respiratory system. This study demonstrates that multi-scale analysis combining nano and bulk analytical techniques is a powerful approach to investigate the multi-parameters of metal-bearing nanoparticles in heterogeneous PM samples.

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

PubMed

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

2004-10-01

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

Speciation and leaching of trace metal contaminants from e-waste contaminated soils.

PubMed

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.

Heavy metal speciation and uptake in crayfish and tadpoles

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

Bundy, K.J.; Berzins, D.; Millet, L.

1996-12-31

Developing valid pollution recording methods is central to assessing environmental damage and remediation. This often is difficult, however, because of speciation and multiphase distribution of contaminants. Polarography, an electroanalytical technique capable of detection and quantification of trace levels of elements and ionic complexes, is a promising method for analyzing environmental samples. Here, polarography has been used to determine lead concentration in water, sediment, bullfrogs, tadpoles, and adsorbed onto kaolin. It has also been used to measure hexavalent chromium concentration in crayfish. This research involves field studies and two laboratory experiments. Studies of a Louisiana swamp have shown lead`s affinity formore » sediment and water particulate phases, rather than being ionically dissolved in the aqueous phase. In swamp bullfrogs, lead was found in greater concentrations in bone compared to muscle. In the first laboratory experiment, lead uptake originating from water and sediment increased in tadpoles as exposure time and concentration increased. Also, this animal`s development was hindered at higher concentrations. The second laboratory experiment exposed crayfish to aqueous hexavalent chromium. Total chromium uptake increased with exposure time and concentration. The chromium tissue abundance was hepatopancreas > gills > muscle. A substantial portion of tissue hexavalent chromium converted to the less toxic trivalent form.« less

Effect of Transport and Aging Processes on Metal Speciation in Iron Oxyhydroxide Aggregates, Tar Creek Superfund Site, Oklahoma

NASA Astrophysics Data System (ADS)

Estes, E. R.; Schaider, L. A.; Shine, J. P.; Brabander, D. J.

2010-12-01

Following the cessation of mining activity in the late 20th century, Tar Creek Superfund Site was left highly contaminated by Pb, Zn, and Cd. Tar Creek, which flows through the site and into the Neosho River, has been studied extensively because of its potential to transport metals from the mining site to downstream communities. Previous research identified aggregated iron oxyhydroxide material, which forms when mine seepage mixes with Tar Creek surface water, as a major transport vector of metals. Frequent flooding in Tar Creek deposits aggregates on downstream floodplains, where wetting and drying processes alter the speciation of iron and other metals. This study seeks to better quantify those changes and to determine how transport and aging affects the human and ecological health risk. Sequential extractions of aggregate samples collected from the creek demonstrate that Fe is present in both amorphous (10-35% of Fe extracted) and more crystalline (8-23% of Fe extracted) phases. Substantial portions of heavy metals sorb to amorphous iron oxyhydroxide phases (accounting for 10-30% of Pb and Zn extracted) but are not associated with more crystalline iron oxide phases (representing only 1% or less of the Pb and Zn extracted). Samples have a high organic matter content (18-25% mass loss on ignition), but only Fe was significantly extracted by the oxidizing step targeting organic matter (1-2% of Pb and Zn extracted, but 10-26% of Fe extracted). The majority of metals were extracted by the soluble or residual steps. If metals and organic matter inhibit transformation of amorphous iron oxyhydroxide material to nano and crystalline iron oxides, then a steady-state volume of amorphous iron oxyhydroxide material with a high total sorption capacity may exist within Tar Creek, enhancing the metal flux accommodated by this transport mechanism. Once transported downstream and deposited on floodplains, however, it is hypothesized that repeated changes in soil matrix composition and thermodynamic conditions could facilitate a transformation to more crystalline iron phases and increase metal bioavailability. While preliminary data from in-creek aggregates show no clear trend in mineralogical composition with downstream transport, only the furthest downstream samples have 2-line ferrihydrite in amounts detectable by XRD.

Donnan membrane speciation of Al, Fe, trace metals and REEs in coastal lowland acid sulfate soil-impacted drainage waters.

PubMed

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.

Living organisms as an alternative to hyphenated techniques for metal speciation. Evaluation of baker's yeast immobilized on silica gel for Hg speciation*1

NASA Astrophysics Data System (ADS)

Pérez-Corona, Teresa; Madrid-Albarrán, Yolanda; Cámara, Carmen; Beceiro, Elisa

1998-02-01

The use of living organisms for metal preconcentration and speciation is discussed. Among substrates, Saccharomyces cerevisiae baker's yeast has been successfully used for the speciation of mercury [Hg(II) and CH 3Hg +], selenium [Se(IV) and Se(VI)] and antimony [Sb(III) and Sb(V)]. To illustrate the capabilities of these organisms, the analytical performance of baker's yeast immobilized on silica gel for on-line preconcentration and speciation of Hg(II) and methylmercury is reported. The immobilized cells were packed in a PTFE microcolumn, through which mixtures of organic and inorganic mercury solutions were passed. Retention of inorganic and organic mercury solutions took place simultaneously, with the former retained in the silica and the latter on the yeast. The efficiency uptake for both species was higher than 95% over a wide pH range. The speciation was carried out by selective and sequential elution with 0.02 mol L -1 HCl for methylmercury and 0.8 mol L -1 CN - for Hg(II). This method allows both preconcentration and speciation of mercury. The preconcentration factors were around 15 and 100 for methylmercury and mercury(II), respectively. The method has been successfully applied to spiked sea water samples.

How Does Boiling in the Earth's Crust Influence Metal Speciation and Transport?

NASA Astrophysics Data System (ADS)

Kam, K.; Lemke, K.

2014-12-01

The presence of large quantities of precious metals, such as gold and copper, near the Earth's surface (upper crust) is commonly attributed to transport in aqueous solution and precipitation upon variations in temperature and pressure. As a consequence, gold exploration is closely linked to solution chemistry, i.e. hydrothermal processes involving aqueous fluids with densities of around unity. However, as crustal fluids buoyantly ascend, boiling produces a coexisting low-density aqueous liquid with fundamentally different physical and chemical properties, and a, most importantly, a high affinity for coinage metals (Heinrich et al., Econ Geol., 1992, 87, 1566). From recent experimental studies of Au (Hurtig and Williams-Jones, 2014, Geochim. Cosmochim. Acta,, 127, 304), we know that metal speciation in this low-density phase differs fundamentally from that observed in bulk solution, clearly, with important implications for Au, and metal speciation in general, transport and ore concentrations processes (these processes would also be operable in industrial geothermal plants given the quite special solvent properties of steam). In brief, this study focuses on the speciation of select metal halides in bulk solution as well as in water vapor, and is driven by our need to understand the solvent properties of around 2.0x109 cubic kilometers of free water (or 2,500 times as much water as stored in all lakes and rivers) present in the Earth's crust. The scope of this study has particular applications in the geothermal and oil industries, as both deal with high temperature low-density aqueous fluids. Understanding how metal halide species behave upon boiling can also provide insight into how metals, such as copper and silver, coat turbine equipment and steam piping in geothermal plants, ultimately rendering these components inoperable. This study will also provide preliminary results from mass spectrometric experiments of transition metal halides, and will be augmented with results from molecular simulations of metal halides that are aimed at characterizing the nature (i.e. relativistic structures and energies) of metal clusters in water vapor.

Metal loading levels influence on REE distribution on humic acid: Experimental and Modelling approach

NASA Astrophysics Data System (ADS)

Marsac, R.; Davranche, M.; Gruau, G.; Dia, A.

2009-04-01

In natural organic-rich waters, rare earth elements (REE) speciation is mainly controlled by organic colloids such as humic acid (HA). Different series of REE-HA complexation experiments performed at several metal loading (REE/C) displayed two pattern shapes (i) at high metal loading, a middle-REE (MREE) downward concavity, and (ii) at low metal loading, a regular increase from La to Lu (e.g. Sonke and Salters, 2006; Pourret et al., 2007). Both REE patterns might be related to REE binding with different surface sites on HA. To understand REE-HA binding, REE-HA complexation experiments at various metals loading were carried out using ultrafiltration combined with ICP-MS measurements, for the 14 REE simultaneously. The patterns of the apparent coefficients of REE partition between HA and the inorganic solution (log Kd) evolved regularly according to the metal loading. The REE patterns presented a MREE downward concavity at low loading and a regular increase from La to Lu at high loading. The dataset was modelled with Model VI by adjusting two specific parameters, log KMA, the apparent complexation constant of HA low affinity sites and DLK2, the parameter increasing high affinity sites binding strength. Experiments and modelling provided evidence that HA high affinity sites controlled the REE binding with HA at low metal loading. The REE-HA complex could be as multidentate complexes with carboxylic or phenolic sites or potentially with sites constituted of N, P or S as donor atoms. Moreover, these high affinity sites could be different for light and heavy REE, because heavy REE have higher affinity for these sites, in low density, and could saturate them. These new Model VI parameter sets allowed the prediction of the REE-HA pattern shape evolution on a large range of pH and metal loading. According to the metal loading, the evolution of the calculated REE patterns was similar to the various REE pattern observed in natural acidic organic-rich waters (pH<7 and DOC>10 mg L-1). As a consequence, the metal loading could be the key parameter controlling the REE pattern in organic-rich waters.

Photochemical changes in cyanide speciation in drainage from a precious metal ore heap

USGS Publications Warehouse

Johnson, C.A.; Leinz, R.W.; Grimes, D.J.; Rye, R.O.

2002-01-01

In drainage from an inactive ore heap at a former gold mine, the speciation of cyanide and the concentrations of several metals were found to follow diurnal cycles. Concentrations of the hexacyanoferrate complex, iron, manganese, and ammonium were higher at night than during the day, whereas weak-acid-dissociable cyanide, silver, gold, copper, nitrite, and pH displayed the reverse behavior. The changes in cyanide speciation, iron, and trace metals can be explained by photodissociation of iron and cobalt cyanocomplexes as the solutions emerged from the heap into sunlight-exposed channels. At midday, environmentally significant concentrations of free cyanide were produced in a matter of minutes, causing trace copper, silver, and gold to be mobilized as cyanocomplexes from solids. Whether rapid photodissociation is a general phenomenon common to other sites will be important to determine in reaching a general understanding of the environmental risks posed by routine or accidental water discharges from precious metal mining facilities.

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

In-situ determination of metallic variation and multi-association in single particles by combining synchrotron microprobe, sequential chemical extraction and multivariate statistical analysis.

PubMed

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.

Arsenic speciation and spatial and interspecies differences of metal concentrations in mollusks and crustaceans from a South China estuary.

PubMed

Zhang, Wei; Wang, Wen-Xiong; Zhang, Li

2013-05-01

Arsenic speciation and concentrations were determined in mollusks and crustaceans in the intertidal zone from twelve locations in Zhanjiang estuary, South China. Metal concentrations (Ag, As, Cd, Cu, Hg, Ni, Pb, and Zn) were also concurrently determined in these species. Arsenic speciation analysis showed that the less-toxic arsenobetaine (AsB) constituted 80.6-98.8 % of all As compounds, and dimethylarsinic acid (DMA) constituted 0.47-3.44 %. Monomethylarsonic acid (MMA) and As(V) were only detected in the whelk Drupa fiscella and the crab Heteropilumnus ciliatus, respectively. Arsenite [As(III)] was not detected in any of the sampled specimens, but there were also unidentified other As species. A strong spatial variation of metals in the oyster Saccostrea cucullata was found in the estuary, confirming that oysters can be used as a good biomonitor of metal contamination in the studied area. The concentrations of eight metals in the studied mollusks and crustaceans clearly revealed that these invertebrates accumulated different metals to different degrees. Furthermore, As, Cd, Cu, Hg, and Pb contents in mollusks and crustacean samples were below the Food and Agricultural Organization (FAO) safe concentrations, thus there was no obvious health risk from the intake of the metals through marine mollusks and crustaceans consumption.

Applications of time-resolved laser fluorescence spectroscopy to the environmental biogeochemistry of actinides.

PubMed

Collins, Richard N; Saito, Takumi; Aoyagi, Noboru; Payne, Timothy E; Kimura, Takaumi; Waite, T David

2011-01-01

Time-resolved laser fluorescence spectroscopy (TRLFS) is a useful means of identifying certain actinide species resulting from various biogeochemical processes. In general, TRLFS differentiates chemical species of a fluorescent metal ion through analysis of different excitation and emission spectra and decay lifetimes. Although this spectroscopic technique has largely been applied to the analysis of actinide and lanthanide ions having fluorescence decay lifetimes on the order of microseconds, such as UO , Cm, and Eu, continuing development of ultra-fast and cryogenic TRLFS systems offers the possibility to obtain speciation information on metal ions having room-temperature fluorescence decay lifetimes on the order of nanoseconds to picoseconds. The main advantage of TRLFS over other advanced spectroscopic techniques is the ability to determine in situ metal speciation at environmentally relevant micromolar to picomolar concentrations. In the context of environmental biogeochemistry, TRLFS has principally been applied to studies of (i) metal speciation in aqueous and solid phases and (ii) the coordination environment of metal ions sorbed to mineral and bacterial surfaces. In this review, the principles of TRLFS are described, and the literature reporting the application of this methodology to the speciation of actinides in systems of biogeochemical interest is assessed. Significant developments in TRLFS methodology and advanced data analysis are highlighted, and we outline how these developments have the potential to further our mechanistic understanding of actinide biogeochemistry. American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America.

