Transport and sediment–water partitioning of trace metals in acid mine drainage: an example from the abandoned Kwangyang Au–Ag mine area, South Korea

Transport and sediment–water partitioning of trace metals (Cr, Co, Fe, Pb, Cu, Ni, Zn, Cd) in acid mine drainage were studied in two creeks in the Kwangyang Au–Ag mine area, southern part of Korea. Chemical analysis of stream waters and the weak acid (0.1 N HCl) extraction, strong acid (HF–HNO₃–HClO₄) extraction, and sequential extraction of stream sediments were performed. Heavy metal pollution of sediments was higher in Chonam-ri creek than in Sagok-ri creek, because there is a larger source of base metal sulfides in the ores and waste dump upstream of Chonam-ri creek. The sediment–water distribution coefficients (K _d) for metals in both creeks were dependent on the water pH and decreased in the order Pb ≈ Al > Cu > Mn > Zn > Co > Ni ≈ Cd. K _d values for Al, Cu and Zn were very sensitive to changes in pH. The results of sequential extraction indicated that among non-residual fractions, Fe–Mn oxides are most important for retaining trace metals in the sediments. Therefore, the precipitation of Fe(–Mn) oxides due to pH increase in downstream sites plays an important role in regulating the concentrations of dissolved trace metals in both creeks. For Al, Co, Cu, Mn, Pb and Zn, the metal concentrations determined by 0.1 N HCl extraction (Korean Standard Method for Soil Pollution) were almost identical to the cumulative concentrations determined for the first three weakly-bound fractions (exchangeable + bound to carbonates + bound to Fe–Mn oxides) in the sequential extraction procedure. This suggests that 0.1 N HCl extraction can be effectively used to assess the environmentally available and/or bioavailable forms of trace metals in natural stream sediments.     

Heavy metal content in the stream sediments adjacent to a sanitary landfill

Samples of stream sediments were collected along two streams adjacent to a sanitary landfill. One of the streams drained the landfill directly. In addition, control of background samples were also analyzed from a stream not affected by the landfill. All samples were analyzed for Ag, Zn, Cu, Cd, and Pb content using atomic adsorption techniques. The pH of the three streams were monitored since pH differences in the streams may affect the quantities of metals adsorbed or precipitated on the sediments. The comparison between the content of Ag, Zn, and Cu in the sediments of the two study streams and the same metals in the control sediments indicated the landfill emitted these metals into the two adjacent streams. However, since the Cd and Pb contents in the sediments of both streams were similar to that of the control stream sediments, these metals may not be emitted into the two study streams from the landfill and they represent only background quantities. The comparisons of each metal in the sediments of each stream were made by the use of a metal trend chart, the individual calculated mean metal content values, and by the statistical two sample t-test. No decreasing trends of the quantities of Ag, Zn, or Cu as a function of increasing distance from the landfill was present in the sediments along the stream that drained the landfill directly. These sediments might have been affected by stream action and became mixed with other sediments downstream.     

Distribution and immobilization of heavy metals in Pliocene aquifer sediments in Wadi El Natrun depression, Western Desert

