Sorbed metals fractionation and risk assessment of release in river sediment and particulate matter

Fractionation of metals in natural sediment and suspended particulate matter (SPM) of Tadjan River is investigated. Competitive sorption, sorption capacities of sediment and SPM as well as fractionation of metal-loaded sediment and SPM are also examined. A risk assessment code (RAC) is applied to estimate the risk of heavy metals release into the environment during the sorption process. Results revealed that sediments and SPM containing more than 25 % of clay minerals and higher amounts of calcite have great capacity of metal sorption, particularly for Cu, Ni, and Mn. Assessing the risk of metals release prior to and following sorption tests indicates that RAC of metals would significantly increase from the level of no or low risk in natural sediment and SPM to high or very high risk after sorption. The Langmuir model reveals that the highest affinity for Cu, Mn, and Ni in sediment is the organic fraction. The classic isotherm models of Freundlich and Langmuir can fit the data from chemical extraction studies of adsorbed metals, indicating that although sorption was apparently a physical and chemical process in the river, isotherm models can be used to simulate the sorption and accumulation in different geochemical phases within the particulate matter.     

Heavy metal speciation in the composting process

Composting is one of the more efficient and environment friendly methods of solid waste disposal and has many advantages when compared with landfill disposal on which the UK and Ireland are currently heavily dependent. Composting is a very complicated process involving intensive microbial activity and the detailed mechanisms of the process have yet to be fully understood. Metal speciation information can provide an insight into the metal-microbial interaction and would help in the evaluation of the quality of compost. This would facilitate the exploitation of composts in remediation of heavy metal contaminated land. In this work a systematic approach to metal speciation in compost has been taken by applying the three-step method for operationally defined metal speciation of soils and sediments, developed by the European Commission's Standards, Measurement and Testing Programme to monitor the change in metal speciation with time (up to 106 days) for four different waste composting processes. The results have shown that in general metals become less available for the first extraction step as the composting process proceeds. This implies that composting tends to redistribute the metals from more labile forms to more fixed forms which may explain why the application of composts could be useful for with heavy metal contaminated land. There are exceptions to this trend and in some cases, certain metals appear to behave differently depending on the source of the compost.     

Remote in situ voltammetric techniques to characterize the biogeochemical cycling of trace metals in aquatic systems

The contamination of aquatic ecosystems by natural and anthropogenic metals has lead to a need to better characterize their impact in the environment. To a large extent, the fate and the (eco)toxicity of these elements in aquatic systems are related to their chemical speciation, which may vary continuously in space and time. Detailed measurements of the fraction of specific metal species or groups of homologous metal species and their variation as a function of the bio-physicochemical conditions of the natural media are thus of prime importance. To determine these metal fractions as well as redox chemical species regulating their distribution (dissolved oxygen, sulfides, iron and manganese oxides), new analytical tools capable of performing in situ, real-time monitoring in both water columns and sediments with minimum perturbation of the media are required. This paper reviews the challenges associated with metal speciation studies, and the progress made with state of the art voltammetric techniques to measure the speciation of metals in situ. More specifically, it summarizes the specific conceptual, analytical, and technical criteria that must be considered and/or fulfilled to develop rugged, field deployable, non-perturbing sensors and probes. Strategies used to satisfy these criteria are presented by describing the up-to-date most advanced voltammetric sensors, mini-/micro-integrated analytical systems, and submersible equipments developed for in situ measurements of trace metals and main redox species in aquatic systems. The spatial and temporal resolutions achieved by these news tools represent a significant advantage over traditional laboratory techniques, while simultaneously remaining cost effective. The application of these tools to aquatic systems is illustrated by several examples of unattended and remote in situ monitoring and/or profiling in water columns and sediments.     