Effects of heavy metals on plants and resistance mechanisms. A state-of-the-art report with special reference to literature published in Chinese journals.

PubMed

Cheng, Shuiping

2003-01-01

As one of the consequences of heavy metal pollution in soil, water and air, plants are contaminated by heavy metals in some parts of China. To understand the effects of heavy metals upon plants and the resistance mechanisms, would make it possible to use plants for cleaning and remediating heavy metal-polluted sites. The research results on the effects of heavy metals on plants and resistant mechanisms are compiled from Chinese publications from scientific journals and university journals, mostly published during the last decade. Effects of heavy metals on plants result in growth inhibition, structure damage, a decline of physiological and biochemical activities as well as of the function of plants. The effects and bioavailability of heavy metals depend on many factors, such as environmental conditions, pH, species of element, organic substances of the media and fertilization, plant species. But, there are also studies on plant resistance mechanisms to protect plants against the toxic effects of heavy metals such as combining heavy metals by proteins and expressing of detoxifying enzyme and nucleic acid, these mechanisms are integrated to protect the plants against injury by heavy metals. There are two aspects on the interaction of plants and heavy metals. On one hand, heavy metals show negative effects on plants. On the other hand, plants have their own resistance mechanisms against toxic effects and for detoxifying heavy metal pollution. To study the effects of heavy metals on plants and mechanisms of resistance, one must select crop cultivars and/or plants for removing heavy metals from soil and water. More highly resistant plants can be selected especially for a remediation of the pollution site. The molecular mechanisms of resistance of plants to heavy metals should be studied further to develop the actual resistance of these plants to heavy metals. Understanding the bioavailability of heavy metals is advantageous for plant cultivation and phytoremediation. Decrease in the bioavailability to farmlands would reduce the accumulation of heavy metals in food. Alternatively, one could increase the bioavailability of plants to extract more heavy metals.

The importance of ligand speciation in environmental research: a case study.

PubMed

Sillanpää, M; Orama, M; Rämö, J; Oikari, A

2001-02-21

The speciations of EDTA and DTPA in process, waste and river waters are modelled and simulated, specifically to the mode of occurrence in the pulp and paper mill effluents and subsequently in receiving waters. Due to relatively short residence times in bleaching process and waste water treatment and slow exchange kinetics, it is expected that the thermodynamic equilibrium is not necessarily reached. Therefore, the initial speciation plays a key role. As such, the simulations have been extended to the process waters of the pulp and paper industry taking into account estimated average conditions. The results reveal that the main species are; Mn and Ca complexes of EDTA and DTPA in pulp mill process waters; Fe(III) and Mn complexes of EDTA and DTPA in waste waters; Fe(III) and Zn complexes of EDTA and DTPA in receiving waters. It is also shown how the increasing concentration of complexing agents effects the speciation. Alkaline earth metal chelation plays a significant role in the speciation of EDTA and DTPA when there is a noticeable molar excess of complexing agents compared with transition metals.

Speciation of nanoscale objects by nanoparticle imprinted matrices

NASA Astrophysics Data System (ADS)

Hitrik, Maria; Pisman, Yamit; Wittstock, Gunther; Mandler, Daniel

2016-07-01

The toxicity of nanoparticles is not only a function of the constituting material but depends largely on their size, shape and stabilizing shell. Hence, the speciation of nanoscale objects, namely, their detection and separation based on the different species, similarly to heavy metals, is of outmost importance. Here we demonstrate the speciation of gold nanoparticles (AuNPs) and their electrochemical detection using the concept of ``nanoparticles imprinted matrices'' (NAIM). Negatively charged AuNPs are adsorbed as templates on a conducting surface previously modified with polyethylenimine (PEI). The selective matrix is formed by the adsorption of either oleic acid (OA) or poly(acrylic acid) (PAA) on the non-occupied areas. The AuNPs are removed by electrooxidation to form complementary voids. These voids are able to recognize the AuNPs selectively based on their size. Furthermore, the selectivity could be improved by adsorbing an additional layer of 1-hexadecylamine, which deepened the voids. Interestingly, silver nanoparticles (AgNPs) were also recognized if their size matched those of the template AuNPs. The steps in assembling the NAIMs and the reuptake of the nanoparticles were characterized carefully. The prospects for the analytical use of NAIMs, which are simple, of small dimension, cost-efficient and portable, are in the sensing and separation of nanoobjects.The toxicity of nanoparticles is not only a function of the constituting material but depends largely on their size, shape and stabilizing shell. Hence, the speciation of nanoscale objects, namely, their detection and separation based on the different species, similarly to heavy metals, is of outmost importance. Here we demonstrate the speciation of gold nanoparticles (AuNPs) and their electrochemical detection using the concept of ``nanoparticles imprinted matrices'' (NAIM). Negatively charged AuNPs are adsorbed as templates on a conducting surface previously modified with polyethylenimine (PEI). The selective matrix is formed by the adsorption of either oleic acid (OA) or poly(acrylic acid) (PAA) on the non-occupied areas. The AuNPs are removed by electrooxidation to form complementary voids. These voids are able to recognize the AuNPs selectively based on their size. Furthermore, the selectivity could be improved by adsorbing an additional layer of 1-hexadecylamine, which deepened the voids. Interestingly, silver nanoparticles (AgNPs) were also recognized if their size matched those of the template AuNPs. The steps in assembling the NAIMs and the reuptake of the nanoparticles were characterized carefully. The prospects for the analytical use of NAIMs, which are simple, of small dimension, cost-efficient and portable, are in the sensing and separation of nanoobjects. Electronic supplementary information (ESI) available: S1 - instrumentation, S2 - immobilization of AuNPs, S3 - time dependent immobilization, S4 - CVs at matrix-coated substrates, S5 - CVs at AuNP-loaded matrices, S6 - peak potentials for the oxidation of AuNPs of different sizes, S7 - schematics for the change of conductive area of the matrices, S8 - probe CVs before and after AuNPs oxidation, S9 - calculation of adsorbed and reuptaken AuNPs, S10 - CVs of AuNPs adsorbed on non-imprinted matrices, S11 - SEM images of AuNPs adsorbed on non-imprinted matrices, S12 - SEM images after reuptake of AuNPs, S13 - schematic of the effect of thickening the matrix. See DOI: 10.1039/c6nr01106c

Transfer of heavy metals through terrestrial food webs: a review.

PubMed

Gall, Jillian E; Boyd, Robert S; Rajakaruna, Nishanta

2015-04-01

Heavy metals are released into the environment by both anthropogenic and natural sources. Highly reactive and often toxic at low concentrations, they may enter soils and groundwater, bioaccumulate in food webs, and adversely affect biota. Heavy metals also may remain in the environment for years, posing long-term risks to life well after point sources of heavy metal pollution have been removed. In this review, we compile studies of the community-level effects of heavy metal pollution, including heavy metal transfer from soils to plants, microbes, invertebrates, and to both small and large mammals (including humans). Many factors contribute to heavy metal accumulation in animals including behavior, physiology, and diet. Biotic effects of heavy metals are often quite different for essential and non-essential heavy metals, and vary depending on the specific metal involved. They also differ for adapted organisms, including metallophyte plants and heavy metal-tolerant insects, which occur in naturally high-metal habitats (such as serpentine soils) and have adaptations that allow them to tolerate exposure to relatively high concentrations of some heavy metals. Some metallophyte plants are hyperaccumulators of certain heavy metals and new technologies using them to clean metal-contaminated soil (phytoextraction) may offer economically attractive solutions to some metal pollution challenges. These new technologies provide incentive to catalog and protect the unique biodiversity of habitats that have naturally high levels of heavy metals.

Toward understanding the role of individual fluorescent components in DOM-metal binding.

PubMed

Wu, Jun; Zhang, Hua; Yao, Qi-Sheng; Shao, Li-Ming; He, Pin-Jing

2012-05-15

Knowledge on the function of individual fractions in dissolved organic matter (DOM) is essential for understanding the impact of DOM on metal speciation and migration. Herein, fluorescence excitation-emission matrix quenching and parallel factor (PARAFAC) analysis were adopted for bulk DOM and chemically isolated fractions from landfill leachate, i.e., humic acids (HA), fulvic acids and hydrophilic (HyI) fraction, to elucidate the role of individual fluorescent components in metal binding (Cu(II) and Cd(II)). Three components were identified by PARAFAC model, including one humic substance (HS)-like, one protein-like and one component highly correlated with the HyI fraction. Among them, the HS-like and protein-like components were responsible for Cu(II) binding, while the protein-like component was the only fraction involved in Cd(II) complexation. It was further identified that the slight quenching effect of HA fraction by Cd(II) was induced by the presence of proteinaceous materials in HA. Fluorescent substances in the HyI fraction of landfill leachate did not play as important a role as HS did. Therefore, it was suggested that the potential risk of aged leachate (more humified) as a carrier of heavy metal should not be overlooked. Copyright © 2012 Elsevier B.V. All rights reserved.

Characterization and environmental risk assessment of heavy metals in construction and demolition wastes from five sources (chemical, metallurgical and light industries, and residential and recycled aggregates).

PubMed

Gao, Xiaofeng; Gu, Yilu; Xie, Tian; Zhen, Guangyin; Huang, Sheng; Zhao, Youcai

2015-06-01

Total concentrations of heavy metals (Cu, Zn, Pb, Cr, Cd, and Ni) were measured among 63 samples of construction and demolition (C&D) wastes collected from chemical, metallurgical and light industries, and residential and recycled aggregates within China for risk assessment. The heavy metal contamination was primarily concentrated in the chemical and metallurgical industries, especially in the electroplating factory and zinc smelting plant. High concentrations of Cd were found in light industry samples, while the residential and recycled aggregate samples were severely polluted by Zn. Six most polluted samples were selected for deep research. Mineralogical analysis by X-ray fluorescence (XRF) spectrometry and X-ray diffraction (XRD), combined with element speciation through European Community Bureau of Reference (BCR) sequential extraction, revealed that a relatively slight corrosion happened in the four samples from electroplating plants but high transfer ability for large quantities of Zn and Cu. Lead arsenate existed in the acid extractable fraction in CI7-8 and potassium chromium oxide existed in the mobility fraction. High concentration of Cr could be in amorphous forms existing in CI9. The high content of sodium in the two samples from zinc smelter plants suggested severe deposition and erosion on the workshop floor. Large quantities of Cu existed as copper halide and most of the Zn appeared to be zinc, zinc oxide, barium zinc oxide, and zincite. From the results of the risk assessment code (RAC), the samples from the electroplating factory posed a very high risk of Zn, Cu, and Cr, a high risk of Ni, a middle risk of Pb, and a low risk of Cd. The samples from the zinc smelting plant presented a high risk of Zn, a middle risk of Cu, and a low risk of Pb, Cr, Cd, and Ni.

[Research advances in heavy metals pollution ecology of diatom].

PubMed

Ding, Teng-Da; Ni, Wan-Min; Zhang, Jian-Ying

2012-03-01

Diatom, due to its high sensitivity to environmental change, is one of the bio-indicators of aquatic ecosystem health, and some typical diatom species have been applied to indicate the heavy metals pollution of water body. With the focus on the surface water heavy metals pollution, this paper reviewed the research advances in the toxic effect of heavy metals pollution on diatom, biosorption and bioaccumulation of heavy metals by diatom, ecological adaptation mechanisms of diatom to heavy metals pollution, and roles of diatom as bio-indicator and in ecological restoration of heavy metals pollution. The growth tendency of diatom and the morphological change of frustule under heavy metals pollution as well as the differences in heavy metals biosorption and bioaccumulation by diatom, the ecological adaptation mechanisms of diatom on heavy metals surface complexation and ion exchange, and the roles of diatom as bio-indicator and in ecological restoration of heavy metals polluted water body were also discussed. This review could provide scientific evidences for the prevention of aquatic ecosystems heavy metals pollution and related early warning techniques.

Modeling Biogeochemical Cycling of Heavy Metals in Lake Coeur d'Alene Sediments

NASA Astrophysics Data System (ADS)

Sengor, S. S.; Spycher, N.; Belding, E.; Curthoys, K.; Ginn, T. R.