The Pliocene aquifer receives inflow of Miocene and Pleistocene aquifer waters in Wadi El Natrun depression. The aquifer also receives inflow from the agricultural activity and septic tanks. Nine sediment samples were collected from the Pliocene aquifer in Wadi E1 Natrun. Heavy metal (Cu, Sr, Zn, Mn, Fe, Al, Ba, Cr, Ni, V, Cd, Co, Mo, and Pb) concentrations of Pliocene aquifer sediments were investigated in bulk, sand, and mud fractions. The determination of extractable trace metals (Cu, Zn, Fe, Mn, and Pb) in Pliocene aquifer sediments using sequential extraction procedure (four steps) has been performed in order to study environmental pathways (e.g., mobility of metals, bounding states). These employ a series of successively stronger chemical leaching reagents which nominally target the different compositional fractions. By analyzing the liquid leachates and the residual solid components, it is possible to determine not only the type and concentration of metals retained in each phase but also their potential ecological significance. Cu, Sr, Zn, Mn, Fe, and Al concentrations are higher in finer sediments than in coarser sediments, while Ba, Cr, Ni, V, Cd, Co, Mo, and Pb are enriched in the coarser fraction. The differences in relative concentrations are attributed to intense anthropogenic inputs from different sources. Heavy metal concentrations are higher than global average concentrations in sandstone, USEPA guidelines, and other local and international aquifer sediments. The order of trace elements in the bulk Pliocene aquifer sediments, from high to low concentrations, is Fe?>?Al?>?Mn?>?Cr?>?Zn?>?Cu?>?Ni?>?V?>?Sr?>?Ba?>?Pb?>?Mo?>?Cd?>?Co. The Pliocene aquifer sediments are highly contaminated for most toxic metals, except Pb and Co which have moderate contamination. The active soluble (F0) and exchangeable (F1) phases are represented by high concentrations of Cu, Zn, Fe, and Mn and relatively higher concentrations of Pb and Cd. This may be due to the increase of silt and clay fractions (mud) in sediments, which act as an adsorbent, retaining metals through ion exchange and other processes. The order of mobility of heavy metals in this phase is found to be Pb?>?Cd?>?Zn?>?Cu?>?Fe?>?Mn. The values of the active phase of most heavy metals are relatively high, indicating that Pliocene sediments are potentially a major sink for heavy metals characterized by high mobility and bioavailability. Fe–Mn oxyhydroxide phase is the most important fraction among labile fractions and represents 22% for Cd, 20% for Fe, 11% for Zn, 8% for Cu, 5% for Pb, and 3% for Mn. The organic matter-bound fraction contains 80% of Mn, 72% of Cu, 68% of Zn, 60% of Fe, 35% of Pb, and 30% of Cd (as mean). Summarizing the sequential extraction, a very good immobilization of the heavy metals by the organic matter-bound fraction is followed by the carbonate-exchangeable-bound fraction. The mobility of the Cd metal in the active and Fe–Mn oxyhydroxide phases is the highest, while the Mn metal had the lowest mobility.     

Environmental geochemistry of El Temsah Lake sediments, Suez Canal district, Egypt

The heavy metal contents of Mn, Ni, Cu, Zn, Cr, Co, Pb, Cd, Fe, and V in the surface sediments from five selected sites of El Temsah Lake was determined by graphite furnace atomic absorption spectrophotometer. Geochemical forms of elements were investigated using four-step sequential chemical extraction procedure in order to identify and evaluate the mobility and the availability of trace metals on lake sediments, in comparison with the total element content. The operationally defined host fractions were: (1) exchangeable/bound to carbonate, (2) bound to Fe/Mn oxide, (3) bound to organic matter/sulfides, and (4) acid-soluble residue. The speciation data reveals that metals Zn, Cd, Pb, Ni, Mn, Cu, Cr, Fe, and V are sink primarily in organic and Fe–Mn oxyhydroxides phases. Co is mainly concentrated in the active phase. This is alarming because the element is enriched in Al Sayadin Lagoon which is still the main site of open fishing in Ismailia. Average concentration of the elements is mostly above the geochemical background and pristine values of the present study. There is a difference on the elemental composition of the sediment collected at the western lagoon (Al Sayadin Lagoon), junction, the shoreline shipyard workshops, and eastern beach of the lake. Depending upon the nature of elements and local pollution source, high concentration of Zn, Pb, and Cu are emitted by industrial wastewater flow (shoreline workshops), while sanitary and agricultural wastewater (El Bahtini and El Mahsama Drains) emit Co and Cd in Al Sayadin Lagoon. On the other hand, there is a marked decrease in potentially toxic heavy metal concentrations in the sediments at the most eastern side of the lake, probably due to the successive sediment dredging and improvements in water purification systems for navigation objective. These result show that El Temsah receives concentrations in anthropogenic metals that risk provoking more or less important disruptions, which are harmful and irreversible on the fauna and flora of this lake and on the whole ecobiological equilibrium.     