植物内重金属的赋存形态及分布特征分析方法研究进展

植物内重金属分析不仅有助于阐述重金属迁移转化规律,揭示植物修复机理,也是监测评价大气、水及土壤环境重金属污染状况的重要依据。研究针对植物样品中重金属赋存形态及分布特征的分析方法进行综述,分别介绍了其原理、优缺点及应用。提出制定统一高效的分析检测方法,深化植物内重金属的赋存形态及分布特征与环境相关性的研究以及建立数据共享平台是植物样品重金属信息分析方法的未来发展方向。     

Sequential extractions of selenium soils from Stewart Lake: total selenium and speciation measurements with ICP-MS detection

Different techniques have been employed in order to evaluate the most efficient procedure for the extraction of selenium from soil as required for speciation. Selenium contaminated sediments from Stewart Lake Wetland, California were used. A strong acid mineralization of the samples gives quantitative total selenium, which is then used to estimate recoveries for the milder extraction methods. The different extraction methodologies involve the sequential use of water, buffer (phosphate, pH 7) and either acid solution (e.g. HNO3 or HCl) or basic solutions (e.g. ammonium acetate, NaOH or TMAH). Pyrophosphate extraction was also evaluated and showed that selenium was not associated with humic acids. The extractants were subsequently analyzed by size exclusion chromatography (SEC) with UV (254 and 400 nm) and on-line ICP-MS detection; anion exchange chromatography, and ion-pair reversed phase chromatography with ICP-MS detection. For sequential extractions the extraction efficiencies showed that the basic extractions were more efficient than the acidic. The difference between the acidic and the basic extraction efficiency is carried to the sulfite extraction, suggesting that whatever is not extracted by the acid is subsequently extracted by the sulfite. The species identified with the different chromatographies were selenate, selenite, elemental selenium and some organic selenium.     

Factor analysis and linear regression model (LRM) of metal speciation and physico-chemical characters of groundwater samples

An approach is described for viewing the interrelationship between different variables and also tracing the sources of pollution of groundwater of north Chennai (India). The data set of 43 variables which include major ions, minor ions and trace metal speciation (Cu, Pb, Cd and Zn) collected during the pre-monsoon and post-monsoon seasons of the year 2000–2001, was subjected to R-mode factor analysis to comprehend the distribution pattern of the said variables. It was found that first factor measures salinity and hardness which explained 19.12% of the total variance (comprised of variables EC, TDS, Na⁺, K⁺, Ca²⁺, Mg²⁺, total hardness, Cl⁻ and SO₄ ²⁻) during pre-monsoon, while it was 25.08% during post-monsoon. The second and third factors were attributed to speciation of zinc and copper ions during both pre-monsoon and post-monsoon. Although there were two more factors, loaded with speciation parameters of lead and cadmium, the variance of them were less than 10%. From this study it is seen that sea water intrusion, municipal solid waste disposal are the identified sources of component of pollution. The importance of metal ions is taking a secondary role and the anthropogenic origin-industrial activity, is the reason in the evaluation of pollution status as they come in the second, third, fourth and fifth factors. As the trace metal speciation was grouped in separate factors, linear regression model (LRM) with correlation analysis was applied to check its validity for prediction of speciation and to apply LRM for rapid monitoring of water pollution.     