2005-12-01

Mining of precious metals since the late 1800's have left Lake Coeur d'Alene (LCdA) sediments heavily enriched with toxic metals, including Cd, Cu, Pb, and Zn. Indigenous microbes however are capable of catalyzing reactions that detoxify the benthic and aqueous lake environments, and thus constitute an important driving component in the biogeochemical cycles of these metals. Here we report on the development of a quantitative model of transport, fate, exposure and effects of toxic compounds on benthic microbial communities at LCdA. First, chemical data from the LCdA area have been compiled from multiple sources to investigate trends in chemical occurrence, as well as to define model boundary conditions. The model is structured as 1-D diffusive reactive transport model to simulate spatial and temporal distribution of metals through the benthic sediments. Inorganic reaction processes included in the model are aqueous speciation, surface complexation, mineral precipitation/dissolution and abiotic redox reactions. Simulations with and without surface complexation are carried out to evaluate the effect of sorption and the conservative behaviour of metals within the benthic sediments under abiotic and purely diffusive transport. The 1-D inorganic diffusive transport model is then coupled to a biotic reaction network including consortium biodegradation kinetics with multiple electron acceptors, product toxicity, and energy partitioning. Multiyear simulations are performed, with water column chemistry established as a boundary condition from extant data, to explore the role of biogeochemical dynamics on benthic fluxes of metals in the long term.

Uncertainty analysis of the nonideal competitive adsorption-donnan model: effects of dissolved organic matter variability on predicted metal speciation in soil solution.

PubMed

Groenenberg, Jan E; Koopmans, Gerwin F; Comans, Rob N J

2010-02-15

Ion binding models such as the nonideal competitive adsorption-Donnan model (NICA-Donnan) and model VI successfully describe laboratory data of proton and metal binding to purified humic substances (HS). In this study model performance was tested in more complex natural systems. The speciation predicted with the NICA-Donnan model and the associated uncertainty were compared with independent measurements in soil solution extracts, including the free metal ion activity and fulvic (FA) and humic acid (HA) fractions of dissolved organic matter (DOM). Potentially important sources of uncertainty are the DOM composition and the variation in binding properties of HS. HS fractions of DOM in soil solution extracts varied between 14 and 63% and consisted mainly of FA. Moreover, binding parameters optimized for individual FA samples show substantial variation. Monte Carlo simulations show that uncertainties in predicted metal speciation, for metals with a high affinity for FA (Cu, Pb), are largely due to the natural variation in binding properties (i.e., the affinity) of FA. Predictions for metals with a lower affinity (Cd) are more prone to uncertainties in the fraction FA in DOM and the maximum site density (i.e., the capacity) of the FA. Based on these findings, suggestions are provided to reduce uncertainties in model predictions.

Temporal variations and spatial distributions of heavy metals in a wastewater-irrigated soil-eggplant system and associated influencing factors.

PubMed

Ai, Shiwei; Liu, Bailin; Yang, Ying; Ding, Jian; Yang, Wenzhi; Bai, Xiaojuan; Naeem, Sajid; Zhang, Yingmei

2018-05-30

Heavy metal pollution in farmlands is highly concerned as crops' easy-uptake of heavy metal can ultimately affect consumers. In order to offer suggestions on cultivating safe quality vegetable, specifically eggplant which is widely consumed for its nutritional value and antioxidant activity, a field study was undertaken to investigate the temporal variations and spatial distributions of heavy metals in a wastewater-irrigated soil-eggplant system. In the present study, eggplants were planted in the farmlands of Weichuan village (WC) (relatively unpolluted field), Liangzhuang village (LZ) (moderately polluted field) and Minqin village (MQ) (seriously polluted field) to elucidate their temporal uptake processes of heavy metals described by the sigmoid model. Eggplant tissues from severely polluted farmlands were found with higher heavy metal concentrations and lower yields compared with other two groups. What is more, 25 farmlands along the Dongdagou stream (heavy metals polluted stream) were chosen to analyze the spatial distribution of heavy metals in soils and eggplants. Heavy metal concentrations in eggplants decreased with the decline of heavy metal concentrations in soil from upstream (pollution source) to downstream. Moreover, several methods were employed to assess bioavailability of heavy metals in soils. All the bioavailable heavy metals were found in linear positive correlations with heavy metal concentrations. Meanwhile, linear correlations were found between heavy metals in soils and eggplants. At last, redundancy analysis was used to investigate the effects of soil properties (pH, organic matter and texture of soils) and heavy metals on eggplants' uptake. The results indicated that soil heavy metals had a dominant impact on their accumulations in eggplant fruit, with a variance contribution of 78.0%, while soil properties had a regulatory effect, with a variance contribution of 5.2%. Copyright © 2018 Elsevier Inc. All rights reserved.

Sulfur K-edge XANES and acid volatile sulfide analyses of changes in chemical speciation of S and Fe during sequential extraction of trace metals in anoxic sludge from biogas reactors.

PubMed

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.

ELEMENTAL SPECIATION IN ENVIRONMENTAL EXPOSURE ASSESSMENT MATRICES

EPA Science Inventory

Arsenic and tin are two trace metals where exposure assessments have moved towards a speciation based approach because the toxicity is very chemical form dependent. This toxicity difference can be one of many factors which influence the formulation of certain regulations. For a...

Flux of heavy metal accumulation in various organs of the intertidal marine blue crab, Portunus pelagicus (L.) from the Kuwait coast after the Gulf War.

PubMed

Al-Mohanna, S Y; Subrahmanyam, M N

2001-10-01

The metal levels of arsenic, chromium, copper, lead, magnesium, manganese, selenium, vanadium, and zinc concentrations were determined in various body organs, viz., hepatopancreas, gills, gonad, gastric stomach, and muscle of the blue crab, Portunus pelagicus (Crustacea: Decapoda) to assess the bioaccumulation of metals associated with petroleum input a decade after the 1991 Gulf War oil spillage. Sample solutions prepared were analyzed using an atomic absorption spectrophotometry. High concentrations of Zn and Cu in the muscle and hepatopancreas tissues were a strong indicative of high exposure of P. pelagicus to these metals. However, muscle tissue had been found to accumulate the highest values for all metal speciations analyzed. Copper, zinc, and chromium in samples collected from Station II covering the Kuwait City area were often in excess of those present in Station I and III. Arsenic, lead, magnesium, manganese, selenium, and vanadium were greater in individuals obtained from Station I. A significant correlation was found to exist between Se and V in crab muscle with a surge in Se metal concentration, which was found to be inversely proportional to that of V metal concentration irrespective of the sex of the crab. The difference in patterns of metal occurrence and the significant increase in the Cu and Zn concentrations in various organs of the crab were largely associated with the 1991 Gulf War oil spill. Such results could be used as a baseline for the monitoring of the level of metals in marine organisms of future studies.

Assessing potential dietary toxicity of heavy metals in selected vegetables and food crops*

PubMed Central

Islam, Ejaz ul; Yang, Xiao-e; He, Zhen-li; Mahmood, Qaisar

2007-01-01

Heavy metals, such as cadmium, copper, lead, chromium and mercury, are important environmental pollutants, particularly in areas with high anthropogenic pressure. Their presence in the atmosphere, soil and water, even in traces can cause serious problems to all organisms, and heavy metal bioaccumulation in the food chain especially can be highly dangerous to human health. Heavy metals enter the human body mainly through two routes namely: inhalation and ingestion, ingestion being the main route of exposure to these elements in human population. Heavy metals intake by human populations through food chain has been reported in many countries. Soil threshold for heavy metal toxicity is an important factor affecting soil environmental capacity of heavy metal and determines heavy metal cumulative loading limits. For soil-plant system, heavy metal toxicity threshold is the highest permissible content in the soil (total or bioavailable concentration) that does not pose any phytotoxic effects or heavy metals in the edible parts of the crops does not exceed food hygiene standards. Factors affecting the thresholds of dietary toxicity of heavy metal in soil-crop system include: soil type which includes soil pH, organic matter content, clay mineral and other soil chemical and biochemical properties; and crop species or cultivars regulated by genetic basis for heavy metal transport and accumulation in plants. In addition, the interactions of soil-plant root-microbes play important roles in regulating heavy metal movement from soil to the edible parts of crops. Agronomic practices such as fertilizer and water managements as well as crop rotation system can affect bioavailability and crop accumulation of heavy metals, thus influencing the thresholds for assessing dietary toxicity of heavy metals in the food chain. This paper reviews the phytotoxic effects and bioaccumulation of heavy metals in vegetables and food crops and assesses soil heavy metal thresholds for potential dietary toxicity. PMID:17173356

Assessing potential dietary toxicity of heavy metals in selected vegetables and food crops.

PubMed

Islam, Ejaz ul; Yang, Xiao-e; He, Zhen-li; Mahmood, Qaisar

2007-01-01

Heavy metals, such as cadmium, copper, lead, chromium and mercury, are important environmental pollutants, particularly in areas with high anthropogenic pressure. Their presence in the atmosphere, soil and water, even in traces can cause serious problems to all organisms, and heavy metal bioaccumulation in the food chain especially can be highly dangerous to human health. Heavy metals enter the human body mainly through two routes namely: inhalation and ingestion, ingestion being the main route of exposure to these elements in human population. Heavy metals intake by human populations through food chain has been reported in many countries. Soil threshold for heavy metal toxicity is an important factor affecting soil environmental capacity of heavy metal and determines heavy metal cumulative loading limits. For soil-plant system, heavy metal toxicity threshold is the highest permissible content in the soil (total or bioavailable concentration) that does not pose any phytotoxic effects or heavy metals in the edible parts of the crops does not exceed food hygiene standards. Factors affecting the thresholds of dietary toxicity of heavy metal in soil-crop system include: soil type which includes soil pH, organic matter content, clay mineral and other soil chemical and biochemical properties; and crop species or cultivars regulated by genetic basis for heavy metal transport and accumulation in plants. In addition, the interactions of soil-plant root-microbes play important roles in regulating heavy metal movement from soil to the edible parts of crops. Agronomic practices such as fertilizer and water managements as well as crop rotation system can affect bioavailability and crop accumulation of heavy metals, thus influencing the thresholds for assessing dietary toxicity of heavy metals in the food chain. This paper reviews the phytotoxic effects and bioaccumulation of heavy metals in vegetables and food crops and assesses soil heavy metal thresholds for potential dietary toxicity.

Microbes in Heavy Metal Remediation: A Review on Current Trends and Patents.

PubMed

Mishra, Geetesh Kumar

2017-01-01

Heavy metal pollution in the environmental samples like soil, water and runoff water is a worldwide problem. Such contamination of environmental matrices by the heavy metals accumulates due to various activities involving human driven sources and industries, although agriculture and sewage disposal are the largest source for the heavy metal contamination. Disposal of heavy metals or waste products containing heavy metals in the environment postures a trivial threat to public safety and health. Heavy metals are persistence and they can also cause biomagnifications and accumulate in food chain. Microbial bioremediation of heavy metal is emerging as an effective technique. Microbial bioremediation is a highly efficient environmental friendly procedure which also reduces the cost of cleanup process associated with heavy metal contamination. New methods for removal of heavy metals from the environmental samples are under development and most recent advancements have been made in exploring the knowledge of metal-microbes interactions and its use for heavy metal remediation. This review paper will focus on the microbial bioremediation process and highlight some of the newly developed patented methods for microbial bioremediation of the heavy metals from the environmental samples using microbial populations. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

Heavy Metal Contaminated Soil Imitation Biological Treatment Overview

NASA Astrophysics Data System (ADS)

Pan, Chang; Chen, Jun; Wu, Ke; Zhou, Zhongkai; Cheng, Tingting

2018-01-01

In this paper, the treatment methods of heavy metal pollution in soils were analyzed, the existence and transformation of heavy metals in soil were explored, and the mechanism of heavy metal absorption by plants was studied. It was concluded that the main form of plants absorb heavy metals in the soil is exchangeable. The main mechanism was that the plant cell wall can form complex with heavy metals, so that heavy metals fixed on the cell wall, and through the selective absorption of plasma membrane into the plant body. In addition, the adsorption mechanism of the adsorbed material was analyzed. According to the results of some researchers, it was found that the mechanism of adsorption of heavy metals was similar to that of plants. According to this, using adsorbent material as the main material, Imitate the principle of plant absorption of heavy metals in the soil to removing heavy metals in the soil at one-time and can be separated from the soil after adsorption to achieve permanent removal of heavy metals in the soil was feasibility.

Effect of various types of thermochemical processing of sewage sludges on phosphorus speciation, solubility, and fertilization performance.