Heavy metal partitioning in river sediments severely polluted by acid mine drainage in the Iberian Pyrite Belt

This study provides a geochemical partitioning pattern of Fe, Mn and potentially toxic trace elements (As, Cd, Cr, Cu, Ni, Pb, Zn) in sediments historically contaminated with acid mine drainage, as determined by using a 4-step sequential extraction scheme. At the upperstream, the sediments occur as ochreous precipitates consisting of amorphous or poorly crystalline oxy-hydroxides of Fe, and locally jarosite, whereas the estuarine sediments are composed mainly of detrital quartz, illite, kaolinite, feldspars, carbonates and heavy minerals, with minor authigenic phases (gypsum, vivianite, halite, pyrite). The sediments are severely contaminated with As, Cd, Cu, Pb and Zn, especially in the vicinity of the mining pollution sources and some sites of the estuary, where the metal concentrations are several orders of magnitude above background levels. Although a significant proportion of Zn, Cd and Cu is present in a readily soluble form, the majority of heavy metals are bonded to reducible phases, suggesting that Fe oxy-hydroxides have a dominant role in the metal accumulation. In the estuary, the sediments are potentially less reactive than in the riverine environment, because relevant concentrations of heavy metals are immobilised in the crystalline structure of minerals.     

Use of normalized metal concentrations in the Mn oxides/hydrous oxides extraction phase of stream sediments to enhance the difference between a landfill emission plume and background

Normalized concentrations of Fe, Zn, Ba and Co bound to the Mn phase were determined using a ratio of metal concentration to Mn concentration. Metal concentrations were taken from a previous study which found elevated concentrations of heavy metals in the stream sediments in the vicinity of 2 landfills using a HN0₃ extraction of the whole sediment sample and geochemical phases. Results from the normalized metal concentrations for Zn, Fe and Ba showed a clearer distinction between background and emission plume regions along the stream compared to the same for the HN0₃ and Mn phase extractions. Lack of elevated concentrations and normalized concentrations for Co indicated the concentrations represented the background. The small distance used in the study could explain the lack of a decreasing trend of metal concentrations and normalized metal concentrations downstream in the emission plume of the sediments. Although Mn⁺² 2concentrations are known to be incorporated into the natural state of the Mn phase, these concentrations were thought to be small enough not to influence the results from the normalized concentrations. Non-selectivity of extractants and metal redistribution among chemical phases during extraction procedures are thought to be small and did not invalidate the results.     

Metal speciation and attenuation in stream waters and sediments contaminated by landfill leachate

The degree of metal contamination (Zn, Pb, Cu, Ni, Cd) has been investigated in the vicinity of an old unmonitored municipal landfill in Prague, Czech Republic, where the leachate is directly drained into a surface stream. The water chemistry was coupled with investigation of the stream sediment (aqua regia extract, sequential extraction, voltammetry of microparticles) and newly formed products (SEM/EDS, XRD). The MINTEQA2 speciation-solubility calculation showed that the metals (Zn, Pb, Cu, Ni) are mainly present as carbonate complexes in leachate-polluted surface waters. These waters were oversaturated with respect to Fe(III) oxyhydroxides, calcite (CaCO₃) and other carbonate phases. Three metal attenuation mechanisms were identified in leachate-polluted surface waters: (i) spontaneous precipitation of metal-bearing calcite exhibiting significant concentrations of trace elements (Fe, Mn, Mg, Sr, Ba, Pb, Zn, Ni); (ii) binding to Fe(III) oxyhydroxides (mainly goethite, FeOOH) (Pb, Zn, Cu, Ni); and (iii) preferential bonding to sediment organic matter (Cu). These processes act as the key scavenging mechanisms and significantly decrease the metal concentrations in leachate-polluted water within 200 m from the direct leachate outflow into the stream. Under the near-neutral conditions governing the sediment/water interface in the landfill environment, metals are strongly bound in the stream sediment and remain relatively immobile.     

