Heavy metal content and distribution in surface sediments of the Seyhan River, Turkey

Chemical fractionation of seven heavy metals (Cd, Cr, Cu, Mn, Ni, Pb and Zn) was studied using a modified three-step sequential procedure to assess their impacts in the sediments of the Seyhan River, Turkey. Samples were collected from six representative stations in two campaigns in October 2009 and June 2010, which correspond to the wet and dry seasons, respectively. The total metal concentrations in the sediments demonstrated different distribution patterns at the various stations. Cadmium was the only metal that was below detection at all stations during both sampling periods. Metal fractionation showed that, except for Mn and Pb, the majority of metals were found in the residual fraction regardless of sampling time, indicating that these metals were strongly bound to the sediments. The potential mobility of the metals (non-residual fractions) is reflected in the following ranking: Pb > Mn > Zn > Cu > Ni > Cr in October 2009 and Mn > Pb > Zn > Cu > Ni > Cr in June 2010. The second highest proportion of metals was bound to organic matter/sulfides, originating primarily from anthropogenic activities. Non-residual metal fractions for all stations were highest in June 2010, which may be linked to higher organic matter concentrations in the sediment samples with 1.40% and 15.1% in October 2009 and June 2010, respectively. Potential sediment toxicity was evaluated using the Risk Assessment Code (RAC). Based on RAC classification, Cd and Cr pose no risk, Cu and Ni pose low risk, Pb and Zn were classified as medium risk metals, while the environmental risk from Mn was high. In addition, based on the sediment quality guidelines (SQG), the Seyhan River can be classified as a river with no, to moderate, toxicological risks, based on total metal concentrations.     

Biosorption of heavy metals by activated sludge and their desorption characteristics

The biosorption of different metals (Cu2+, Cd2+, Zn2+, Ni2+ and Pb2+) was investigated using activated sludge. The optimum pH was 4 for Cd, Cu and Pb sorption and 5 for Ni and Zn. Biomass metal uptake clearly competed with protons present in the aqueous medium, making pH an important variable in the process. Protons consumed by biomass in control tests versus protons exchange in biosorption tests confirmed a maximum exchange between metal cations and protons at pH 2. The study of the influence of biomass concentration revealed that the amount of protons released from biomass increased with biomass concentration. This would confirm the hypothesis of ion exchange between both types of ions. The application of the Langmuir and Freundlich models showed a better fitting of experimental data to the first model. The maximum sorption uptake of the studied metals by the activated sludge showed the following decreasing order: Pb>Cu>CdZn>Ni. Desorption experiments showed that HCl was a good eluent for the five metals tested, particularly at low pH values (1 and 2). At pH 3 or 4 the desorption yield was significantly lower. However, its use did not allow the reuse of biomass in subsequent loading and unloading cycles. EDTA was also a good desorption agent, achieving the total recovery for the five metals tested at a concentration of 1mM, with the advantage that biomass could be reused for three sorption-desorption cycles.     

Metal distribution and stability in constructed wetland sediment

The A-01 wetland treatment system (WTS) is a surface flow wetland planted with giant bulrush [Schoenoplectus californicus (C.A. Mey.) Palla] that is designed to remove Cu and other metals from the A-01 National Pollution Discharge Elimination System (NPDES) effluent at the Savannah River Site near Aiken, SC. Copper, Zn, and Pb concentrations in water were usually reduced 60 to 80% by passage through the treatment system. The Cu concentrations in the wetland sediments increased from about 4 to 205 and 796 mg kg(-1), respectively, in the organic and floc sediment layers in cell 4A over a 5-yr period. Metal concentrations were higher in the two top layers of sediment (i.e., the floc and organic layers) than in the deeper inorganic layers. Sequential extraction was used to evaluate remobilization and retention of Cu, Pb, Zn, Mn, and Fe in the wetland sediment. Metal remobilization was determined by the potentially mobile fraction (PMF) and metal retention by the recalcitrant factor (RF). The PMF values were high in the floc layer but comparatively low in the organic and inorganic layers. High RF values for Cu, Zn, and Pb in the organic and inorganic layers indicated that these metals were strongly bound in the sediment. The RF values for Mn were lower than for the other elements especially in the floc layer, indicating low retention or binding capacity. Retention of contaminants was also evaluated by distribution coefficient (Kd) values. Distribution coefficient (Kd) values were lower for Cu and Zn than for Pb, indicating a smaller exchangeable fraction for Pb.     