Speciation of metals in bed sediments and water of Qaraaoun Reservoir, Lebanon

Determination of only total element in sediments does not give an accurate estimate of the likely environmental impacts. Speciation study of metals in sediment provides information on the potential availability of metals (toxic) to biota under various environmental conditions. In water, the toxic metal specie is the free hydrated metal ion. The toxicity of metals depends especially on their chemical forms rather than their total metal content. The present study focuses on Qaraaoun Reservoir, Lebanon. Earlier studies focused only on total metal concentrations in sediment and water. The objective of this study was to determine metal speciation (Fe, Cr, Ni, Zn, Cu, Pb, Cd) in the (operationally defined) sediment chemical fractions and metal speciation in reservoir water. This would reflect on metal bioavailability and toxicity. Water samples and bed sediments were collected from nine sites during the dry season and a sequential chemical fraction scheme was applied to the <75-??m sieve sediment fraction. Metal content in each fraction was determined by the FAAS technique. The data showed that the highest percentages of total metal content in sediment fractions were for: Fe in residual followed by reducible, Cr and Ni in residual and in reducible, Cu in organic followed by exchangeable, Zn in residual and in organic, Pb in organic and carbonate, Cd was mainly in carbonate. Total metal content in water was determined by ICP-MS technique and aqueous metal speciation was predicted using AQUACHEM software interfaced to PHREEQC geochemical computer model. The water speciation data predicted that a high percentage of Pb and Ni were present as carbonate complex species and low percentages as free hydrated ions, highest percentage of Zn as carbonate complex species followed by free hydrated ion, highest percentage of Cd as free hydrated ion followed by carbonate complex species. The sensitivity attempt of free hydrated ion of Ni, Zn, Pb, and Cd in reservoir water revealed dependence of Zn and Cd on pH and alkalinity, while Ni and Pb were only dependent on pH.     

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

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.     

Trace element speciation at cell membranes: aqueous, solid and lipid phase effects

Biological interest in trace element speciation has tended to be polarised in very different ways according to the concerns of the investigators. Much of the ecological interest has centred on the effects of metal ions in the external environment with the "free metal ion model" dominating discussions of potential toxicity. By way of contrast biochemists have been much more concerned with the stereochemical and kinetic aspects of specificity in metal protein interactions in the cytoplasm. Separating these two sets of interests are the membrane biophysicists whose studies have concentrated on the channel concept. All three groups have tended to ignore speciation onto the solid phase. In the overall biological context, trace element speciation in the cell is more concerned with kinetics and the evolution of specificity of interaction between diverse ligands than with the conditions for equilibrium.     

Scientific aspects of the framework convention on climate change and national greenhouse gas inventories

Though the principles of the Earth's greenhouse effect have been known for well over a century, it is only recently that advances in climate research have indicated that significant and possibly costly climate change, due to growing emissions of greenhouse gases and their precursors by human activity, is a real possibility. Current estimates of the global human-related emissions of carbon dioxide, methane and nitrous oxide are presented, though many sources remain poorly known or understood. The compilation of national greenhouse inventories as required by the United Nations Framework Convention on Climate Change is likely in the longer term to help improve such global estimates, as long as comparable methodologies are used. The development of the IPCC Guidelines for National Greenhouse Gas Inventories is described, emphasizing the strategies employed to gain wide international participation.     

The mismatch of bioaccumulated trace metals (Cu,Pb and Zn) in field and transplanted oysters (<Emphasis Type="Italic">Saccostrea glomerata</Emphasis>) to ambient surficial sediments and suspended particulate matter in a highly urbanised estuary (Sydney estuary,Australia)

A significant correlation between sedimentary metals, particularly the ‘bio-available’ fraction, and bioaccumulated metal concentrations in the native Sydney rock oyster (Saccostrea glomerata) tissues has been successfully demonstrated previously for Cu and Zn in a number of estuaries in New South Wales, Australia. However, this relationship has been difficult to establish in a highly modified estuary (Sydney estuary, Australia) where metal contamination is of greatest concern and where a significant relationship would be most useful for environmental monitoring. The use of the Sydney rock oyster as a biomonitoring tool for metal contamination was assessed in the present study by investigating relationships between metals attached to sediments and suspended particulate matter (SPM) to bioaccumulated concentrations in oyster tissues. Surficial sediments (both total and fine-fraction), SPM and wild oysters were collected over 3 years from three embayments (Chowder Bay, Mosman Bay and Iron Cove) with each embayment representing a different physiographic region of Sydney estuary. In addition, a transplant experiment of farmed oysters was conducted in the same embayments for 3 months. No relationship was observed between sediments or SPM metals (Cu, Pb and Zn) to tissue of wild oysters; however, significant relationship was observed against transplanted oysters. The mismatch between wild and farmed, transplanted oysters is perplexing and indicates that wild oysters are unsuitable to be used as a biomonitoring tool due to the involvement of unknown complex factors while transplanted oysters hold strong potential.     