Distribution of heavy metals in the clastic fine-grained sediments of Gavkhuni playa lake (Southeast of Isfahan,Iran)

The sedimentary basin of Gavkhuni playa lake includes two sedimentary environments of delta and playa lake. These environments consist of mud, sand and salt flats. There are potentials for concentration of heavy metals in the fine-grained sediments (silt and clay) of the playa due to existence of Pb/Zn ore deposits, industrial and agricultural regions in the water catchment of Zayandehrud River terminating to this area. In order to study the concentration of heavy metals and the controlling factors on their distribution in the fine-grained sediments, 13 samples were taken from the muddy facies and concentration of the heavy metals were determined. The results showed that the heavy metal concentrations range in the sediments (in ppm) are Mn (395.5–1,040), Sr (100.4–725.76), Pb (14.66–91.06), Zn (23.59–80.9), Ni (37–73.66), Cu (13.83–29.83), Co (5.73–13.78), Ag (3.03–4.76) and Cd (2.3–5.5) in their order of abundances. The concentration of Ag is noticeable in the sediments relative to the average concentration of this element in mud sediments. The amounts of Pb and Zn are relatively high in all the samples in comparison with the other elements. The concentration of Ni is relatively high in the oxidized samples. The distribution of Pb is directly related to organic matter content of the sediments. The concentrations of Zn, Sr, Cu, Co and Cd in the samples of the playa are lower than those in the delta. The amount of illite is another factor influencing Zn and Pb concentrations. Sr is more concentrated in the sediments with the high content of calcium carbonate. The distribution pattern of Cu, Co, Pb and Mn resembles to that of the clay content of the sediments. The clay content shows positive correlations with Co, Cu and Mn concentrations and negative correlation with Ag. The Sr and Ag concentrations are positively correlated with the amount of CaCO₃. The amounts of Co, Cu, Ni and Mn show negative correlations with the calcium carbonate content. Pb and Co are noticeably correlated with Mn.     

Application of equilibrium partitioning approach to derive sediment quality criteria for heavy metals in a shallow eutrophic lake, Lake Chaohu, China

In this study, the equilibrium partitioning approach was used to derive the sediment quality criteria (SQC) recommended values of eight heavy metals (Cr, Cu, Pb, Zn, Cd, As, Fe and Mn) for surface sediments taken from Lake Chaohu. The concentration of the heavy metal in the interstitial water (C _IW) was determined by the film diffusion gradient technology to obtain the metal partitioning coefficient (K _P). Moreover, the metal fractionation of the sediments were analyzed using European Community Bureau of Reference sequential extraction procedure and the partitioning of bound phases including total organic carbon (TOC), grain sizes and acid volatile sulfide (AVS) were also investigated. The values of K _P for Cr, Cu, Pb, Zn, Cd, As, Fe and Mn were 3,924.84, 2,276.23, 17,811.30, 738.35, 10,986.54, 718.74, 5,875.34 and 341.20 L/kg, respectively. Sediment quality criteria were normalized on the basis of fine materials, AVS, TOC and the residual metals (M _R). SQC values for Cr, Cu, Pb, Zn, Cd, As, Fe and Mn based on Chinese surface water quality criteria were derived with the values of 78.53, 56.95, 362.93, 74.68, 23.90, 71.84, 3,546.53 and 68.42 mg/kg, respectively. The suggested SQC values in this study were compared SQCs from different countries and areas, which indicated SQCs from different countries or regions appeared to have great discrepancies attributed to the difference of the physical and chemical characteristics of sediments.     

