The effect of heavy metal speciation in sediment on bioavailability to tubificid worms

The bioavailability of heavy metals in sediment to freshwater tubificid worms was compared with measures of chemical extractability using a sequential extraction procedure. In order to provide a range of test sediments of different quality, various mineral phases were prepared, in which the metals were spiked by adsorption or coprecipitation and these were then mixed with a bulk base sediment in known proportions. Results indicated good correlation between worm metal burden and metal mobilised from the sediments in the first (exchangeable) sequential extraction step for Cd, Cu and Pb. Of the other metals tested, Zn levels in the worms were found to be constant, suggesting regulation, and Ni uptake was too small for accurate measurement. In general, metals spiked to the sediment directly, or adsorbed on the clay mineral phase were found to be much more available than those bound to sewage sludge, carbonate or hydrous ferric oxide phases.     

Assessment of Heavy Metal Contamination in the Sediments of the Shuangtaizi Estuary Using Multivariate Statistical Techniques

In order to assess heavy metal pollution of sediment samples collected from Shuangtaizi estuary, contamination factor (CF) and multivariate statistical analyses, including principal component analysis (PCA), cluster analysis (CA) and correlation analysis, are carried out in this paper. CF confirms that Pb, Cu and Hg concentrations are very low and all fall within the range of background, while Zn and Cd demonstrate moderate contamination (in A10, A13, A15, A16 and A17 sites) and very high contamination (in A10, A13, A15 and A17 sites), respectively. The PCA indicates that four significant principal components (PCs) are extracted, explaining 88.959% of total variance, which suggests that Pb, Cu and Zn are mainly associated with organic carbon (OC). The result from CA is consistent with that obtained from PCA, classifying that the heavy metals in two clusters derive from different sources. Correlation analysis supports the conclusions from PCA and CA, elucidating the relationships between heavy metals and particle sizes of the sediments.     

Effect of sample pretreatment upon the metal speciation in sediments by a sequential extraction procedure

Abstract

Sample pretreatment, such as drying, is sometimes necessary for the speciation analysis of trace metals in sediments. However, this pretreatment may exert some effects upon the speciation distribution. In this study, the heavy metals (Cu, Pb, Cr, Cd, Zn and Ni) in reservoir surface sediments were fractionated to water soluble, exchangeable and carbonate bound (B1), Fe-Mn oxide bound (B2), organic matter and sulfide bound (B3) by a three-stage sequential extraction procedure. The effect of different drying methods (oven-drying at 85^oC, air-drying at 20°C and freeze-drying) on metal speciation distribution was investigated. Compared to the fresh wet sample, none of the drying methods completely preserve the initial chemical speciation distribution of the elements. The B1 fraction was particularly sensitive to sample pretreatment methods. Among the elements, zinc was especially perturbed by air-drying, care must be exercised because air-drying was commonly used in sediment pretreatment.     

Sludge-Derived Cu and Zn in a Humic-Gley Soil: Effect of Dissolved Metal-Organic Matter Complexes on Sorption and Partitioning

A sequential extraction scheme was combined with sorption isotherm analysis in order to investigate sorption of sewage sludge-derived Cu and Zn to the A-horizon of a humic-gley soil as a whole, and to the operationally defined exchangeable (1?M MgCl₂), carbonate (1?M NaOAc), Fe/Mn oxide (0.04?M NH₂OH.HCl), and organic (0.02?M HNO₃+30% H₂O₂) soil fractions. Sorption parameters were compared for a sample of sludge leachate (with 97.4% of Cu and 63.2% of Zn present as dissolved metal-organic matter complexes, as calculated by geochemical modeling involving MINTEQA2 and verified using an ion exchange resin method) with that of a reference solution exhibiting the same chemical characteristics as the leachate, except for the presence of dissolved organic material. Dissolved metal-organic matter complexes were found to significantly (P<0.05) depress sorption to the bulk soil and each fraction. The greatest depression of Cu and Zn sorption was observed for the exchangeable, carbonate, and Fe/Mn oxide fractions, while the organic fraction of the soil was the least affected. This reflects a greater affinity for the exchangeable, carbonate, and Fe/Mn oxide fractions by the free divalent metal (Cu²⁺, Zn²⁺), with sorption by these fractions attributed to cation exchange, chemisorption, and co-precipitation processes. The sorption characteristics of the organic fraction indicated that Cu and Zn sorption by soil organic matter mostly involved dissolved metal-organic matter complexes. This may be attributed to hydrophobic interactions between nonpolar regions of the dissolved metal-organic matter complexes and solid-phase soil organic matter.     