Concentration and distribution characteristic of main toxic metals in suspended particle material in Nanjing reach, Changjiang River

Six stations in the lower reach region of Changjiang River within Baguazhou Island, Nanjing reach were chosen to investigate the toxic metals pollution characteristic in suspended particle material (SPM). SPM concentration, as well as reflectance spectroscopy characteristic, toxic metal concentrations, and lead isotopes of suspended particle material were studied. SPM concentrations were obtained from fluvial cross-sectional sampling near the surface (20 cm) and the study presents the cross-sectional averages. SPM concentrations varied around 170?C300 mg L^???1. Reflectance spectroscopy measurements differed from each other over each cross-section but no common pattern characterizing the cross-sectional behavior of the measurements was observed. The metal concentrations in the SPM decreased in the sequence: Mn > Zn > Cu > Cr > Pb > Cd. The result of lead isotopes analysis proved that lead isotopes composition in SPM are mainly produced by natural contributions and influenced by anthropogenic activity at the same time.     

Speciation of heavy metals in biosolids of wastewater treatment plants at Mysore,Karnataka, India

Urban wastewater treatment leads to the generation of large quantities of biosolids. Accumulation of biosolids is a problem of environmental relevance due to the existence of heavy metals in the biosolids. Determination of total metal in biosolid provides information relating pollution levels. Determination of their mobilization capacity and behaviour in the environment is an important task. An experimental approach commonly used for studying the mobility, transport and bioavailability of metal in biosolids is the use of selective sequential extraction procedure. In the present study an attempt has been made to study the heavy metal properties in biosolid samples collected from urban wastewater treatment plants located at Mysore, Karnataka. Few heavy metals selected for the present study are cadmium, chromium, copper, iron, nickel and zinc. The concentration of these metals in biosolids and their partition in different fractions are studied. The speciation of metals based on the sequential extraction scheme was carried out. The concentration of heavy metals is lower than that established by European legislation. The residual fraction has the maximum percentage of heavy metals whereas, only a small fraction of heavy metals (Fe, Zn and Cd) are extracted in the most soluble fractions, exchangeable and carbonate fractions.     

A case study of trace metals in suspended particulate matter and biota before wastewater treatment plant from the Izmir Bay,Turkey

The concentrations of trace metals (Cu, Zn, Mn, Ni, and Fe) from suspended particulate matter (SPM) and biota in Izmir Bay (Eastern Aegean Sea) were studied in order to evaluate the environmental impact of the anthropogenic metals before building of Wastewater Treatment Plant. SPM samples were collected in wet and dry periods from Izmir Bay. Metal concentrations in SPM (Cu, 0.36–2.19; Mn, 0.07–11.3; Ni, 0.43–7.81; Zn, 7.33–269; Fe, 1.00–266 μgdm^− 3) were comparable to those reported for other moderately polluted bays. Maximum metal concentrations in SPM were observed during summer season. SPM metal concentrations displayed a clear spatial trend with values increasing with proximity to urban centers. Cu and Zn concentrations in SPM were especially high in the inner bay. SPM were found to be contaminated by Zn. The vertical profile of Mn, Zn, and Ni concentrations in SPM had a maximal value at the upper layer and decreased to minimal value at the bottom layer of the inner bay in summer, in contrast to the observed pattern of Fe and Cu. Maximum Cu concentrations were obtained in Penaeus kerathurus. Also, maximum Zn and Fe concentrations were found in Mytilus galloprovincialis. Relatively high Cu levels were found in Sardina pilcardus and Mullus barbatus than other fish species. Besides, Cu levels were lower in Diplodus annularis and Merluccius merluccius. Finally, metal levels in biota tissues were lower than the limits of European Dietary Standards and Guidelines.     