Partitioning of heavy metals in surface Black Sea sediments

Bulk heavy metal (Fe, Mn, Co, Cr, Ni, Cu, Zn and Pb) distributions and their chemical partitioning, together with TOC and carbonate data, were studied in oxic to anoxic surface sediments (0–2 cm) obtained at 18 stations throughout the Black Sea. TOC and carbonate contents, and available hydrographic data, indicate biogenic organic matter produced in shallower waters is transported and buried in the deeper waters of the Black Sea. Bulk metal concentrations measured in the sediments can be related to their geochemical cycles and the geology of the surrounding Black Sea region. Somewhat high Cr and Ni contents in the sediments are interpreted to reflect, in part, the weathering of basic-ultrabasic rocks on the Turkish mainland. Maximum carbonate-free levels of Mn (4347 ppm), Ni (355 ppm) and Co (64 ppm) obtained for sediment from the shallow-water station (102 m) probably result from redox cycling at the socalled ‘Mn pump zone’ where scavenging-precipitation processes of Mn prevail. Chemical partitioning of the heavy metals revealed that Cu, Cr and Fe seem to be significantly bound to the detrital phases whereas carbonate phases tend to hold considerable amounts of Mn and Pb. The sequential extraction procedures used in this study also show that the metals Fe, Co, Ni, Cu, Zn and Pb associated with the ‘oxidizable phases’ are in far greater concentrations than the occurrences of these metals with detrital and carbonate phases. These results are in good agreement with the recent studies on suspended matter and thermodynamic calculations which have revealed that organic compounds and sulfides are the major metal carriers in the anoxic Black Sea basin, whereas Fe-Mn oxyhydroxides can also be important phases of other metals, especially at oxic sites. This study shows that, if used with a suitable combination of the various sequential extraction techniques, metal partitioning can provide important information on the varying geological sources and modes of occurrence and distribution of heavy metals in sediments, as well as, on the physical and chemical conditions prevailing in an anoxic marine environment.     

Accumulation discrepancy of heavy metal and organic pollutants in three near-shore depositional environments, southeastern China

Heavy metal and organic pollutants in sediments along the coastal zone of southeastern China have been investigated. Sediment samples are retrieved from three depositional environments: coast, estuary, and tide-affected river mouth. The relative abundance of heavy metal and organic pollutants is related to their geochemical properties as well as depositional environments and anthropogenic discharge. Based on a sequential extraction method, it is revealed that anthropogenic Pb, Cr, Cu, and Cd are mainly bound to Fe–Mn oxides, suggesting that adsorption and co-precipitation of Fe–Mn oxides are in the control of their transfer processes from water column to sediment. Heavy metal bound to carbonates is also an important pool especially for Cd, Mn, and Pb. The main organic pollutants found in the study area include petroleum-related alkanes, phthalic acid ester, organic silicon, chlorophenol, phenyl ether, and amine. The accumulation of heavy metals and organics in surficial sediments has a decrease tendency from estuarine environment to coastal environment and to tide-affected river mouth.     

Removal of trace elements from landfill leachate by calcite precipitation

Spontaneous precipitation of secondary calcite (CaCO₃) has been observed in 25 samples of landfill leachate-polluted stream waters. During the 6-month precipitation experiment, the formation of calcite acts as a principal trace-element scavenging process. The concentrations of Fe, Sr, Ba and Mn and other trace elements in solution significantly decreased as calcite formed during the experiments. The PHREEQC-2 geochemical code indicated high supersaturation of the initial leachate-polluted waters with respect to calcite. The chemical/mineralogical study (SEM/EDS, XRD, ICP MS) revealed that this newly formed calcite contains considerable amounts of metals and metalloids removed from solution. Such a geochemical process can be considered to be important for spontaneous decontamination in landfill-affected environments (stream sediments, soils) or landfill technical facilities (settling basins). This removal takes place especially during dry periods with low rain precipitation, when the landfill waters exhibit both higher alkalinity and higher trace element concentrations.     