EDTA-Enhanced Phytoremediation of Heavy Metals: A Review

The increase in heavy metal terrestrial ecosystems’ contamination through anthropogenic activities is a widespread and serious global problem due to their various environmental and human implications. For these reasons, several techniques, including phytoremediation of heavy metals, have been extensively studied. In spite of significant recent advancement, ethylene diamine tetraacetic acid (EDTA)-enhanced heavy metal phytoextraction as well as related ecological risks are still topical and remain an important area of research. In fact, EDTA favors the solubilization of metals and metalloids in soils, and was therefore extensively studied during the last two decades in order to improve phytoextraction efficiency and reduce treatment duration. This review highlights the recent findings (2010–2012) and mechanisms behind EDTA-enhanced (1) solubilization of heavy metals in soil, (2) mobilization/transport of soluble metals towards plant root zone, and (3) metal absorption by plant roots and translocation towards aerial parts. The review also presents potential risks associated with EDTA-enhanced phytoextraction: (1) environmental persistence of EDTA and/or metal-EDTA complex; (2) potential toxicity of EDTA and/or metal-EDTA complex to plants; and (3) leaching and contamination of groundwater. Moreover, field-scale cost of EDTA-enhanced remediation and the role of EDTA in time required for heavy metal remediation is discussed.     

Trace elements in suspended particulate matter from the Yarra River,Australia

Suspended particulate matter (SPM) was collected from two sites in the Yarra River, Australia under a range of flow conditions using a continuous flow centrifuge. The SPM from the upstream, largely rural, site at Warrandyte had higher concentrations of organic matter, phosphorus and manganese. SPM collected from the downstream, largely urban, site at Heidelberg had elevated concentrations of lead and zinc. The concentrations of iron, copper and chromium in the SPM changed little between the two sites.Over the study period, the flow-weighted mean concentration of SPM increased 5-fold between the two sites and the load increased 7-fold. The annual load of SPM transported past Heidelberg was estimated to be 170 000 tonne, with approximately 80% occurring during high flows (> 15 m³ s^-1 ). Detailed study of the SPM concentrations during flood events suggests that the northern tributaries to the Yarra are the main contributors of SPM in the region between Warrandyte and Heidelberg.The mean annual load of total phosphorus transported by the Yarra River at Heidelberg was estimated to be 220 tonne, approximately 2.5 times greater than at Warrandyte. Approximately 60% of this load was associated with SPM. The majority (ca. 80%) of this SPM-bound phosphorus was extractable with 0.1 M NaOH, and is therefore potentially biologically available.There was little difference between the two sites in the flow-weighted mean concentrations of iron, copper and chromium in SPM. The manganese concentration was approximately halved between Warrandyte and Heidelberg, with most of the loss occurring in the exchangeable and reducible fractions. Lead and zinc concentrations in SPM increased 15 to 16-fold between the two sites, with most of this increase occurring in the exchangeable and reducible fractions. This is some cause for concern, since metals in both these fractions could become available to biota under conditions known to exist in the Yarra estuary.     

Roadside Topsoil Concentrations of Lead and Other Heavy Metals in Ibadan,Nigeria

Concentrations of Pb, Zn, Cd, Cu, Cr, Co, and Ni were determined in roadside topsoil collected from locations of varied vehicular traffic densities in the city of Ibadan, Nigeria, with a view to determining the level of contamination and the contribution of traffic density. Levels of Pb, Zn, Cd, and Cu were elevated above background concentrations measured in control areas. Average values (ppm) for all sample locations were Pb — 81±140; Zn — 48±37; Cd — 0.55±0.49; Cu — 17±17; Cr — 22.1±9.6; Co — 7.9±3.8; Ni — 10.5±9.7. Factors of accumulation of metals in roadsides relative to control sites were highest for Pb. Vehicular traffic was not an important source of chromium, cobalt and nickel, for which roadside concentrations were about those of the control sites. Metal concentrations were poorly correlated with traffic volumes. An average of about 60% of total soil concentration of the metals were determined to be held in bioavailable geochemical phases, of which the highest concentrations were mostly held in either the reducible or oxidizable phase. Levels of the metals in the topsoil were generally lower than the soil quality criteria of some developed countries.     

Effects of biochar amendments on speciation and bioavailability of heavy metals in coal-mine-contaminated soil

An incubation experiment was executed on applying biochar as a soil remediation amendment to discuss an effect of the various addition rates on the speciation and bioavailability of heavy metals in mining-contaminated soil. The result showed that the content of Cd in soil was 9.51 times higher than the Huainan soil background values. The contents of Cu, Zn and As were 2.97, 1.60 and 1.42 times the background values, respectively, and the total contents of all heavy metals were higher than the standard values of soil environment quality GB15618-1995 set by the China Ministry of Environmental Protection. Speciation analysis indicated that Cu and Cd were mainly associated with the reducible fraction, while Zn and As were dominated by the residual fraction. After biochar was added to contaminated soil, the residual fractions of heavy metals increased, while the acid-soluble fractions reduced. According to the results of CaCl₂ extraction experiment, CaCl₂-extractable concentrations of Cu, Zn, As, and Cd were observed with a biochar dosage rate of 10%, which were 57.26%, 51.37%, 6.94% and 42.04% lower than those of control soil samples, respectively, but there were no obvious changes of CaCl₂-extractable As.     