PubMed

Steckenmesser, Daniel; Vogel, Christian; Adam, Christian; Steffens, Diedrich

2017-04-01

Sewage sludge has one of the highest phosphorus (P) recovery potentials of all waste materials. Therefore, P-recycling from sewage sludge could contribute to closing the P-cycle. Recently, various thermal processes for P-recovery have been developed, but there is still a demand for information on the effect of different process parameters (e.g. additives and temperature) on P-speciation and especially on the fertilization performance. In the present study, two common methods (low-temperature conversion at 400-500°C and thermochemical treatment at 950°C) were investigated and combined to produce highly bioavailable P-fertilizers from two different types of sewage sludge based on chemical phosphorus precipitation (Chem-P) and enhanced biological phosphorus removal (Bio-P). The results of P-fractionation, X-ray diffraction analysis, and pot experiments with maize showed that Bio-P sludges attain high P-plant-availability after treatment at low temperatures (400°C). In contrast, Chem-P sludges can adequately be treated at higher temperatures under reductive conditions with sodium additives to form highly bioavailable calcium-sodium-phosphate. Additionally, also highly heavy-metal contaminated sludges can be thermochemically treated at high temperatures to achieve the legal requirements for fertilizers. Copyright © 2017 Elsevier Ltd. All rights reserved.

Ecological risk and pollution history of heavy metals in Nansha mangrove, South China.

PubMed

Wu, Qihang; Tam, Nora F Y; Leung, Jonathan Y S; Zhou, Xizhen; Fu, Jie; Yao, Bo; Huang, Xuexia; Xia, Lihua

2014-06-01

Owing to the Industrial Revolution in the late 1970s, heavy metal pollution has been regarded as a serious threat to mangrove ecosystems in the region of the Pearl River Estuary, potentially affecting human health. The present study attempted to characterize the ecological risk of heavy metals (Cd, Cr, Cu, Mn, Ni, Pb and Zn) in Nansha mangrove, South China, by estimating their concentrations in the surface sediment. In addition, the pollution history of heavy metals was examined by determining the concentrations of heavy metals along the depth gradient. The phytoremediation potential of heavy metals by the dominant plants in Nansha mangrove, namely Sonneratia apetala and Cyperus malaccensis, was also studied. Results found that the surface sediment was severely contaminated with heavy metals, probably due to the discharge of industrial sewage into the Pearl River Estuary. Spatial variation of heavy metals was generally unobvious. The ecological risk of heavy metals was very high, largely due to Cd contamination. All heavy metals, except Mn, decreased with depth, indicating that heavy metal pollution has been deteriorating since 1979. Worse still, the dominant plants in Nansha mangrove had limited capability to remove the heavy metals from sediment. Therefore, we propose that immediate actions, such as regulation of discharge standards of industrial sewage, should be taken by the authorities concerned to mitigate the ecological risk posed by heavy metals. Copyright © 2014 Elsevier Inc. All rights reserved.

Recovering heavy rare earth metals from magnet scrap

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

Ott, Ryan T.; McCallum, Ralph W.; Jones, Lawrence L.

A method of treating rare earth metal-bearing permanent magnet scrap, waste or other material in a manner to recover the heavy rare earth metal content separately from the light rare earth metal content. The heavy rare earth metal content can be recovered either as a heavy rare earth metal-enriched iron based alloy or as a heavy rare earth metal based alloy.

METHODS FOR THE SPECIATION OF METALS IN SOILS: A REVIEW

EPA Science Inventory

The inability to determine metal species in soils hampers efforts to understand the mobility, bioavailability, and fate of contaminant metals in environmental systems, to assess health risks posed by them, and to develop methods to remediate metal contaminated sites. Fortunately,...

METAL SPECIATION IN SOIL, SEDIMENT, AND WATER SYSTEMS VIA SYNCHROTRON RADIATION RESEARCH

EPA Science Inventory

Metal contaminated environmental systems (soils, sediments, and water) have challenged researchers for many years. Traditional methods of analysis have employed extraction methods to determine total metal content and define risk based on the premise that as metal concentration in...

Monitoring of heavy metal levels in the major rivers and in residents' blood in Zhenjiang City, China, and assessment of heavy metal elimination via urine and sweat in humans.

PubMed

Sheng, Jianguo; Qiu, Wenhui; Xu, Bentuo; Xu, Hui; Tang, Chong

2016-06-01

The coastal areas of China face great challenges, owing to heavy metal contamination caused by rapid industrialization and urbanization. To our knowledge, this study is the first report of the levels of heavy metals in the major rivers of Zhenjiang, one of the most important cities of the Yangtze River Delta in China. In addition, we measured heavy metal levels in the blood of 76 residents of Zhenjiang. The results suggest that the presence of heavy metals in the blood may threaten human health and the distribution appeared to correspond to most highly populated areas and/or areas with high traffic. We also found that the concentration of heavy metals in human blood showed an accumulation effect with increase in age. Moreover, the levels of most heavy metals were lower in participants who regularly exercised than in those who did not. We studied heavy metal levels in the urine and sweat of another 17 volunteers to monitor the elimination of bioaccumulated heavy metal. Heavy metals were found in the urine and sweat of all the 17 participants and were more concentrated in sweat. Induced micturition and sweating appear to be potential methods for the elimination of heavy metals from the human body.

Heavy Metal Distribution in Street Dust from Traditional Markets and the Human Health Implications.

PubMed

Kim, Jin Ah; Park, Jin Hee; Hwang, Won Ju

2016-08-13

Street dust is a hazard for workers in traditional markets. Exposure time is longer than for other people, making them vulnerable to heavy metals in street dust. This study investigated heavy metal concentrations in street dust samples collected from different types of markets. It compared the results with heavy metal concentrations in heavy traffic and rural areas. Street dust was significantly enriched with most heavy metals in a heavy traffic area while street dust from a fish market was contaminated with cupper (Cu), lead (Pb) and zinc (Zn). Street dust from medicinal herb and fruit markets, and rural areas were not contaminated. Principal component and cluster analyses indicated heavy metals in heavy traffic road and fish market dust had different sources. Relatively high heavy metal concentration in street dust from the fish market may negatively affect worker's mental health, as depression levels were higher compared with workers in other markets. Therefore, intensive investigation of the relationship between heavy metal concentrations in street dust and worker's health in traditional marketplaces should be conducted to elucidate the effect of heavy metals on psychological health in humans.

Speciation Mapping of Environmental Samples Using XANES Imaging

EPA Science Inventory

Fast X-ray detectors with large solid angles and high dynamic ranges open the door to XANES imaging, in which millions of spectra are collected to image the speciation of metals at micrometre resolution, over areas up to several square centimetres. This paper explores how such mu...

Evaluating the potential of chelation therapy to prevent and treat gadolinium deposition from MRI contrast agents

DOE PAGES

Rees, Julian A.; Deblonde, Gauthier J. -P.; An, Dahlia D.; ...

2018-03-13

Several MRI contrast agent clinical formulations are now known to leave deposits of the heavy metal gadolinium in the brain, bones, and other organs of patients. This persistent biological accumulation of gadolinium has been recently recognized as a deleterious outcome in patients administered Gd-based contrast agents (GBCAs) for MRI, prompting the European Medicines Agency to recommend discontinuing the use of over half of the GBCAs currently approved for clinical applications. Here, to address this problem, we find that the orally-available metal decorporation agent 3,4,3-LI(1,2-HOPO) demonstrates superior efficacy at chelating and removing Gd from the body compared to diethylenetriaminepentaacetic acid, amore » ligand commonly used in the United States in the GBCA Gadopentetate (Magnevist). Using the radiotracer 153Gd to obtain precise biodistribution data, the results herein, supported by speciation simulations, suggest that the prophylactic or post-hoc therapeutic use of 3,4,3-LI(1,2-HOPO) may provide a means to mitigate Gd retention in patients requiring contrast-enhanced MRI.« less

Evaluating the potential of chelation therapy to prevent and treat gadolinium deposition from MRI contrast agents

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

Rees, Julian A.; Deblonde, Gauthier J. -P.; An, Dahlia D.

Several MRI contrast agent clinical formulations are now known to leave deposits of the heavy metal gadolinium in the brain, bones, and other organs of patients. This persistent biological accumulation of gadolinium has been recently recognized as a deleterious outcome in patients administered Gd-based contrast agents (GBCAs) for MRI, prompting the European Medicines Agency to recommend discontinuing the use of over half of the GBCAs currently approved for clinical applications. Here, to address this problem, we find that the orally-available metal decorporation agent 3,4,3-LI(1,2-HOPO) demonstrates superior efficacy at chelating and removing Gd from the body compared to diethylenetriaminepentaacetic acid, amore » ligand commonly used in the United States in the GBCA Gadopentetate (Magnevist). Using the radiotracer 153Gd to obtain precise biodistribution data, the results herein, supported by speciation simulations, suggest that the prophylactic or post-hoc therapeutic use of 3,4,3-LI(1,2-HOPO) may provide a means to mitigate Gd retention in patients requiring contrast-enhanced MRI.« less

SWASV speciation of Cd, Pb and Cu for the determination of seawater contamination in the area of the Nicole shipwreck (Ancona coast, Central Adriatic Sea).

PubMed

Annibaldi, Anna; Illuminati, Silvia; Truzzi, Cristina; Scarponi, Giuseppe

2011-12-01

The study reports for the first time on the heavy metal contamination of the waters surrounding a shipwreck lying on the sea floor. Square wave anodic stripping voltammetry has been used for a survey of the total and dissolved Cd, Pb and Cu contents of the seawater at the site of the sinking of the Nicole M/V (Coastal Adriatic Sea, Italy). Results show that the hulk has a considerable impact as regards all three metals in the bottom water, especially for the particulate fraction concentrations, which increased by factors of ≈ 9 (Cd), ≈ 3 (Pb) and ≈ 5 (Cu). The contaminated plume extended downstream for about 2 miles. Much lower contamination was observed for dissolved bottom concentrations; nevertheless Pb (0.56 ± 0.03 nmol/L) is higher than the Italian legal limits established for 2015 and Cd (0.23 ± 0.03 nmol/L) is very close the limit of Cd will be exceeded if the hulk is not removed. Copyright © 2011. Published by Elsevier Ltd.

Response of rhizosphere microbial community structure and diversity to heavy metal co-pollution in arable soil.

PubMed

Deng, Linjing; Zeng, Guangming; Fan, Changzheng; Lu, Lunhui; Chen, Xunfeng; Chen, Ming; Wu, Haipeng; He, Xiaoxiao; He, Yan

2015-10-01

Due to the emerging environmental issues related to heavy metals, concern about the soil quality of farming lands near manufacturing district is increasing. Investigating the function of soil microorganisms exposed to long-term heavy metal contamination is meaningful and important for agricultural soil utilization. This article studied the potential influence of several heavy metals on microbial biomass, activity, abundance, and community composition in arable soil near industrial estate in Zhuzhou, Hunan province, China. The results showed that soil organic contents (SOC) were significantly positive correlated with heavy metals, whereas dehydrogenase activity (DHA) was greatly depressed by the heavy metal stress. Negative correlation was found between heavy metals and basal soil respiration (BSR), and no correlation was found between heavy metals and microbial biomass content (MBC). The quantitative PCR (QPCR) and polymerase chain reaction-denaturing gradient gel electrophoresis (PCR-DGGE) analysis could suggest that heavy metal pollution has significantly decreased abundance of bacteria and fungi and also changed their community structure. The results could contribute to evaluate heavy metal pollution level in soil. By combining different environmental parameters, it would promote the better understanding of heavy metal effect on the size, structure, and activity of microbial community in arable soil.

Chemical Speciation and Metallomics.

PubMed

de Jesus, Jemmyson Romário; da Costa, Luana Ferreira; Lehmann, Eraldo Luiz; Galazzi, Rodrigo Moretto; Madrid, Katherine Chacón; Arruda, Marco Aurélio Zezzi

2018-01-01

Chemical speciation approaches is an inherent part of metallomics, once metals/metalloids and organic structures need to be currently evaluated for attaining metallomics studies. Then, this chapter focuses on the applications of the chemical speciation applied to the human health risk, food and human diet, drugs, forensic, nanoscience, and geological metallomics, also pointing out the advances in such area. Some aspects regarding sample preparation is commented along this chapter, and some strategies for maintaining the integrity of the metallomics information are also emphasized.

The phosphorus speciations in the sediments up- and down-stream of cascade dams along the middle Lancang River.