Chemical forms of some heavy metals in Huanghe River sediments (China) and comparison with data from Rhine River sediments (West Germany)

The chemical forms of Fe, Mn, Zn, Cu, Cr, Pb and Cd in the Huanghe River sediments have been studied by sequential extraction techniques and the comparison with data from the Rhine River sediments has been made. In the Huanghe River sediments the average contents of metals, without exception, are below their respective contents in average shales and very close to their levels in Ca-poor granites. The major portion of metals is combined with the detrital and moderately reducible phases. Both in the Huanghe River and in the Rhine River sediments the distribution ratios of metals between the moderately reducible and the easily reducible phases are generally more than unity. However, the distribution ratios of Mn, Zn and Cd are obviously lower than those of Fe, Cr, Cu and Pb. As a result of contamination, the ratios of Fe, Cr, Cu and Pb show an apparent increase, but no remarkable ratio variation is observed for Mn, Zn and Cd. Metals in the Huanghe River sediments, especially Cu and Zn, show a tendency to be associated with the organic phase. The effect of carbonate on metal association preference seems to be less important than that in the Rhine River although there is higher content of carbonate in the Huanghe River sediments. Cd has a greater percentage of the exchangeable phase, which is similar to the result from the Rhine River sediments.     

Competitive adsorption,release and speciation of heavy metals in the Yellow River sediments,China

The competitive adsorption and the release of selected heavy metals and their speciation distribution before and after adsorption in the Yellow River sediments are discussed. The adsorption of metals onto sediments increases with increasing pH value and decreases with increasing ionic strength. The competitive coefficient K _c and the distribution coefficient K _d are obtained to analyze the competitive abilities of selected heavy metals, which are ranked as Pb > Cu >> Zn > Cd. The competition among selected heavy metals becomes more impetuous with increasing ion concentration in water. Speciation analysis was done by an improved analytical procedure involving five steps of sequential extraction. Cu, Pb and Zn were mainly transformed into the carbonate-bound form (50.8–87.7%) in adsorption. Most of (60.7–77.3%) Cd was transformed into the exchangeable form, and the percentage of carbonate-bound Cd was 19.7–30.4%. The release reaction was so quick that the release capacity of selected heavy metals from sediments to aqueous solution reached half of the maximum value only in 30 s. As opposed to adsorption, the release capacities of selected heavy metals were ranked as Cd > Zn >> Cu > Pb. In this study, Cd produces the most severe environmental hazards, because its concentration in the release solution is 85.8 times more than the human health criteria of US EPA.     

Heavy metal distribution and assessment in stream sediments of River Orle,Southwestern Nigeria

Ten heavy metals, namely, Ag, As, Cd, Co, Cr, Cu, Hg, Ni, Pb and Zn were partially extracted using aqua regia digestion method and analysed by ICP-AES from 56 stream sediment samples collected from River Orle, Igarra area, southwestern Nigeria. The analytical results were used to produce geochemical distribution maps for the elements and were subjected to univariate statistical analysis in order to evaluate the distribution and abundance of the heavy metals in the study area. The degree of pollution of these stream sediments by these heavy metals was evaluated by calculating such parameters as enrichment factors (EF), as well as pollution load and geo-accumulation indices (PLI and Igeo). Co, Cr, Cu, Ni, Pb and Zn are widely distributed in the drainage system while the distribution of Ag, Cd, As and Hg is restricted to only parts of the drainage system with Ag and Cd being localized to one sample site each near Epkeshi in the southern part of the study area. Cr and Pb display anomalously high concentrations, each from a site, also in the same locality where Ag and Cd were detected, indicating the likelihood that the four elements, Cr, Pb, Ag and Cd, are genetically related. Calculation of the enrichment factor (EF), pollution load index (PLI) and geo-accumulation index (Igeo) yielded results that indicate that all the 56 stream sediment sites, except one located about 4 km southeast of Epkeshi in the southern part of the Orle drainage system, are practically unpolluted by heavy metals. The relatively high metal concentration of this anomalous site having Pb EF of 62.5, PLI of 1.14 and Pb Igeo of 2.44 signifies Pb pollution. Both natural and anthropogenic sources of the Pb contamination around Epkeshi locality are possible. In conclusion, the levels of concentrations of heavy metals in the study area, in general, do not constitute any serious environmental risk except for Pb which needs to be monitored at only one site in the study area. Therefore the concentration ranges for the different heavy metals in the study area can serve as baseline environmental data against which the degree of pollution of these heavy metals can be evaluated in future.     