Sorption of hazardous metals from single and multi-element solutions by saltbush biomass in batch and continuous mode: interference of calcium and magnesium in batch mode

Batch studies were performed to determine the interference of calcium (Ca) and magnesium (Mg) on the sorption of Cu(II), Cd(II), Cr(III), Cr(VI), Pb(II), and Zn(II) [from CuSO(4), K(2)Cr(2)O(7), Pb(NO(3))(2), Cr(NO(3))(3), ZnCl(2), and Cd(NO(3))(2)] by saltbush (Atriplex canescens) biomass. The results demonstrated that Ca and Mg at concentrations of at least 20 times higher than the concentration of most of the target metals did not interfere with the metal binding. The data show that the batch binding capacity from a multimetal solution at pH 5.0 was (micromol/g) about 260 for Cr(III) and Pb, and about 117, 54, and 49 for Cu, Zn, and Cd, respectively. The use of 0.1M HCl allowed the recovery of 85-100% of the bound Cu, Cr(III), and Pb, and more than 37% of the bound Cd and Zn. The column binding capacity for Pb was about 49 micromol/g from both the single and multimetal solutions, while it was, respectively about 35 and 23 micromol/g for Cr(III). The binding capacity for Cu and Zn from the single and multimetal column experiments was 35 micromol/g and less than 10 micromol/g, respectively. The stripping data from the single column experiment showed that 0.1M HCl allowed the recovery of all the bound Cu and Zn, 90% and 74% of the bound Pb and Cr(VI), respectively, and less than 25% of the bound Cd and Cr(III), while the stripping from the multimetal experiment showed that 0.1M HCl allowed the recovery of all the bound Cu and about 74%, 54%, 43%, and 40% of the bound Pb, Zn, Cd, and Cr(III), respectively.     

Biosorption of Cu(II), Zn(II), Ni(II) and Pb(II) ions by cross-linked metal-imprinted chitosans with epichlorohydrin

Cross-linked metal-imprinted chitosan microparticles were prepared from chitosan, using four metals (Cu(II), Zn(II), Ni(II), and Pb(II)) as templates, and epichlorohydrin as the cross-linker. The microparticles were characterized by Fourier transform infrared spectroscopy, solid state (13)C nuclear magnetic resonance spectroscopy, and energy-dispersive X-ray spectroscopy. They were used for comparative biosorption of Cu(II), Zn(II), Ni(II) and Pb(II) ions in an aqueous solution. The results showed that the sorption capacities of Cu(II), Zn(II), Ni(II), and Pb(II) on the templated microparticles increased from 25 to 74%, 13 to 46%, 41 to 57%, and 12 to 43%, respectively, as compared to the microparticles without metal ion templates. The dynamic study showed that the sorption process followed the second-order kinetic equation. Three sorption models, Langmuir, Freundlich, and Dubinin-Radushkevich, were applied to the equilibrium isotherm data. The result showed that the Langmuir isotherm equation best fitted for monolayer sorption processes. Furthermore, the microparticles can be regenerated and reused for the metal removal.     

Cadmium solubility and sorption in a long-term sludge-amended arable soil

Cadmium solubility and sorption in an arable clay loam soil that had received sewage sludge for 41 years were compared to an unsludged control in batch studies. Soil pH dominated Cd sorption, explaining >92% of the variation in Kd values in both treatments. At any pH, Cd sorption was apparently slightly but significantly (p < 0.05) smaller in the sludge-amended soil compared to the control, even though the organic carbon content was 70% larger and the ammonium oxalate-extractable iron content was roughly doubled. Correction for dissolved organic carbon (DOC) complexation with the speciation model WHAM reduced the difference in sorption between treatments, but the sludged soil still had significantly smaller Kd values (p < 0.01). Batch equilibrations without addition of Cd showed that there was no significant difference in the solubility of "native" cadmium (defined as EDTA-extractable Cd) in sludged and control soils. The reason for the lack of increase in Cd sorption in the sludge-amended soil has not been established, but it may be due to competition for sorption sites on humic compounds with sludge-derived Fe and trace metals such as zinc. The fact that the pyrophosphate-extractable (i.e., organically associated) iron content was seven times larger in the sludged soil provides some supporting evidence for this hypothesis.     