PubMed

Liu, Qi; Liu, Shiliang; Zhao, Haidi; Deng, Li; Wang, Cong; Zhao, Qinghe; Dong, Shikui

2015-02-01

We detected the longitudinal variability of phosphorus speciations and its relation to metals and grain size distribution of sediments in three cascade canyon reservoirs (Xiaowan, Manwan and Dachaoshan) along Lancang River, China. Five phosphorus speciations including loosely bound P (ex-P), reductant soluble P (BD-P), metal oxide-bound P (NaOH-P) calcium-bound P (HCl-P) and residual-P were extracted and quantified. Results showed that in Manwan Reservoir HCl-P accounted for the largest part of total phosphorus (TP) (49.69%), while in Xiaowan and Dachaoshan reservoirs, NaOH-P was the most abundant speciation which accounted for 57.21% and 55.19% of total phosphorus respectively. Higher contents of bio-available phosphorus in Xiaowan and Dachaoshan reservoirs suggested a high rate of P releasing from sediments. Results also showed ex-P and HCl-P had positive correlation with Ca. Total phosphorus was positively correlated with Fe. The silt/clay contents of the sediments had close relationship with ex-P (r=0.413, p<0.05), NaOH-P (r=0.428, p<0.05) and BAP (r=0.458, p<0.05). The concentration of Ca, Mn and silt/clay speciation in the sediments explained 40%, 10% and 4% of the spatial variation of phosphorus speciations, respectively. Copyright © 2014 Elsevier Ltd. All rights reserved.

Effects of natural factors on the spatial distribution of heavy metals in soils surrounding mining regions.

PubMed

Ding, Qian; Cheng, Gong; Wang, Yong; Zhuang, Dafang

2017-02-01

Various studies have shown that soils surrounding mining areas are seriously polluted with heavy metals. Determining the effects of natural factors on spatial distribution of heavy metals is important for determining the distribution characteristics of heavy metals in soils. In this study, an 8km buffer zone surrounding a typical non-ferrous metal mine in Suxian District of Hunan Province, China, was selected as the study area, and statistical, spatial autocorrelation and spatial interpolation analyses were used to obtain descriptive statistics and spatial autocorrelation characteristics of As, Pb, Cu, and Zn in soil. Additionally, the distributions of soil heavy metals under the influences of natural factors, including terrain (elevation and slope), wind direction and distance from a river, were determined. Layout of sampling sites, spatial changes of heavy metal contents at high elevations and concentration differences between upwind and downwind directions were then evaluated. The following results were obtained: (1) At low elevations, heavy metal concentrations decreased slightly, then increased considerably with increasing elevation. At high elevations, heavy metal concentrations first decreased, then increased, then decreased with increasing elevation. As the slope increased, heavy metal contents increased then decreased. (2) Heavy metal contents changed consistently in the upwind and downwind directions. Heavy metal contents were highest in 1km buffer zone and decreased with increasing distance from the mining area. The largest decrease in heavy metal concentrations was in 2km buffer zone. Perennial wind promotes the transport of heavy metals in downwind direction. (3) The spatial extent of the influence of the river on Pb, Zn and Cu in the soil was 800m. (4) The influence of the terrain on the heavy metal concentrations was greater than that of the wind. These results provide a scientific basis for preventing and mitigating heavy metal soil pollution in areas surrounding mines. Copyright © 2016 Elsevier B.V. All rights reserved.

Identification of the typical metal particles among haze, fog, and clear episodes in the Beijing atmosphere.

PubMed

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.

Ecotoxic heavy metals transformation by bacteria and fungi in aquatic ecosystem.

PubMed

Chaturvedi, Amiy Dutt; Pal, Dharm; Penta, Santhosh; Kumar, Awanish

2015-10-01

Water is the most important and vital molecule of our planet and covers 75% of earth surface. But it is getting polluted due to high industrial growth. The heavy metals produced by industrial activities are recurrently added to it and considered as dangerous pollutants. Increasing concentration of toxic heavy metals (Pb(2+), Cd(2+), Hg(2+), Ni(2+)) in water is a severe threat for human. Heavy metal contaminated water is highly carcinogenic and poisonous at even relatively low concentrations. When they discharged in water bodies, they dissolve in the water and are distributed in the food chain. Bacteria and fungi are efficient microbes that frequently transform heavy metals and remove toxicity. The application of bacteria and fungi may offer cost benefit in water treatment plants for heavy metal transformation and directly related to public health and environmental safety issues. The heavy metals transformation rate in water is also dependent on the enzymatic capability of microorganisms. By transforming toxic heavy metals microbes sustain aquatic and terrestrial life. Therefore the application of microbiological biomass for heavy metal transformation and removal from aquatic ecosystem is highly significant and striking. This paper reviews the microbial transformation of heavy metal, microbe metal interaction and different approaches for microbial heavy metal remediation from water bodies.

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.

[Analysis of heavy-metal-mediated disease and development of a novel remediation system based on fieldwork and experimental research].

PubMed

Yajima, Ichiro; Zou, Cunchao; Li, Xiang; Nakano, Chizuru; Omata, Yasuhiro; Kumasaka, Mayuko Y

2015-01-01

Heavy-metal pollution occurs in various environments, including water, air and soil, and has serious effects on human health. Since heavy-metal pollution in drinking water causes various diseases including skin cancer, it has become a global problem worldwide. However, there is limited information on the mechanism of development of heavy-metal-mediated disease. We performed both fieldwork and experimental studies to elucidate the levels of heavy-metal pollution and mechanisms of development of heavy-metal-related disease and to develop a novel remediation system. Our fieldwork in Bangladesh, Vietnam and Malaysia demonstrated that drinking well water in these countries was polluted with high concentrations of several heavy metals including arsenic, barium, iron and manganese. Our experimental studies based on the data from our fieldwork demonstrated that these heavy metals caused skin cancer and hearing loss. Further experimental studies resulted in the development of a novel remediation system with which toxic heavy metals were absorbed from polluted drinking water. Implementation of both fieldwork and experimental studies is important for prediction, prevention and therapy of heavy-metal-mediated diseases.

[Investigation and analysis of heavy metal pollution related to soil-Panax notoginseng system].

PubMed

Chen, Lu; Mi, Yan-Hua; Lin, Xin; Liu, Da-Hui; Zeng, Min; Chen, Xiao-Yan

2014-07-01

In this study, five heavy metals contamination of soil and different parts of Panax notoginseng in the plantation area was investigated. Analysis of heavy metals correlation between the planting soil and P. notoginseng; and the absorption and accumulation characteristics and translocation of soil heavy metals by P. notoginseng plants was revealed. Through field investigation and laboratory analytical methods, analysis of China's 30 different soil P. notoginseng origin and content of heavy metals in five different parts of the P. notoginseng plant content of heavy metals. The results revealed that the soil heavy metals should not be neglected in the plantation area Referring to the national soil quality standards (GB15608-1995), the excessive degree of soil heavy metals pollution showed Hg > As > Cd > Cr in the plantation area, and Pb content of soil was in the scope of the standard. Refer to 'Green Industry Standards for Import and Export of Medical Plants and Preparations', the excessive degree of heavy metals content of P. notoginseng plants showed As > Pb > Cr > Cd, and Hg content of plants was in the scope of the standard. Concentrations of five heavy metals of underground parts of P. notoginseng plants are higher than aboveground, and heavy metals elements are more concentrated in the root, followed by the rhizome of P. notoginseng plants. Heavy metal accumulation characteristics of the different parts of the P. notoginseng of the overall performance is the root > the rhizome > the root tuber > leaves > stems. From the point of view BCF value analysis of various parts of the P. notoginseng plants to absorb heavy metals in soil, BCF values of all samples were less than 1, description P. notoginseng not belong Hyperaccumulator. From the view of transportation and related analysis of the soil-P. notoginseng systems, the rhizome of P. notoginseng and the content of As and Cr in soil was significantly correlated, the root of P. notoginseng and the content of Cd in soil was significantly correlated, and no significant correlation between the other indicators. Through the analysis of transportation transfer coefficient showed: Pb, As and Cr are not easy to transport aboveground part from the underground, but Cd and Hg are relatively easy to transport stems from rhizome, the migration of five heavy metals in the aerial part is relatively strong, and heavy metal of stems is easily transported to the leaves. P. notoginseng does not belong to the enrichment of heavy metals in crops, especially for Hg in soil with strong patience. In survey area, the content of heavy metals of P. notoginseng's planting soil is relatively high, and the heavy metals As, Pb, Cr, Cd of P. notoginseng also exist heavy metals exceeded problems. Due to the presence of heavy metals in crops internal absorption and translocation of special laws, accumulation of heavy metals varied significantly in different parts of P. notoginseng. The overall, the performance for the heavy metal content of the underground parts is more than aboveground, it explain heavy metals of P. notoginseng plants is still the main source of the soiL Therefore, the key to control of planting area soil environmental quality and reduce exogenous harmful substances secondary pollution of soil in the cultivation process are to study and solve the heavy metals pollution problem of P. notoginseng.

Heavy Metal Distribution in Street Dust from Traditional Markets and the Human Health Implications

PubMed Central

Kim, Jin Ah; Park, Jin Hee; Hwang, Won Ju

2016-01-01

Street dust is a hazard for workers in traditional markets. Exposure time is longer than for other people, making them vulnerable to heavy metals in street dust. This study investigated heavy metal concentrations in street dust samples collected from different types of markets. It compared the results with heavy metal concentrations in heavy traffic and rural areas. Street dust was significantly enriched with most heavy metals in a heavy traffic area while street dust from a fish market was contaminated with cupper (Cu), lead (Pb) and zinc (Zn). Street dust from medicinal herb and fruit markets, and rural areas were not contaminated. Principal component and cluster analyses indicated heavy metals in heavy traffic road and fish market dust had different sources. Relatively high heavy metal concentration in street dust from the fish market may negatively affect worker’s mental health, as depression levels were higher compared with workers in other markets. Therefore, intensive investigation of the relationship between heavy metal concentrations in street dust and worker’s health in traditional marketplaces should be conducted to elucidate the effect of heavy metals on psychological health in humans. PMID:27529268

Heavy metals in drinking water: Occurrences, implications, and future needs in developing countries.

PubMed

Chowdhury, Shakhawat; Mazumder, M A Jafar; Al-Attas, Omar; Husain, Tahir

2016-11-01

Heavy metals in drinking water pose a threat to human health. Populations are exposed to heavy metals primarily through water consumption, but few heavy metals can bioaccumulate in the human body (e.g., in lipids and the gastrointestinal system) and may induce cancer and other risks. To date, few thousand publications have reported various aspects of heavy metals in drinking water, including the types and quantities of metals in drinking water, their sources, factors affecting their concentrations at exposure points, human exposure, potential risks, and their removal from drinking water. Many developing countries are faced with the challenge of reducing human exposure to heavy metals, mainly due to their limited economic capacities to use advanced technologies for heavy metal removal. This paper aims to review the state of research on heavy metals in drinking water in developing countries; understand their types and variability, sources, exposure, possible health effects, and removal; and analyze the factors contributing to heavy metals in drinking water. This study identifies the current challenges in developing countries, and future research needs to reduce the levels of heavy metals in drinking water. Copyright © 2016 Elsevier B.V. All rights reserved.

Bioassessment of heavy metal toxicity and enhancement of heavy metal removal by sulfate-reducing bacteria in the presence of zero valent iron.

PubMed

Guo, Jing; Kang, Yong; Feng, Ying

2017-12-01

A simple and valid toxicity evaluation of Zn 2+ , Mn 2+ and Cr 6+ on sulfate-reducing bacteria (SRB) and heavy metal removal were investigated using the SRB system and SRB+Fe 0 system. The heavy metal toxicity coefficient (β) and the heavy metal concentration resulting in 50% inhibition of sulfate reduction (I) from a modeling process were proposed to evaluate the heavy metal toxicity and nonlinear regression was applied to search for evaluation indices β and I. The heavy metal toxicity order was Cr 6+  > Mn 2+  > Zn 2+ . Compared with the SRB system, the SRB+Fe 0 system exhibited a better capability for sulfate reduction and heavy metal removal. The heavy metal removal was above 99% in the SRB+Fe 0 system, except for Mn 2+ . The energy-dispersive spectroscopy (EDS) analysis showed that the precipitates were removed primarily as sulfide for Zn 2+ and hydroxide for Mn 2+ and Cr 6+ .The method of evaluating the heavy metal toxicity on SRB was of great significance to understand the fundamentals of the heavy metal toxicity and inhibition effects on the microorganism and regulate the process of microbial sulfate reduction. Copyright © 2017 Elsevier Ltd. All rights reserved.

Leaf responsiveness of Populus tremula and Salix viminalis to soil contaminated with heavy metals and acidic rainwater.