Suspended particulate matter estimates using optical and acoustic sensors: application in Nestos River plume (Thracian Sea,North Aegean Sea)

The present study investigates the use of combined methods of optical and acoustic sensors, in collaboration with direct in situ measurements, for the calibration and validation of a model transforming acoustic backscatter intensity series into suspended particulate matter (SPM) concentration datasets. The model follows previously elaborated techniques, placing particular attention to the parameterization of the acoustic absorption index as a function of water physical properties. Results were obtained from the annual deployment (during 2007–2008) of an upward-facing acoustic Doppler current profiler (ADCP) (307 kHz), equipped with a Wave Array, and an optical backscatter sensor (OBS), at the bottom of Thassos Passage near Nestos River plume (Thracian Sea, Northern Greece). The OBS was calibrated through linear regression, using 2007 and 2012 field sampling data, exhibiting an error of 13–14 % due to chlorophyll presence. The ADCP signal was calibrated through simultaneous measurements of backscatter intensity and turbidity profiles. Harmonic analysis on the model-produced SPM concentrations explained the tidal influence on their variability, especially during the summer. Empirical orthogonal functions analysis revealed the impact of waves and wave-induced currents on SPM variability. Finally, Nestos River sediment load was found uncorrelated to the SPM change in Thassos Passage, due to the dispersal and sediment deposition near the river mouth.     

Copper fractionation with dissolved organic matter in natural waters and wastewater--a mixed micelle mediated methodology (cloud point extraction) employing flame atomic absorption spectrometry

A cloud point extraction-preconcentration methodology for the speciation analysis of free and organically complexed metal species in natural waters is presented. The method is based on the neutralization of the electrostatic charge of the humate-metal complexes with a positively charged surfactant in a high ionic strength solution environment. The resulting complexes are conveniently solubilized in the micelles of a non-ionic surfactant medium and are thus separated from the bulk aqueous phase. Free metal species are also determined by complexation with a conventional chelating agent under mild conditions. The overall procedure is easy, rapid and allows for a high sample throughput in terms of massive analysis of many samples in the same time period. The method offers substantially low detection limits of 8.5 and 0.9 micrograms l-1 for bound and labile species respectively, with a calibration curve rectilinear in the wide range 40-150 micrograms l-1 for the humate associated and 4-40 micrograms l-1 for the free metal species. The method is free from interferences yielding recoveries in the range 97-102% for various samples of different matrixes.     

Colloidal mercury (Hg) distribution in soil samples by sedimentation field-flow fractionation coupled to mercury cold vapour generation atomic absorption spectroscopy

Diverse analytical techniques are available to determine the particle size distribution of potentially toxic elements in matrices of environmental interest such as soil, sediments, freshwater and groundwater. However, a single technique is often not exhaustive enough to determine both particle size distribution and element concentration. In the present work, the investigation of mercury in soil samples collected from a polluted industrial site was performed by using a new analytical approach which makes use of sedimentation field-flow fractionation (SdFFF) coupled to cold vapour generation electrothermal atomic absorption spectroscopy (CV-ETAAS). The Hg concentration in the SdFFF fractions revealed a broad distribution from about 0.1 to 1 μm, roughly following the particle size distributions, presenting a maximum at about 400-700 nm in diameter. A correlation between the concentration of Hg in the colloidal fraction and organic matter (O.M.) content in the soil samples was also found. However, this correlation is less likely to be related to Hg sorption to soil O.M. but rather to the presence of colloidal mercuric sulfide particles whose size is probably controlled by the occurrence of dissolved O.M. The presence of O.M. could have prevented the aggregation of smaller particles, leading to an accumulation of mercuric sulfides in the colloidal fraction. In this respect, particle size distribution of soil samples can help to understand the role played by colloidal particles in mobilising mercury (also as insoluble compounds) and provide a significant contribution in determining the environmental impact of this toxic element.     