Recovery and distribution of biosolids-derived trace metals in a clay loam soil

The long-term mobility of trace metals has been cited as a potential hazard by critics of EPA 503 rule governing the land application of biosolids. The objectives of this study were to assess the accumulation of Cu, Ni, Cd, and Zn within the soil profile; the distribution of exchangeable, specifically adsorbed, organic, and oxide fractions of each metal; and mass balance of Cu, Ni, and Zn 17 yr after a single biosolids application. Biosolids were applied to 1.5- x 2.3-m confined plots of a Davidson clay loam (fine, kaolinitic, thermic Rhodic Kandiudult) in 1984 at 0, 42, 84, 126, 168, and 210 Mg ha(-1). The highest biosolids application supplied 4.5, 750, 43, and 600 kg ha(-1) of Cd, Cu, Ni, and Zn, respectively. Soils were sampled to a depth of 0.9 m and sectioned into 5-cm increments after separating the Ap horizon. Total (EPA-3050B), bioavailable (Mehlich-I), sequential extraction, and dispersible clay analyses were performed on samples from the control, 126 Mg ha(-1), and 210 Mg ha(-1) treatments. Trace metals are still concentrated in the top 0.2 m with slight enrichment down to 0.3 m. More than 85% of applied Cu, Ni, and Zn are still found in the topsoil where biosolids was incorporated and 95% or more of the applied metals were accounted for with mass balance calculations. Mehlich-I results showed a slight increase in metal concentration down to 0.35 m. Biosolids application increased the concentrations of trace metals in all the extracted fractions. The major portions of Cu, Zn, and Ni are associated with the metal-oxides fraction. Dispersible clay content and water-soluble metal contents were low and except for water-soluble Zn they were not affected by biosolids application. Results from this study showed that 17 yr after biosolids application there was negligible movement of trace metals through the soil profile and consequently there is little risk of contamination of ground water at this site.     

Sorption of trace metals by standard and micro suction cups in the absence and presence of dissolved organic carbon

Both the bioavailability of a trace metal (TM) in a soil and the risk of leaching to the ground water are linked to the metals concentration in the soil solution. Sampling soil solution by tension lysimetry with suction cups is a simple and established technique that is increasingly used for monitoring dissolved TM in soils. Of major concern, however, is the sorption of TM by the walls of the samplers. Metal sorption by different materials used in suction cups can vary widely, depending also on the chemistry of the soil solution. We compared the sorption of Cu, Zn, Cd, and Pb by different standard-size and micro suction cups in the laboratory at two pH values (4.5 and 7.5 or 8.0) in absence and presence of dissolved organic carbon (DOC). In addition, we investigated the sorption of DOC from different origins by the cup materials. At both pH values, the weakest sorption of all four TMs was exhibited by standard-size suction cups based on nylon membranes and by hollow fibers made from polyvinyl alcohol (PVA). At alkaline pH, borosilicate glass, ceramic materials, and polytetrafluorethylene (PTFE) mixed with silicate were characterized by generally strong sorption of all investigated TMs. In addition, Cu and Pb were strongly sorbed at low pH by PTFE-silicate and a ceramic material used for the construction of standard-size suction cups. On the other hand, sorption of Cu, Zn, and Cd by ceramic capillaries produced from pure aluminum oxide was negligible at low pH. Micro suction cups made of an unknown polymerous tube sorbed Cu strongly, but were well suited to monitor Zn, Cd, and Pb at low pH, and, in the presence of DOC, also at high pH. Major cations (Na+, Mg2+, K+, Ca2+) and anions (Cl-, NO3-, SO4(2-)) were not or very weakly sorbed by all cup materials, except for Mg2+, K+, and Ca2+ by borosilicate glass at pH 7.5. Trace metal sorption by suction cups was generally greatly reduced in the presence of DOC, especially at alkaline pH. The sorption of DOC itself depended on its source. Dissolved organic carbon from leaf litter extracts with a probably large hydrophobic fraction was sorbed more strongly than mainly hydrophilic DOC from a mineral soil solution.     