PubMed

Hermle, Sandra; Vollenweider, Pierre; Günthardt-Goerg, Madeleine S; McQuattie, Carolyn J; Matyssek, Rainer

2007-11-01

Fast-growing trees such as Salix viminalis L. and Populus tremula L. are well suited to phytoremediate heavy metal contaminated soils. However, information on tree performance, particularly leaf function, under conditions of heavy metal contamination is scarce. We used yearly coppiced saplings of S. viminalis and P. tremula growing in model ecosytems to test four hypotheses: (1) heavy metal contamination impairs photosynthesis by injuring leaf structure; (2) the effects of heavy metal contamination are enhanced by acidified rainwater and low soil pH; (3) heavy metal contamination increases dark respiration and, thus, repair processes; and (4) heavy metal contamination is tolerated and remediated better by S. viminalis than by P. tremula. We investigated heavy metal accumulation, tissue injury and gas exchange in leaves of plants subjected to controlled soil contamination with heavy metal dust. Additional treatments included acidic and calcareous natural forest subsoils in combination with irrigation with rainwater at pH 5.5 or 3.5. In both provenances of P. tremula that were studied, but not in S. viminalis, heavy metal treatment reduced photosynthesis and transpiration by varying amounts, except in the hot and dry summer of 2003, but had no effect on dark respiration. At light saturation, net CO(2) uptake and water-use efficiency were reduced by heavy metal contamination, whereas the CO(2) concentration in the leaf intercellular air space was increased. Rainwater pH and subsoil pH only slightly modified the effects of the heavy metal treatment on P. tremula. Gas exchange responses of P. tremula to heavy metals were attributed to leaf structural and ultrastructural changes resulting from hypersensitive-response-like processes and accelerated mesophyll cell senescence and necroses in the lower epidermis, especially along the transport pathways of heavy metals in the leaf lamina. Overall, the effects of heavy metals on P. tremula corroborated Hypothesis 1, but refuted Hypotheses 2 and 3, and were inconclusive for Hypothesis 4. Both P. tremula and S. viminalis showed appreciable potential for storing heavy metals in aging foliage.

Determination of heavy metals in the ambient atmosphere.

PubMed

Suvarapu, Lakshmi Narayana; Baek, Sung-Ok

2017-01-01

Heavy metal determination in ambient air is an important task for environmental researchers because of their toxicity to human beings. Some heavy metals (hexavalent chromium (Cr), arsenic (As), cadmium (Cd) and nickel (Ni)) have been listed as carcinogens. Furthermore, heavy metals in the atmosphere can accumulate in various plants and animals and enter humans through the food chain. This article reviews the determination of heavy metals in the atmosphere in different areas of the world since 2006. The results showed that most researchers concentrated on toxic metals, such as Cr, Cd, Ni, As and lead. A few studies used plant materials as bio-monitors for the atmospheric levels of heavy metals. Some researchers found higher concentrations of heavy metals surrounding industrial areas compared with residential and/or commercial areas. Most studies reported the major sources of the particulate matter and heavy metals in the atmosphere to be industrial emissions, vehicular emissions and secondary aerosols.

A novel heavy metal ATPase peptide from Prosopis juliflora is involved in metal uptake in yeast and tobacco.

PubMed

Keeran, Nisha S; Ganesan, G; Parida, Ajay K

2017-04-01

Heavy metal pollution of agricultural soils is one of the most severe ecological problems in the world. Prosopis juliflora, a phreatophytic tree species, grows well in heavy metal laden industrial sites and is known to accumulate heavy metals. Heavy Metal ATPases (HMAs) are ATP driven heavy metal pumps that translocate heavy metals across biological membranes thus helping the plant in heavy metal tolerance and phytoremediation. In the present study we have isolated and characterized a novel 28.9 kDa heavy metal ATPase peptide (PjHMT) from P. juliflora which shows high similarity to the C-terminal region of P 1B ATPase HMA1. It also shows the absence of the invariant signature sequence DKTGT, and the metal binding CPX motif but the presence of conserved regions like MVGEGINDAPAL (ATP binding consensus sequence), HEGGTLLVCLNS (metal binding domain) and MLTGD, GEGIND and HEGG motifs which play important roles in metal transport or ATP binding. PjHMT, was found to be upregulated under cadmium and zinc stress. Heterologous expression of PjHMT in yeast showed a higher accumulation and tolerance of heavy metals in yeast. Further, transgenic tobacco plants constitutively expressing PjHMT also showed increased accumulation and tolerance to cadmium. Thus, this study suggests that the transport peptide from P. juliflora may have an important role in Cd uptake and thus in phytoremediation.

Thermodynamics of binding interactions between extracellular polymeric substances and heavy metals by isothermal titration microcalorimetry.

PubMed

Yan, Peng; Xia, Jia-Shuai; Chen, You-Peng; Liu, Zhi-Ping; Guo, Jin-Song; Shen, Yu; Zhang, Cheng-Cheng; Wang, Jing

2017-05-01

Extracellular polymeric substances (EPS) play a crucial role in heavy metal bio-adsorption using activated sludge, but the interaction mechanism between heavy metals and EPS remains unclear. Isothermal titration calorimetry was employed to illuminate the mechanism in this study. The results indicate that binding between heavy metals and EPS is spontaneous and driven mainly by enthalpy change. Extracellular proteins in EPS are major participants in the binding process. Environmental conditions have significant impact on the adsorption performance. Divalent and trivalent cations severely impeded the binding of heavy metal ions to EPS. Electrostatic interaction mainly attributed to competition between divalent cations and heavy metal ions; trivalent cations directly competed with heavy metal ions for EPS binding sites. Trivalent cations were more competitive than divalent cations for heavy metal ion binding because they formed complexing bonds. This study facilitates a better understanding about the interaction between heavy metals and EPS in wastewater treatment. Copyright © 2017 Elsevier Ltd. All rights reserved.

Effect of hydrothermal carbonization on migration and environmental risk of heavy metals in sewage sludge during pyrolysis.

PubMed

Liu, Tingting; Liu, Zhengang; Zheng, Qingfu; Lang, Qianqian; Xia, Yu; Peng, Nana; Gai, Chao

2018-01-01

The heavy metals distribution during hydrothermal carbonization (HTC) of sewage sludge, and pyrolysis of the resultant hydrochar was investigated and compared with raw sludge pyrolysis. The results showed that HTC reduced exchangeable/acid-soluble and reducible fraction of heavy metals and lowered the potential risk of heavy metals in sewage sludge. The pyrolysis favored the transformation of extracted/mobile fraction of heavy metals to residual form especially at high temperature, immobilizing heavy metals in the chars. Compared to the chars from raw sludge pyrolysis, the chars derived from hydrochar pyrolysis was more alkaline and had lower risk and less leachable heavy metals, indicating that pyrolysis imposed more positive effect on immobilization of heavy metals for the hydrochar than for sewage sludge. The present study demonstrated that HTC is a promising pretreatment prior to pyrolysis from the perspective of immobilization of heavy metals in sewage sludge. Copyright © 2017 Elsevier Ltd. All rights reserved.

Mobility, bioavailability and speciation of potentially toxic metals in a sludges-polluted agricultural soil under remediation with poplar trees and native grasses

NASA Astrophysics Data System (ADS)

Adamo, Paola; Agrelli, Diana; Giandonato Caporale, Antonio; Fiorentino, Nunzio; Duri, Luigi; Fagnano, Massimo

2017-04-01

For the assessment of health and environmental risks deriving from the pollution of agricultural soils, it is critical the identification and the chemical characterization of the contaminants and of the polluted soil, because these characteristics influence the mobility and bioavailability of the contaminants and therefore their transfer from soil to other environmental compartments and to the food chain. In addition, these information are crucial to assess the effectiveness of remediation and management actions. Our study site is an agricultural area of 6 ha, currently under sequestration, located in the province of Naples (Campania Region), interested by past illegal dumping of industrial wastes, mainly tannery sludges. In the area, after an intense phase of soil characterization by geophysical and geochemical surveys, it is realizing an environmental remediation project with poplar trees and native grass species, also with the aim of analyzing the possible absorption and accumulation of contaminants in the vegetables. The soil sampling was carried out by taking punctual samples of soil according to a grid of 20 x 20 m, at three depths (0-20; 30-60; 70-90 cm). Furthermore, materials attributable to the buried sludges were sampled from pedological profiles opened in the field. All the samples were analyzed for the content of potentially toxic metals and of heavy hydrocarbons (C>12). On selected samples were determined the main chemical and physical characteristics, mobile and bioavailable fractions of the major metal contaminants and their distribution in the soil geochemical fractions, with water (solid/liquid partition coefficient), 1 M NH4NO3 and 0.05 M EDTA pH 7 extractions, and EU-BCR sequential fractionation. The data showed a significant, widespread and disorderly contamination by chromium, zinc and heavy hydrocarbons (up to values of: 4500 mg/kg for Cr, 1850 mg/kg for Zn 1250 mg/kg for hydrocarbons C>12). In certain sub-areas it has also been observed a punctual contamination by lead, copper, cadmium, and arsenic. Chromium was always found poorly mobile and bioavailable, unlike zinc, that was extracted in significant amounts in EDTA and NH4NO3 and was found mainly distributed among the HOAc-extractable and reducible fraction of the soil. Chromium, instead, was found principally associated with the oxidizable and to a lesser extent the reducible fractions of the soil, presumably bound to organic matter and iron oxides, as also highlighted by SEM-EDS analysis. Given the high chromium content of the soil and buried materials, on selected samples was also determined the content of Cr(VI) and assessed the oxidizing potential of the soil in respect to the Cr(III). Keywords: chromium, zinc, metal speciation, bioavailability, polluted site.

Application of SEC-ICP-MS for comparative analyses of metal-containing species in cancerous and healthy human thyroid samples.

PubMed

Boulyga, Sergei F; Loreti, Valeria; Bettmer, Jörg; Heumann, Klaus G

2004-09-01

Size exclusion chromatography (SEC) was coupled on-line to inductively coupled plasma mass spectrometry (ICP-MS) for speciation study of trace metals in cancerous thyroid tissues in comparison to healthy thyroids aimed to estimation of changes in metalloprotein speciation in pathological tissue. The study showed a presence of species binding Cu, Zn, Cd and Pb in healthy thyroid tissue with a good reproducibility of chromatographic results, whereas the same species could not be detected in cancerous tissues. Thus, remarkable differences with respect to metal-binding species were revealed between healthy and pathological thyroid samples, pointing out a completely different distribution of trace metals in cancerous tissues. The metal-binding species could not be identified in the frame of this work because of a lack of appropriate standards. Nevertheless, the results obtained confirm the suitability of SEC-ICP-MS for monitoring of changes in trace metal distribution in cancerous tissue and will help to better understand the role of metal-containing species in thyroid pathology.

A review of phytoremediation technology: heavy metals uptake by plants

NASA Astrophysics Data System (ADS)

Sumiahadi, A.; Acar, R.

2018-03-01

Heavy metal is one of the serious environmental pollutions for now days as impact of industrial development in several countries. Heavy metals give toxic effects on human health and cause several serious diseases. Several techniques have been using for removing heavy metal contaminants from the environmental but these techniques have limitations such as high cost, long time, logistical problems and mechanical complexity. Phytoremediation can be used as an alternative solution for heavy metal remediation process because of its advantages as a cost-effective, efficient, environment- and eco-friendly technology based on the use of metal-accumulating plants. According to previous studies, several plants have a high potential as heavy metals bioaccumulator and can be used for phytoremediation process of heavy metals.

Divergent biology of facultative heavy metal plants.

PubMed

Bothe, Hermann; Słomka, Aneta

2017-12-01

Among heavy metal plants (the metallophytes), facultative species can live both in soils contaminated by an excess of heavy metals and in non-affected sites. In contrast, obligate metallophytes are restricted to polluted areas. Metallophytes offer a fascinating biology, due to the fact that species have developed different strategies to cope with the adverse conditions of heavy metal soils. The literature distinguishes between hyperaccumulating, accumulating, tolerant and excluding metallophytes, but the borderline between these categories is blurred. Due to the fact that heavy metal soils are dry, nutrient limited and are not uniform but have a patchy distribution in many instances, drought-tolerant or low nutrient demanding species are often regarded as metallophytes in the literature. In only a few cases, the concentrations of heavy metals in soils are so toxic that only a few specifically adapted plants, the genuine metallophytes, can cope with these adverse soil conditions. Current molecular biological studies focus on the genetically amenable and hyperaccumulating Arabidopsis halleri and Noccaea (Thlaspi) caerulescens of the Brassicaceae. Armeria maritima ssp. halleri utilizes glands for the excretion of heavy metals and is, therefore, a heavy metal excluder. The two endemic zinc violets of Western Europe, Viola lutea ssp. calaminaria of the Aachen-Liège area and Viola lutea ssp. westfalica of the Pb-Cu-ditch of Blankenrode, Eastern Westphalia, as well as Viola tricolor ecotypes of Eastern Europe, keep their cells free of excess heavy metals by arbuscular mycorrhizal fungi which bind heavy metals. The Caryophyllaceae, Silene vulgaris f. humilis and Minuartia verna, apparently discard leaves when overloaded with heavy metals. All Central European metallophytes have close relatives that grow in areas outside of heavy metal soils, mainly in the Alps, and have, therefore, been considered as relicts of the glacial epoch in the past. However, the current literature favours the idea that hyperaccumulation of heavy metals serves plants as deterrent against attack by feeding animals (termed elemental defense hypothesis). The capability to hyperaccumulate heavy metals in A. halleri and N. caerulescens is achieved by duplications and alterations of the cis-regulatory properties of genes coding for heavy metal transporting/excreting proteins. Several metallophytes have developed ecotypes with a varying content of such heavy metal transporters as an adaption to the specific toxicity of a heavy metal site. Copyright © 2017 Elsevier GmbH. All rights reserved.