Bacterial enzyme activity and metal speciation in urban river sediments

The effects of stormwater and combined sewer overflows on receiving waters were investigated using measurements of bacterial enzyme activity and metal speciation in the sediments of five urban rivers. Free flowing urban rivers had high enzyme activity and low metal concentration in sediments, indicating a lack of contribution by stormwater sediments. More stagnant urban rivers, which tended to trap sewer-discharged sediments, were characterised by inhibited enzyme activity and high ammonium acetate- and EDTA-extractable metal concentrations. Profiles along two urban rivers showed a direct inhibition of enzyme activity at sites of stormwater and industrial discharge. Deposited sewage, from combined sewer overflows, was indicated by highly elevated enzyme activity and metal concentrations.The results of this study demonstrate that the ecologically relevant enzyme activity measurement may be a useful complement to metal speciation analysis when investigating the effects of stormwater discharges on urban rivers.     

强还原过程对设施菜地土壤重金属形态转化的影响

设施菜地由于污水灌溉、粪肥施用等导致重金属污染.本文通过土柱淹水同时添加玉米秸秆培养和后期通水淋洗,研究强还原法对设施土壤重金属(Cd、Cu、Pb和Zn)形态转化的影响.结果表明: 强还原处理使土壤pH显著降低,玉米秸秆处理变化更显著;土壤氧化还原电位(Eh)迅速下降至-280 mV左右.玉米秸秆处理可以促进土壤中Cd、Cu、Pb和Zn活化,第9天土壤中有机物及硫化物结合态和残渣态Cd、Cu、Pb和Zn含量比重下降;至15 d培养结束,土壤中4种重金属含量较对照分别减少18.1%、19.0%、16.1%和15.7%.玉米秸秆处理可以增加土壤中Cd和Zn的溶出量,但是Cu的溶出量减少;胶体结合态Cd和Pb含量较对照增加、Cu较对照显著减少、Zn没有显著变化.强还原可以引起设施土壤重金属活化,提高蔬菜积累重金属的风险,而且其随土壤水分的运移可能导致水体的污染.     

Accumulative phases for heavy metals in limnic sediments

Data from mechanical concentrates of recent sediments indicate that clay minerals, clay-rich aggregates and heavy minerals are the major carriers of heavy metals in detrital sediment fractions. Hydrous Fe/Mn oxides and carbonates and sulfides, in their specific environments, are the predominant accumulative phases for heavy metals in autochthonous fractions. Sequential chemical extraction techniques permit the estimation of characteristic heavy metal bonding forms: exchangeable metal cations, easily reducible, moderately reducible, organic and residual metal fractions, whereby both diagenetic processes and the potential availability of toxic compounds can be studied. The data from lakes affected by acid precipitation indicate that zinc, cobalt and nickel are mainly released from the easily reducible sediment fractions and cadmium from organic phases. In contrast at pH 4.4, neither lead nor copper seem to be remobilized to any significant extent. Immobilization by carbonate precipitation seems to provide an effective mechanism for the reduction of dissolved inputs 9f metals such as zinc and cadmium in pH-buffered, hard water systems.     

Cumulative Title Index

Abstract

Metal fractionation is a powerful tool for studying the mobility, bioavailability and toxicity of metals in sediments and soils. A seven-step sequential extraction technique was used to determine the potential mobility of selected heavy metals (Fe, Mn, Zn, Cu, Pb, Cd and Ni) in the sediments of Lake Naivasha. Results indicate that residual fraction was the most important phase for the elements Fe, Mn, Cu and Zn. However, Pb and Cd are highly enriched in the non-residual phases. Nickel on the other hand was distributed evenly between the non-residual and the residual fractions.

The total concentrations of the heavy metals suggested a decreasing order of iron ?> manganese ? zinc > nickel > copper ? lead > cadmium. However, the detailed sequential extraction data indicated an order of release or mobility of cadmium > lead ? nickel ? zinc > manganese > copper > iron. The high percentage of Cd and Pb in the mobile fractions suggests high bioavailability of these two elements in the study area and maybe a pointer to anthropogenic input of the two elements in the study area.     