Concentration, pH, and surface charge effects on cadmium and lead sorption in three tropical soils

Reactions of heavy metals with soil are important in determining metal fates in the environment. Sorption characteristics of two heavy metals, Cd and Pb, in three tropical soils (Mollisol, Oxisol, and Ultisol) from Puerto Rico were assessed at varying metal concentrations (0 to 1.2 mM) and pH values (approximately 2 to 7). All soils sorbed more Pb than Cd. Sorption maxima were obtained for each metal for the Oxisol and Ultisol soils, but not the Mollisol. Sorption appeared to depend more on soil mineralogy than organic matter content. Sorption isotherms were linear within the sorption envelope with similar slopes for each soil-metal curve, when plotting metal sorption as a function of pH. Cadmium and Pb isotherms yielded average slopes of approximately 36+/-1 and 28+/-1 units (percent increase in metal sorption per 1-unit increase in pH), respectively. Metal sorption depended more on metal type than soil composition. Cadmium sorption displayed a greater pH dependence than Pb. Cadmium sorption was less than or equal to the amount of negative surface charge except at pH values greater than the point of zero net charge (PZNC). This suggests that Cd was probably sorbed via electrostatic surface reactions and/or possible inner-sphere complexation at pH > 3.7. However, the amount of Pb sorbed by the Oxisol was greater than the amount of negative surface charge, suggesting that Pb participates in inner-sphere surface reactions. Lead was sorbed more strongly than Cd in our soils and poses less of a threat to underlying ground water systems due to its lower mobility and availability.     

Distribution and movement of sludge-derived trace metals in selected Nigerian soils

Use of metal-rich sewage sludge as soil fertilizer may result in trace- metal contamination of soils. This study was conducted to evaluate the effects of long-term sludge application on trace-metal (Zn, Cu, Pb, and Ni) distribution and potential bioavailability in Nigerian soils under a tropical wet-dry climate. Total metal analyses, sequential chemical fractionation, and DTPA extractions were carried out on samples of control and sludge-amended pedons in Nigeria (a Rhodic Kandiustult and two Rhodic Kandiustalfs from Nigeria, respectively). The sewage sludge applied to the soils contained higher levels of Zn and Cu than Pb and Ni. The control pedon contained low levels of all four metals. Soil enrichment factors (EF) were calculated for each metal in the sludge-amended pedons. Compared with the control soil, the sludge-amended pedons showed elevated levels of Zn and Cu, reflecting the trace-metal composition of the sewage sludge. Zinc and Cu in the sludge-amended soils were strongly enriched at all depths in the profile, indicating that they had moved below the zone of sludge application. The sequential extraction and DTPA analyses indicated that the sludge-amended soils contained more readily extractable and bioavailable metal ions than the unamended soil.     

Trace Metal Concentrations in an Intensive Agricultural Watershed in British Columbia,Canada1

Abstract: Effects of agricultural intensification and a naturally occurring landslide of asbestos material upon water and sediment quality in a transboundary watershed were investigated. The water and sediments of the Sumas River watershed were analyzed for copper (Cu), zinc (Zn), chromium (Cr), and nickel (Ni) concentrations in 1993/1994 and 2003/2004 and differences within sites over time were examined. Based upon a review of the literature, Cu and Zn were used as indicators of agricultural impacts while Cr and Ni were used as indicators of impacts from an asbestos landslide. Animal unit equivalents (AUEs) were calculated on a per area basis as an indicator of livestock density using detailed statistical census data. Whatman #42 filtered metals, bioavailable metals, and sediment‐bound metals (in the <63 μm fraction) were determined at 22 sites along the mainstem and tributaries, including two reference sites. Temperature, pH, and dissolved organic carbon (DOC) were also measured. The bioavailable metal fraction was determined using the diffusive gradient thin film technique (DGT). Sediment‐bound results were compared with British Columbia’s Interim Sediment Quality Guidelines (ISQGs) and Severe Effects Levels (SELs). A Wilcoxon signed rank test was used to determine if the concentrations of metals changed significantly within sites between 1993/1994 and 2003/2004. Spearman rank correlation analysis was used to determine relationships between trace metals, water quality parameters, and AUEs/hectare. The results indicate that Cu and Zn levels in sediments increased significantly to concentrations above the ISQGs of 35.7 mg/kg and 123 mg/kg, respectively from 1993/1994 to 2003/2004 in streams, where associated land use was dominated by intensive agriculture. Higher AUEs/hectare were significantly correlated with greater bioavailable levels of Zn as well as higher sediment‐bound Zn concentrations. Neither Cu nor Cr were detected by the DGTs on any of the sampling occasions. The Cr and Ni sediment concentrations were highest in Swift Creek, the headwater tributary affected by the natural landslide of asbestos material, and decreased in the Sumas River downstream from the point of input. Cr and Ni concentrations have increased in the mid‐region of the Sumas River since 1993/1994, suggesting downstream movement of the asbestos material over time. DGT results indicated that bioavailable Zn is significantly positively correlated to sediment‐bound Zn and livestock density, and bioavailable Ni is significantly correlated to sediment‐bound Ni.     