TRACE METAL TRANSFORMATION MECHANISMS DURING COAL COMBUSTION

EPA Science Inventory

The article reviews mechanisms governing the fate of trace metals during coal combustion and presents new theoretical results that interpret existing data. Emphasis is on predicting the size-segregated speciation of trace metals in pulverized-coal-fired power plant effluents. Thi...

Feasibility analysis of EDXRF method to detect heavy metal pollution in ecological environment

NASA Astrophysics Data System (ADS)

Hao, Zhixu; Qin, Xulei

2018-02-01

The change of heavy metal content in water environment, soil and plant can reflect the change of heavy metal pollution in ecological environment, and it is important to monitor the trend of heavy metal pollution in eco-environment by using water environment, soil and heavy metal content in plant. However, the content of heavy metals in nature is very low, the background elements of water environment, soil and plant samples are complex, and there are many interfering factors in the EDXRF system that will affect the spectral analysis results and reduce the detection accuracy. Through the contrastive analysis of several heavy metal elements detection methods, it is concluded that the EDXRF method is superior to other chemical methods in testing accuracy and method feasibility when the heavy metal pollution in soil is tested in ecological environment.

Chromium speciation, bioavailability, uptake, toxicity and detoxification in soil-plant system: A review.

PubMed

Shahid, Muhammad; Shamshad, Saliha; Rafiq, Marina; Khalid, Sana; Bibi, Irshad; Niazi, Nabeel Khan; Dumat, Camille; Rashid, Muhammad Imtiaz

2017-07-01

Chromium (Cr) is a potentially toxic heavy metal which does not have any essential metabolic function in plants. Various past and recent studies highlight the biogeochemistry of Cr in the soil-plant system. This review traces a plausible link among Cr speciation, bioavailability, phytouptake, phytotoxicity and detoxification based on available data, especially published from 2010 to 2016. Chromium occurs in different chemical forms (primarily as chromite (Cr(III)) and chromate (Cr(VI)) in soil which vary markedly in term of their biogeochemical behavior. Chromium behavior in soil, its soil-plant transfer and accumulation in different plant parts vary with its chemical form, plant type and soil physico-chemical properties. Soil microbial community plays a key role in governing Cr speciation and behavior in soil. Chromium does not have any specific transporter for its uptake by plants and it primarily enters the plants through specific and non-specific channels of essential ions. Chromium accumulates predominantly in plant root tissues with very limited translocation to shoots. Inside plants, Cr provokes numerous deleterious effects to several physiological, morphological, and biochemical processes. Chromium induces phytotoxicity by interfering plant growth, nutrient uptake and photosynthesis, inducing enhanced generation of reactive oxygen species, causing lipid peroxidation and altering the antioxidant activities. Plants tolerate Cr toxicity via various defense mechanisms such as complexation by organic ligands, compartmentation into the vacuole, and scavenging ROS via antioxidative enzymes. Consumption of Cr-contaminated-food can cause human health risks by inducing severe clinical conditions. Therefore, there is a dire need to monitor biogeochemical behavior of Cr in soil-plant system. Copyright © 2017 Elsevier Ltd. All rights reserved.

Effects of biochars derived from chicken manure and rape straw on speciation and phytoavailability of Cd to maize in artificially contaminated loess soil.

PubMed

Zhao, Baowei; Xu, Renzhi; Ma, Fengfeng; Li, Yewei; Wang, Lu

2016-12-15

While biochar can reduce the bioavailability of heavy metals in acidic soils and reduce their risk of entering the food chain, conditions for alkaline soils such as loess soils with high pH values, high carbonate content and low organic matter content remain unclear. Pot experiments were conducted to assess the effects of four rates (1%, 5%, 10%, and 15% w/w) of biochars prepared at 600 °C from chicken manure and rape straw (CBC and RBC) on soil properties, Cd speciation and phytoavailability, and plant growth in Cd contaminated (20 mg kg -1 ) light sierozem using maize (Zea mays L.) as an indicator plant. Biochar additions significantly (P < 0.05) increased soil pH values, cation exchange capacity (CEC) and soil organic matter (OM). The results showed that Cd speciation turned somewhat into stable state as biochar application increased. When CBC and RBC was applied at the rate of 15%, the content of acid-extractable Cd decreased only by 16.3% and 11.64%, respectively. The uptake of Cd by maize shoots scarcely decreased with CBC and RBC amendment at the rate of 1% and 5%, respectively. Although it seemed that additions of more than 5% CBC or RBC significantly (P < 0.05) reduced Cd contents in maize shoots, maize growth was largely inhibited due to the high value of soil pH. These results could provide different implications for immobilization remediation of loess soils (e.g., light sierozem) contaminated with Cd. Copyright © 2016 Elsevier Ltd. All rights reserved.

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

Microscale Investigations of Soil Heterogeneity: Impacts on Zinc Retention and Uptake in Zinc-Contaminated Soils

DOE PAGES

Rosenfeld, Carla E.; Chaney, Rufus L.; Tappero, Ryan V.; ...

2017-03-17

Here, metal contaminants in soils can persist for millennia, causing lasting negative impacts on local ecosystems. Long-term contaminant bioavailability is related to soil pH and to the strength and stability of solid-phase associations. We combined physical density separation with synchrotron-based microspectroscopy to reduce solid-phase complexity and to study Zn speciation in field-contaminated soils. We also investigated Zn uptake in two Zn-hyperaccumulating ecotypes of Noccaea caerulescens (Ganges and Prayon). Soils were either moderately contaminated (500–800 mg Zn kg –1 via contaminated biosolids application) or grossly enriched (26,000 mg Zn kg –1 via geogenic enrichment). Soils were separated using sodium polytungstate intomore » three fractions: light fraction (LF) (<1.6 g cm –3), medium fraction (MF) (1.6–2.8 g cm –3), and heavy fraction (HF) (>2.8 g cm –3). Approximately 45% of the total Zn was associated with MF in biosolids-contaminated soils. From these data, we infer redistribution to the MF after biosolids application because Zn in biosolids is principally associated with HF and LF. Our results suggest that increasing proportions of HF-associated Zn in soils may be related to greater relative Zn removal by Zn hyperaccumulating plants. Using density fractions enabled assessment of Zn speciation on a microscale despite incomplete fractionation. Analyzing both density fractions and whole soils revealed certain phases (e.g., ZnS, Zn coprecipitated with Fe oxides) that were not obvious in all analyses, indicating multiple views of the same soils enable a more complete understanding of Zn speciation.« less

An evaluation of technologies for the heavy metal remediation of dredged sediments.

PubMed

Mulligan, C N; Yong, R N; Gibbs, B F

2001-07-30

Sediments dewatering is frequently necessary after dredging to remediate and treat contaminants. Methods include draining of the water in lagoons with or without coagulants and flocculants, or using presses or centrifuges. Treatment methods are similar to those used for soil and include pretreatment, physical separation, thermal processes, biological decontamination, stabilization/solidification and washing. However, compared to soil treatment, few remediation techniques have been commercially used for sediments. In this paper, a review of the methods that have been used and an evaluation of developed and developing technologies is made. Sequential extraction technique can be a useful tool for determining metal speciation before and after washing. Solidification/stabilization techniques are successful but significant monitoring is required, since the solidification process can be reversible. In addition, the presence of organics can reduce treatment efficiency. Vitrification is applicable for sediments but expensive. Only if a useful glass product can be sold will this process be economically viable. Thermal processes are only applicable for removal of volatile metals, such as mercury and costs are high. Biological processes are under development and have the potential to be low cost. Since few low cost metal treatment processes for sediments are available, there exists significant demand for further development. Pretreatment may be one of the methods that can reduce costs by reducing the volumes of sediments that need to be treated.

Evaluating Heavy Metal Stress Levels in Rice Based on Remote Sensing Phenology.

PubMed

Liu, Tianjiao; Liu, Xiangnan; Liu, Meiling; Wu, Ling

2018-03-14

Heavy metal pollution of croplands is a major environmental problem worldwide. Methods for accurately and quickly monitoring heavy metal stress have important practical significance. Many studies have explored heavy metal stress in rice in relation to physiological function or physiological factors, but few studies have considered phenology, which can be sensitive to heavy metal stress. In this study, we used an integrated Normalized Difference Vegetation Index (NDVI) time-series image set to extract remote sensing phenology. A phenological indicator relatively sensitive to heavy metal stress was chosen from the obtained phenological periods and phenological parameters. The Dry Weight of Roots (WRT), which directly affected by heavy metal stress, was simulated by the World Food Study (WOFOST) model; then, a feature space based on the phenological indicator and WRT was established for monitoring heavy metal stress. The results indicated that the feature space can distinguish the heavy metal stress levels in rice, with accuracy greater than 95% for distinguishing the severe stress level. This finding provides scientific evidence for combining rice phenology and physiological characteristics in time and space, and the method is useful to monitor heavy metal stress in rice.

Noninvasive Evaluation of Heavy Metal Uptake and Storage in Micoralgae Using a Fluorescence Resonance Energy Transfer-Based Heavy Metal Biosensor1[C][W][OPEN

PubMed Central

Rajamani, Sathish; Torres, Moacir; Falcao, Vanessa; Ewalt Gray, Jaime; Coury, Daniel A.; Colepicolo, Pio; Sayre, Richard

2014-01-01

We have developed a fluorescence resonance energy transfer (FRET)-based heavy metal biosensor for the quantification of bioavailable free heavy metals in the cytoplasm of the microalga Chlamydomonas reinhardtii. The biosensor is composed of an end-to-end fusion of cyan fluorescent protein (CFP), chicken metallothionein II (MT-II), and yellow fluorescent protein (YFP). In vitro measurements of YFP/CFP fluorescence emission ratios indicated that the addition of metals to the purified biosensor enhanced FRET between CFP and YFP, consistent with heavy metal-induced folding of MT-II. A maximum YFP/CFP FRET ratio of 2.8 was observed in the presence of saturating concentrations of heavy metals. The sensitivity of the biosensor was greatest for Hg2+ followed by Cd2+ ≈ Pb2+ > Zn2+ > Cu2+. The heavy metal biosensor was unresponsive to metals that do not bind to MT-II (Na+ and Mg2+). When expressed in C. reinhardtii, we observed a differential metal-dependent response to saturating external concentrations (1.6 mm) of heavy metals (Pb2+ > Cd2+) that was unlike that observed for the isolated biosensor (in vitro). Significantly, analysis of metal uptake kinetics indicated that equilibration of the cytoplasm with externally applied heavy metals occurred within seconds. Our results also indicated that algae have substantial buffering capacity for free heavy metals in their cytosol, even at high external metal concentrations. PMID:24368336

Noninvasive evaluation of heavy metal uptake and storage in micoralgae using a fluorescence resonance energy transfer-based heavy metal biosensor.

PubMed

Rajamani, Sathish; Torres, Moacir; Falcao, Vanessa; Ewalt Gray, Jaime; Coury, Daniel A; Colepicolo, Pio; Sayre, Richard

2014-02-01

We have developed a fluorescence resonance energy transfer (FRET)-based heavy metal biosensor for the quantification of bioavailable free heavy metals in the cytoplasm of the microalga Chlamydomonas reinhardtii. The biosensor is composed of an end-to-end fusion of cyan fluorescent protein (CFP), chicken metallothionein II (MT-II), and yellow fluorescent protein (YFP). In vitro measurements of YFP/CFP fluorescence emission ratios indicated that the addition of metals to the purified biosensor enhanced FRET between CFP and YFP, consistent with heavy metal-induced folding of MT-II. A maximum YFP/CFP FRET ratio of 2.8 was observed in the presence of saturating concentrations of heavy metals. The sensitivity of the biosensor was greatest for Hg2+ followed by Cd2+≈Pb2+>Zn2+>Cu2+. The heavy metal biosensor was unresponsive to metals that do not bind to MT-II (Na+ and Mg2+). When expressed in C. reinhardtii, we observed a differential metal-dependent response to saturating external concentrations (1.6 mm) of heavy metals (Pb2+>Cd2+) that was unlike that observed for the isolated biosensor (in vitro). Significantly, analysis of metal uptake kinetics indicated that equilibration of the cytoplasm with externally applied heavy metals occurred within seconds. Our results also indicated that algae have substantial buffering capacity for free heavy metals in their cytosol, even at high external metal concentrations.