Impact of fluorides on the removal of heavy metals from an electroplating effluent using a flocculent brewer’s yeast strain of Saccharomyces cerevisiae

Abstract

Besides several toxic heavy metals, electroplating effluents can have in solution different cations and anions, which may influence heavy metals removal by the biomass. Among them, fluorides are commonly used in the electroplating industries and thus can be found in the respective wastewaters. In the present work, the effect of the presence of fluorides in the efficiency of chromium(III), copper(II) and nickel(II) removal, from an effluent, by heat-inactivated cells of a brewing flocculent strain of Saccharomyces cerevisiae was evaluated. The presence of fluorides severely decreased (>60%) the removal of chromium(III) by yeast biomass. This effect impaired the effective treatment of the effluent according to the US Environmental Protection Agency and the Portuguese law; conversely, a higher removal of copper(II) and nickel(II) was observed. This behaviour can be understood by metal speciation. In the presence of fluorides, chromium(III) was mainly complexed, becoming unavailable for yeast accumulation; this effect decreased the efficiency of chromium(III) removal. Thus, in the presence of fluorides, less chromium(III) is associated with biomass and consequently more yeast binding sites remain available for the uptake of other metals present in solution. This fact explains the increase of copper(II) and nickel(II) removal in the presence of fluorides.     

Inventory of heavy metals and organic micropollutants In an urban water catchment drainage basin

The Linggi River drainage basin in Negeri Sembilan Malaysia is the major source of potable water for the townships of Seremban and Port Dickson. Water quality is threatened by industrial and commercial development taking place in the basin. This study investigated the concentrations and distribution of organic micro-pollutants and heavy metals within the catchment. Arsenic, copper, cadmium, lead, mercury and zinc were determined in water and sediment samples. All heavy metal concentrations were increased down the basin; arsenic and copper concentration in particular were elevated probably due respectively to flow in of arsenical herbicides in rubber and oil palm plantations and copper sulphate and an additive in pig food.Total phenol concentration also increased considerably within the catchment as a result of urbanisation. Five priority phenolic pollutants (2,4-dimethylphenol; 4-chloro-3-methylphenol; 2,4,6-trichlorophenol; 4-introphenol; pentachlorophenol) were found.     

Pesticides and heavy metals in Danish streambed sediment

The role of streambed sediment as a sink for pesticides and heavy metals was investigated in 30 Danish lowland streams. The investigated streams drain catchments varying in hydrology, topography, soil type and land use. The <250 m newly accumulated fraction of the uppermost 1–2 cm layer of streambed sediment was analysed for 19 old and modern pesticides and 9 heavy metals. DDE was present in the sediment of all the streams. Of the herbicides, fungicides and insecticides currently in use, the most frequently detected was diuron (50.0%), fenpropimorph (66.7%) and lambda-cyhalothrin (6.7%), respectively. The pesticides detected in the highest concentration were fenpropimorph (1700 ng g^–1), propiconazole (130 ng g^–1) and isoproturon (110 ng g^–1). The heavy metals are listed in order of increasing median concentration: Cd (0.80 g g^–1), Co (9.1 g g^–1), As (12.0 g g^–1), Ni (19.0 g g^–1), Cr (19.2 g g^–1), Pb (19.7 g g^–1), Cu (20.1 g g^–1), V (28.5 g g^–1), Zn (103 g g^–1). The average number of pesticides detected in the 27 streams draining predominantly agricultural catchments was (3.7±2.0) being higher (p=0.077) than in the three streams draining non-agricultural catchments (1.7±0.6). Pesticides were significantly related to catchment size, soil type and hydrological regime. Several heavy metals (Cr, Cu, Pb, V and Zn) were related to urban activity and soil type.     

Vanadium as a tracer of oil pollution in the sediments of Kuwait

Vanadium is important as an indicator of oil pollution since oil is one of the main contributors of vanadium to the environment and because most crude oils contain relatively high concentrations of vanadium (30.6 ± 14.3 mg kg^–1 were measured in nine different Kuwait crudes). If oil has settled to the bottom and biodegradation has taken place, it is obvious that enrichment of vanadium in the sediment may be observed.More than 200 sampling sites were selected in the coastal zone of Kuwait and sediment samples were analyzed for grain size distribution, CaC0₃ content, heavy metals and TOC. The analytical results were normalized by taking into account the natural background levels of vanadium in different sediment fractions.After evaluation of the results, vanadium enrichments of as much as 10 to 77 mg kg^–1 were found at 15 sampling locations and of 1 to 10 mg kg^–1 at many others. The areas of vanadium enrichment in the sediments were located 3–5 km from the shoreline in the areas of wastewater discharges, near oil loading piers and in the shipping channels. There was no correlation between vanadium and TOC indicating that biodegradation of oils had taken place. However, high TOC values in the sediments were determined in the near shore sediments around the outlets.