Total Contents and Sequential Extraction of Heavy Metals in Soils Irrigated with Wastewater,Akaki, Ethiopia

The Akaki River, laden with untreated wastes from domestic, industrial, and commercial sources, serves as a source of water for irrigating vegetable farms. The purpose of this study is to identify the impact of waste-water irrigation on the level of heavy metals and to predict their potential mobility and bioavailability. Zn and V had the highest, whereas Hg the lowest, concentrations observed in the soils. The average contents of As, Co, Cr, Cu, Ni, Zn, V, and Hg of both soils; and Pb and Se from Fluvisol surpassed the mean + 2 SD of the corresponding levels reported for their uncontaminated counterparts. Apparently, irrigation with waste water for the last few decades has contributed to the observed higher concentrations of the above elements in the study soils (Vertisol and Fluvisol) when compared to uncontaminated Vertisol and Fluvisol. On the other hand, Vertisol accommodated comparatively higher average levels of Cr, Cu, Ni, Zn, etc V, and Cd, whereas high contents of Pb and Se were observed in Fluvisol. Alternatively, comparable levels of Co and Hg were found in either soil. Except for Ni, Cr, and Cd in contaminated Vertisol, heavy metals in the soils were not significantly affected by the depth (0–20 and 30–50 cm). When the same element from the two soils was compared, the levels of Cr, Cu, Ni, Pb, Se, Zn, V, Cd at 0–20 cm; and Cr, Ni, Cu, Cd, and Zn at 30–50 cm were significantly different. Organic carbon (in both soils), CEC (Fluvisol), and clay (Vertisol) exhibited significant positive correspondences with the total heavy metal levels. Conversely, Se and Hg contents revealed perceptible associations with carbonate and pH. The exchangeable fraction was dominated by Hg and Cd, whereas the carbonate fraction was abounded with Cd, Pb, and Co. conversely, V and Pb displayed strong affinity to reducible fraction, where as Cr, Cu, Zn, and Ni dominated the oxidizable fraction. Cr, Hg, Se, and Zn (in both soils) showed preference to the residual fraction. Generally, a considerable proportion of the total levels of many of the heavy metals resided in non residual fractions. The enhanced lability is generally expected to follow the order: Cd > Co > Pb > Cu > Ni > Se > V and Pb > Cd > Co > Cu > Ni > Zn in Vertisol and Fluvisol, respectively. For the similar wastewater application, the soil variables influence the status and the distribution of the associated heavy metals among the different soil fractions in the study soils. Among heavy metals that presented relatively elevated levels and with potential mobility, Co, Cu, Ni (either soil), V (Vertisol), Pb, and Zn (Fluvisol) could pose health threat through their introduction into the food chain in the wastewater irrigated soils.     

Mobilization of trace metals and inorganic compounds during resuspension of anoxic sediments from Trepangier Bayou, Louisiana

The release of trace metals (Mn, Ni, Co, Cu, Zn, Pb, and Cd) and inorganic compounds (As) from initially anoxic Trepangier Bayou sediments, Louisiana and the sources of the released metals were investigated. After 1 to 2 d aeration, significant amounts of trace metals (Mn, Zn, Cd, Ni, and Co) were released to the aqueous phase with increased acidity, primarily due to the oxidation of acid-volatile sulfide and ferrous iron and iron sulfide minerals. The addition of a bacterial inhibitor, NaN,, to the Trepangier sediment during resuspension inhibited metal release, suggesting that microbial catalysis can regulate metal mobilization during sediment resuspension. In a well buffered system, oxidation of iron sulfides alone did not appear to induce trace metal release. Moreover, when Trepangier sediment was resuspended in anoxic conditions at neutral pH, <1% of the trace metal content was released, whereas a significant release of metal was observed under acidic anoxic conditions. Although oxidation of iron sulfide minerals is an essential prerequisite for the release of Zn, Co, Cd, and Ni, carbonates and oxides also play a role. The trace metals and inorganic compounds investigated could be classified into three groups according to their release characteristics: (i) Mn, Zn, Cd, Ni, and Co; (ii) Fe, Pb, and As; and (iii) Cu. The groupings appeared to depend on the sources of compounds and their relative affinity, after oxidation, to iron oxyhydroxides or organic matter.     