Can heavy metal pollution defend seed germination against heat stress? Effect of heavy metals (Cu(2+), Cd(2+) and Hg(2+)) on maize seed germination under high temperature.

PubMed

Deng, Benliang; Yang, Kejun; Zhang, Yifei; Li, Zuotong

2016-09-01

Heavy metal pollution, as well as greenhouse effect, has become a serious threat today. Both heavy metal and heat stresses can arrest seed germination. What response can be expected for seed germination under both stress conditions? Here, the effects of heavy metals (Cu(2+), Cd(2+) and Hg(2+)) on maize seed germination were investigated at 20 °C and 40 °C. Compared with 20 °C, heat stress induced thermodormancy. However, this thermodormancy could be significantly alleviated by the addition of a low concentration of heavy metals. Heavy metals, as well as heat stress induced H2O2 accumulation in germinating seeds. Interestingly, this low concentration of heavy metal that promoted seed germination could be partly blocked by DMTU (a specific ROS scavenger), irrespective of temperature. Accordingly, H2O2 addition reinforced this promoting effect on seed germination, which was induced by a low concentration of heavy metal. Furthermore, we found that the NADPH oxidase derived ROS was required for seed germination promoted by the heavy metals. Subsequently, treatment of seeds with fluridone (a specific inhibitor of ABA) or ABA significantly alleviated or aggravated thermodormancy, respectively. However, this alleviation or aggravation could be partly attenuated by a low concentration of heavy metals. In addition, germination that was inhibited by high concentrations of heavy metals was also partly reversed by fluridone. The obtained results support the idea that heavy metal-mediated ROS and hormone interaction can finally affect the thermodormancy release or not. Copyright © 2016 Elsevier Ltd. All rights reserved.

Toxicity of heavy metals and metal-containing nanoparticles on plants.

PubMed

Mustafa, Ghazala; Komatsu, Setsuko

2016-08-01

Plants are under the continual threat of changing climatic conditions that are associated with various types of abiotic stresses. In particular, heavy metal contamination is a major environmental concern that restricts plant growth. Plants absorb heavy metals along with essential elements from the soil and have evolved different strategies to cope with the accumulation of heavy metals. The use of proteomic techniques is an effective approach to investigate and identify the biological mechanisms and pathways affected by heavy metals and metal-containing nanoparticles. The present review focuses on recent advances and summarizes the results from proteomic studies aimed at understanding the response mechanisms of plants under heavy metal and metal-containing nanoparticle stress. Transport of heavy metal ions is regulated through the cell wall and plasma membrane and then sequestered in the vacuole. In addition, the role of different metal chelators involved in the detoxification and sequestration of heavy metals is critically reviewed, and changes in protein profiles of plants exposed to metal-containing nanoparticles are discussed in detail. Finally, strategies for gaining new insights into plant tolerance mechanisms to heavy metal and metal-containing nanoparticle stress are presented. This article is part of a Special Issue entitled: Plant Proteomics--a bridge between fundamental processes and crop production, edited by Dr. Hans-Peter Mock. Copyright © 2016 Elsevier B.V. All rights reserved.

A novel method for the sequential removal and separation of multiple heavy metals from wastewater.

PubMed

Fang, Li; Li, Liang; Qu, Zan; Xu, Haomiao; Xu, Jianfang; Yan, Naiqiang

2018-01-15

A novel method was developed and applied for the treatment of simulated wastewater containing multiple heavy metals. A sorbent of ZnS nanocrystals (NCs) was synthesized and showed extraordinary performance for the removal of Hg 2+ , Cu 2+ , Pb 2+ and Cd 2+ . The removal efficiencies of Hg 2+ , Cu 2+ , Pb 2+ and Cd 2+ were 99.9%, 99.9%, 90.8% and 66.3%, respectively. Meanwhile, it was determined that solubility product (K sp ) of heavy metal sulfides was closely related to adsorption selectivity of various heavy metals on the sorbent. The removal efficiency of Hg 2+ was higher than that of Cd 2+ , while the K sp of HgS was lower than that of CdS. It indicated that preferential adsorption of heavy metals occurred when the K sp of the heavy metal sulfide was lower. In addition, the differences in the K sp of heavy metal sulfides allowed for the exchange of heavy metals, indicating the potential application for the sequential removal and separation of heavy metals from wastewater. According to the cumulative adsorption experimental results, multiple heavy metals were sequentially adsorbed and separated from the simulated wastewater in the order of the K sp of their sulfides. This method holds the promise of sequentially removing and separating multiple heavy metals from wastewater. Copyright © 2017 Elsevier B.V. All rights reserved.

The mechanisms of heavy metal immobilization by cementitious material treatments and thermal treatments: A review.

PubMed

Guo, Bin; Liu, Bo; Yang, Jian; Zhang, Shengen

2017-05-15

Safe disposal of solid wastes containing heavy metals is a significant task for environment protection. Immobilization treatment is an effective technology to achieve this task. Cementitious material treatments and thermal treatments are two types of attractive immobilization treatments due to that the heavy metals could be encapsulated in their dense and durable wasteforms. This paper discusses the heavy metal immobilization mechanisms of these methods in detail. Physical encapsulation and chemical stabilization are two fundamental mechanisms that occur simultaneously during the immobilization processes. After immobilization treatments, the wasteforms build up a low permeable barrier for the contaminations. This reduces the exposed surface of wastes. Chemical stabilization occurs when the heavy metals transform into more stable and less soluble metal bearing phases. The heavy metal bearing phases in the wasteforms are also reviewed in this paper. If the heavy metals are incorporated into more stable and less soluble metal bearing phases, the potential hazards of heavy metals will be lower. Thus, converting heavy metals into more stable phases during immobilization processes should be a common way to enhance the immobilization effect of these immobilization methods. Copyright © 2017 Elsevier Ltd. All rights reserved.

Plant rhamnogalacturonan II complexation of heavy metal cations

DOEpatents

O`Neill, M.A.; Pellerin, P.J.M.; Warrenfeltz, D.; Vidal, S.; Darvill, A.G.; Albersheim, P.

1999-03-02

The present invention provides rhamnogalacturonan-II (RG-II) and relates to its ability to complex specific multivalent heavy metal cations. In the presence of boric acid, RG-II monomers form dimers that are cross-linked by a borate ester. The yield of such borate ester cross-linked dimers of RG-II is enhanced in the presence of specific heavy metal cations. The present invention further relates to the utility of RG-II in assays for the detection of specific heavy metal contamination; as a reagent useful in the removal of specific heavy metal cations contaminating foods and liquids, for example, fish, wines, etc.; as a pharmaceutical composition useful as an antidote in specific heavy metal cation poisoning; as a treatment for the detoxification of specific heavy metal cations from blood and/or tissues; and in a method of remediation of waters and soils contaminated with specific heavy metal cations. 15 figs.

Plant rhamnogalacturonan II complexation of heavy metal cations

DOEpatents

O'Neill, Malcolm A.; Pellerin, Patrice J. M.; Warrenfeltz, Dennis; Vidal, Stephane; Darvill, Alan G.; Albersheim, Peter

1999-01-01

The present invention provides rhamnogalacturonan-II (RG-II) and relates to its ability to complex specific multivalent heavy metal cations. In the presence of boric acid, RG-II monomers form dimers that are cross-linked by a borate ester. The yield of such borate ester cross-linked dimers of RG-II is enhanced in the presence of specific heavy metal cations. The present invention further relates to the utility of RG-II in assays for the detection of specific heavy metal contamination; as a reagent useful in the removal of specific heavy metal cations contaminating foods and liquids, for example, fish, wines, etc.; as a pharmaceutical composition useful as an antidote in specific heavy metal cation poisoning; as a treatment for the detoxification of specific heavy metal cations from blood and/or tissues; and in a method of remediation of waters and soils contaminated with specific heavy metal cations.

Bioremediation mechanisms of combined pollution of PAHs and heavy metals by bacteria and fungi: A mini review.

PubMed

Liu, Shao-Heng; Zeng, Guang-Ming; Niu, Qiu-Ya; Liu, Yang; Zhou, Lu; Jiang, Lu-Hua; Tan, Xiao-Fei; Xu, Piao; Zhang, Chen; Cheng, Min

2017-01-01

In recent years, knowledge in regard to bioremediation of combined pollution of polycyclic aromatic hydrocarbons (PAHs) and heavy metals by bacteria and fungi has been widely developed. This paper reviews the species of bacteria and fungi which can tackle with various types of PAHs and heavy metals entering into environment simultaneously or successively. Microbial activity, pollutants bioavailability and environmental factors (e.g. pH, temperature, low molecular weight organic acids and humic acids) can all affect the bioremediation of PAHs and heavy metals. Moreover, this paper summarizes the remediation mechanisms of PAHs and heavy metals by microbes via elucidating the interaction mechanisms of heavy metals with heavy metals, PAHs/PAHs metabolites with PAHs and PAHs with heavy metals. Based on the above reviews, this paper also discusses the potential research needs for this field. Copyright © 2016 Elsevier Ltd. All rights reserved.

COMPETITIVE INFLUENCE OF PHOSPHORUS AND CALCIUM ON PB IN-VITRO BIOAVAILABILITY

EPA Science Inventory

The bioavailability of a metal is heavily related to the speciation of the particular metal. Further, the complexity of examining metal bioavailability is compounded by the presence of competitive ions. Thus, equally contaminated soils with varying concentrations of competitive e...

sources and processes identification for Zn cycling in the Seine river, France

NASA Astrophysics Data System (ADS)

gelabert, A.; Jouvin, D.; Morin, G.; Louvat, P.; Guinoiseau, D.; Benedetti, M. F.

2011-12-01

Because the availability of global freshwater stocks is predicted to become a major problem in a near future, new directives on water policy have been established in Europe. As a result, an accurate determination of the ecological status of the Seine river watershed is required. However, important evaluation limitation still exist, partly because the metal cycling in this system is not fully understood with for instance half the Seine river Zn not having clearly identified sources. Recent developments in isotopic measurements for new stable isotopes (Zn, Cu) allow many progresses in understanding the dynamics of metals in natural systems. But this technique alone does not always provide a precise distinction between mixing of water sources and biochemical processes able to induce isotopic fractionation. Along with an isotopic approach, this study propose to use XAS (X-ray Absorption Spectroscopy) to determine precisely the speciation of Zn complexes, and thus to define the proportion of water mixing vs. processes for Zn transfer in the watershed. A geographical sampling transect has been performed downstream Paris. Significant isotopic signature variations have been observed, varying from δ66Zn = 0.04 ± 0.04 to 0.18 ± 0.04 in the particulate part, and from δ66Zn= -0.28 ± 0.04 to 0.08 ± 0.04 for the dissolved part. The XAS analysis performed on the same samples at the Zn K-edge confirmed this heterogeneity by showing different speciations with a major contribution of sulfides, iron oxides and organic ligands. Interestingly, the wastewater treatment plant in Achères constitutes an important location in the system by contributing to the enrichment of heavy Zn to the Seine River particulate material. This change in isotopic signature follows a change in Zn speciation with decrease in sulfides contribution after Achères. A second important location is the confluence between the Seine and a minor river (Epte river) with a significant decrease in the δ66Zn for the particulate part. However, no major changes in Zn speciation have been observed. The cause for this isotopic decrease remains unclear but could be either 1) the mobilization of unknown sources, especially in this area (for the sampling point after the convergence) where the river is connected to numerous small lakes, or 2) the presence of biogeochemical processes able to induce a Zn isotopic fractionation. For instance, microorganisms present in freshwaters are known to be able to fractionate Zn during sorption processes, and they do not necessarily induce a change in the first shells of the Zn complexes if the sorbed metal was previously complexed with organic ligands in the river (fulvic substances with carboxylic or phenolic functional groups for instance). Although additional studies on the Seine river need to be conducted in order to reach a more complete understanding of this watershed functioning, these important results demonstrate the value of combining both the XAS and isotopic approaches in order to understand the behaviour of metals in such complex environments.

In Situ Distribution And Speciation Of Toxic Copper, Nickel, And Zinc In Hydrated Roots Of Cowpea

EPA Science Inventory

The phytotoxicity of trace metals is of global concern due to contamination of the landscape by human activities. Using synchrotron-based X-ray fluorescence microscopy and X-ray absorption spectroscopy, the distribution and speciation of Cu, Ni, and Zn was examined in situ