Reactivity, interactions and transport of trace elements, organic carbon and particulate material in a mountain range river system (Adour River, France)

The background levels, variability, partitioning and transport of eleven trace elements-Ag, Al, As, Cd, Co, Cr, Cu, Mn, Pb, Zn and U-were investigated in a mountain range river system (Adour River, France). This particular river system displayed a turbulent hydrodynamic regime, characterized by flash-transient discharge conditions leading to fast shifts in suspended particulate matter (SPM) concentrations as high as two orders of magnitude (12 to 600 mg l(-1)). The distribution of SPM was accurately predicted with a "hysteresis" transport model, indicating that about 75% of the annual solids load was exported within 20 to 40 days. Dissolved and particulate concentrations of most trace elements were low compared to their concentrations in other reference river systems expect for Pb and Cr, associated with historical anthropogenic activities. Although dissolved and particulate metal concentrations were steady for most elements during low and average discharge conditions, significant changes were observed with increasing river discharge. The changes in trace element concentrations in the two compartments was found to induce a partitioning anomaly referred to as the particulate concentration effect. This anomaly was significant for Cr, Mn, Pb, Zn, Cu and organic carbon (p < 0.03). The processes driving this anomaly were possibly linked to the modification and/or increase of colloidal organic and inorganic vectors, suggested by the significant increase of DOC (p < 0.001) and dissolved Al concentrations (p < 0.05) during flood conditions. A complementary process linked to the influence of coarse particles of low complexation capacity and transported mainly during high discharge may also effect trace element concentrations. Annual metal fluxes transported by this river system were estimated using the hysteresis SPM model with consideration of these fate processes. Metals in the Adour River system are primarily exported into the Bay of Biscay (Atlantic Ocean).     

Air quality assessment along Dhanbad - Jharia road

Road ambient air pollution status along Dhanbad – Jharia road isstudied and presented in this article. The selection of this areais made considering the importance of the road in Dhanbad district and the nature of activities taking place along the road, which reflect that the portion of road upto Dhansar can be considered as having commercial areas on both sides and that from Dhansar to Jharia as having industrial areas on both sides.For the assessment of the ambient air quality along the road monitoring is done at the following five locations: Indian Schoolof Mines (ISM), main gate; Bankmore; Dhansar police check post; Dhansar opencast project agent office and a residential house beside the Rajapur opencast project. The location of ISM, maingate is specially chosen as this represents a commercial shoppingcomplexes and the situation can be compared with that at Bankmore. Monitoring of ambient air quality is done following thestandard procedure prescribed in IS: 5182. In addition the concentration of lead, zinc, copper, iron, manganese, cadmium metals in SPM is also monitored. The ambient air quality is monitored in the months of September and November 1999, respectively, to represent monsoon and winter seasons. The SPM concentration observed at all the five locations in the winterseason is more than the permissible limits for commercial andindustrial areas. However, in the monsoon season, the SPM concentration is higher than the permissible limit at the twocommercial locations, i.e., ISM gate and Bankmore, while it isless than the prescribed limit for industrial areas at the remaining three locations. At the ISM gate and Bankmore the SPM generation is mainly by vehicular traffic while at other three locations it was in addition due to mining and other activities.     

Arsenic Speciation Analysis in Water Samples: A Review of The Hyphenated Techniques

Interests in the determination of different arsenic species in natural waters is caused by the fact that toxic effects of arsenic are connected with its chemical forms and oxidation states. In determinations of water samples inorganic arsenate (As(III), As(V)), methylated metabolities (MMAA, DMAA) and other organic forms such as AsB, AsC, arsenosugars or arsenic containing lipids have the most importance. This article provides information about occurrence of the dominant arsenic forms in various water environments. The main factors controlling arsenic speciation in water are described. The quantification of species is difficult because the concentrations of different forms in water samples are relatively lowcompared to the detection limits of the available analytical techniques. Several hyphenated methods used in arsenic speciation analysis are described. Specific advantages and disadvantages of methods can define their application for a particular sample analysis. Insufficient selectivity and sensitivity of arsenic speciation methods cause searching for a new or modifications already existing techniques. Some aspects of improvement and modifications of the methods are highlighted.