Relationships between bacterial tolerance levels and forms of copper and zinc in soils

The effects of various fractions of copper (Cu) and zinc (Zn) on soil bacteria were evaluated by the heavy metal tolerance level of the bacterial community (IC50) in soil samples collected near a mine. The IC50 values had no relationship with the total concentrations of Zn and Cu in the soils, but were weakly correlated with the 0.05 M CaCl2-extractable form of each metal in the soils (Cu: R2 = 0.670, p < 0.01; Zn: R2 = 0.453, p < 0.05). It was found that the IC50 correlated strongly with the total concentration of each metal in the extracts from water-saturated soil samples, described below as "soil solution" (Cu: R2 = 0.789, p < 0.01; Zn: R2 = 0.617, p < 0.01). The speciation of these metals in the soil solutions was estimated using an equilibrium thermodynamic computer model, SOILCHEM. Simulated free Cu ion ranged from 18 to 98% of total Cu, and organic complexes of Cu ranged from < 1 to 56%. In all samples, Zn existing as the free ion was estimated to be more than 80% of total Zn in the soil solutions. The IC50 values were also correlated with the estimated free metal ion activities, but with slightly lower correlation coefficients than found for total concentration in the soil solutions (Cu: R2 = 0.735, p < 0.01; Zn: R2 = 0.610, p < 0.01). The results suggest that not only high metal ion activities, but also total dissolved metal concentrations in soil solutions may affect the bacterial community.     

Effect of organic matter oxidation on the fractionation of copper, zinc, lead, and arsenic in sewage sludge and amended soils

Long-term land application of sewage sludge (SS) has caused concern over the potential release of trace metals into the environment following the degradation of organic matter (OM). This study was performed to assess the impact of OM degradation on the relative distribution of Cu, Zn, Pb, and As in SS and SS-amended soils. Three SSs of different ages and two soils treated with SS were subjected to incubation and direct chemical oxidation using diluted HO, followed by a sequential extraction. The majority of Cu, Pb, and As were bound to OM, whereas the majority of Zn was bound with Fe/Mn oxides for all three SSs. Incubation of SS for 6 mo did not result in a substantial decrease in OM content or a change in the relative distribution of Cu, Zn, Pb, and As. Direct OM oxidation to 30 and 70% by diluted HO resulted in a significant decrease in organically bound Cu but increased its exchangeable, carbonate-bound, and Fe/Mn-bound fractions. Oxidation of OM slightly decreased organically bound Zn but significantly increased exchangeable Zn in all SSs. Oxide- and carbonate-bound Zn also decreased following OM oxidation. Exchangeable fractions of As and Pb were minute before and after OM degradation, indicating that release into the environment would be unlikely. The relative distribution of Cu, Zn, Pb, and As in SS-treated soils was similar to that of SS, suggesting a dominant role of SS properties in controlling metal distribution following OM oxidation. Overall, OM oxidation increased the mobility and bioavailability of Zn and Cu, whereas it had less impact on Pb and As.     

超声波去除农用污泥中重金属的试验研究

污水处理厂污泥中的重金属浓度高是污泥农用的主要障碍。为了降低农用污泥中的重金属含量,以Cu、Zn、Ni、Pb为对象,研究了超声波对其的影响。结果表明:超声对污泥中重金属有一定的溶出作用。当超声时间为30min时,溶解状态Cu、Zn、Ni、Pb的析出率分别为42.1%、37.5%、12.7%、14.7%;总的析出率分别为52.7%、44.7%、23.6%、71%。其中析出的Pb大部分以胶体状态存在,而溶解状态只占很少一部分。其他几种金属则以溶解状态为主。     

Effects of wood bark and fertilizer amendment on trace element mobility in mine soils, Broken Hill, Australia: implications for mined land reclamation

Soil amendments can immobilize metals in soils, reducing the risks of metal exposure and associated impacts to flora, fauna and human health. In this study, soil amendments were compared, based on "closed system" water extracts, for reducing metal mobility in metal-contaminated soil from the Broken Hill mining center, Australia. Phosphatefertilizer (bovine bone meal, superphosphate, triple superphosphate, potassium orthophosphate) and pine bark (Pinus radiata) were applied to two soils (BH1, BH2) contaminated with mining waste. Both soils had near neutral to alkaline pH values, were sulfide- or sulfate-rich, and contained metal and metalloid at concentrations that pose high environmental risks (e.g., Pb = 1.25 wt% and 0.55 wt%, Zn = 0.71 wt% and 0.47 wt% for BH1 and BH2, respectively). The addition of fertilizers and/or pine bark to both soil types increased water extractable metals and metalloids concentrations (As, Cd, Cu, Fe, Mn, Pb, Sb, Zn) compared with nonamended soils. One or more of the elements As, Cd, Cu, Mn, Pb, and Zn increased significantly in extracts of a range of different soil+pine bark and soil+fertilizer+piner+pine bark tests in response to increased pine bark doses. By contrast, Fe and Sb concentrations in extracts did not change significantly with pine bark addition. Solution pH was decreased by phosphate fertilizers (except for bovine bone meal) and pine bark, and pine bark enhanced dissolved organic carbon. At least in the short-term, the application of phosphate fertilizers and pine bark proved to be an ineffective method for controlling metal and metalloid mobility in soils that contain admixtures of polymetallic, polymineralic mine wastes.     

Fractionation of selected metals in the sediments of Cochin estuary and Periyar River, southwest coast of India

Cochin estuary is one of the highly polluted aquatic systems of the southwest coast of India. The present study focuses on the assessment of heavy metals (Zn, Cd, Pb, and Cu) present in the sediments of Cochin estuary and the adjoining Periyar River. The sediments were analyzed for total metal content and various chemically bound fractions such as exchangeable, carbonate bound, easily reducible, organic, and residual. Total metal content of sediment was found higher than the average values reported from other Indian rivers. The mean concentration of Zn, Cd, Pb, and Cu in the sediments was 1,249.44, 9.5, 221.37, and 166.14???g/g, respectively. The results of sequential extraction showed that the concentration of Cd was high in the first two weakly bound fractions (exchangeable and carbonate bound) than the other metals, which are high in residual and organic bound fractions. Risk-assessment code analysis and environmental indices (enrichment factor and pollution load index) suggest that the sediments are highly polluted with metals, especially Cd.     

Fate of biosolids trace metals in a dryland wheat agroecosystem

Biosolids land application for beneficial reuse applies varying amounts of trace metals to soils. Measuring plant-available or total soil metals is typically performed to ensure environmental protection, but these techniques do not quantify which soil phases play important roles in terms of metal release or attenuation. This study assessed the distribution of Cd, Cr, Cu, Mo, Ni, Pb, and Zn associated with soluble/exchangeable, specifically adsorbed/carbonate-bound, amorphous Mn hydroxyoxide-bound, amorphous Fe hydroxyoxide-bound, organically complexed, and residual inorganic phases. Biosolids were applied every 2 yr from 1982 to 2002 (except in 1998) at rates of 0, 6.7, 13.4, 26.8, and 40.3 dry Mg biosolids ha(-)(1) to 3.6- by 17.1-m plots. In 2003, 0- to 20-cm and 20- to 60-cm soil depths were collected and subjected to 4 mol L(-1) HNO(3) digestion and sequential extraction. Trace metals were concentrated in the 0- to 20-cm depth, with no significant observable downward movement using 4 mol L(-1) HNO(3) or sequential extraction. The sequential extraction showed nearly all measurable Cd present in relatively mobile forms and Cr, Cu, Mo, Ni, Pb, and Zn present in more resistant phases. Biosolids application did not affect Cd or Cr fractionation but did increase relatively immobile Cu, Mo, and Zn phases and relatively mobile Cu, Ni, and Pb pools. The mobile phases have not contributed to significant downward metal movement. Long-term, repeated biosolids applications at rates considered several times greater than agronomic levels should not significantly contribute to downward metal transport and ground water contamination for soils under similar climatic conditions, agronomic practices, and histories.