Heavy metal relationships in a Pennsylvania soil

Soils of loamy sand on weathered, sandy dolomite were cored from six holes up to 70 ft beneath a municipal waste landfill in central Pennsylvania. Mn, Fe, Ni, Co, Cu, Zn, Cd, Pb, and Ag were determined in exchangeable and non-exchangeable forms in total and < 15 μm soil samples. Most of these metals were bound in Mn oxides, non-exchangeable with 0.5 M CaCl₂. The Mn oxides (often X-ray amorphous) identified when crystalline as todorokite occurred chiefly as coatings on quartz grains.Somewhat higher amounts of acid leachable trace metals were found in the < 15 μm size fraction than in the total soil samples; however, trace metal/Mn ratios were similar in both. In general, the initial mild soil leaching, which dissolved chiefly Mn oxides, gave MnFeX>Co>Ni>Pb>Zn> Cu>Cd>Ag. The final leaching, which dissolved chiefly ferric oxides, gave Fe>Mn>Ni>Zn>Co> Cu>Pb>Cd>Ag. Samples taken from an unpolluted site and from the same soils affected for seven years by leachate from the refuse had similar metal contents.Soil extractable Co, Ni, Cu, and Zn could be predicted from the Mn extracted. Based in part on factor analysis of the data, Mn-rich oxides had at least tenfold higher heavy metal percentages than Fe-rich oxides (crystalline component goethite), reflecting their greater coprecipitation potential. Because of this potential and because of the generally higher solubility of Mn than Fe oxides, more heavy metals may be released from Mn-rich than from Fe-rich soils by disposal of organic-bearing wastes. However, leaching of the moisture-unsaturated soils in situ is rarely severe enough to completely dissolve both Mn and Fe oxides. Based on the Mn content, Cd, Cu, and Pb were depleted in soil moisture beneath the landfill relative to their amounts in the soil. This depletion may reflect factors including heterogeneity in metal content of the soil oxides; preferential resorption of these metals; and removal of the Cd, Cu, and Pb as organic precipitates or as inorganic precipitates such as carbonates.     

太湖MS岩芯重金属元素地球化学形态研究

采用BCR三步提取法对太湖MS岩芯沉积物中Cu、Fe、Mn、Ni、Pb和Zn等6种重金属元素的化学形态进行了研究.结果表明,有效结合态的Cu、Ni和Pb主要以有机物及硫化物结合态、Fe-Mn氧化物结合态存在,Fe和Zn主要以Fe-Mn氧化物结合态存在,Mn主要以可交换态及碳酸盐结合态存在;Fe-Mn氧化物结合态的Ni、Pb和Zn与可还原态的Mn有较好的正相关关系,有机物及硫化物结合态的Cu、Mn、Ni、Pb和Zn与有机碳含量有较好的正相关关系;重金属形态分布体现了重金属元素地球化学性质的差异,以及重金属形态含量与沉积物理化性质的关系.沉积岩芯重金属元素形态垂向变化规律及次生相富集系数表明,Cu、Mn、Ni、Pb和Zn在沉积岩芯13～4 cm有效结合态含量较稳定,为自然沉积;4～0 cm有效结合态含量明显升高,存在一定程度的人为污染.根据137Cs测年结果判断,沉积岩芯Cu、Mn、Ni、Pb和Zn等重金属污染开始于20世纪70年代末期,主要污染元素及污染历史与太湖流域污染工业类型及经济发展阶段相吻合.     

电感耦合等离子体发射光谱法和火焰原子吸收光谱法连续测定化探样品中12个元素

建立了地质化探样品中不同含量和检出限要求的12个元素的连续测定方法。样品经一次取样,用盐酸-氢氟酸-硝酸-高氯酸溶样,电感耦合等离子体发射光谱法测定铜、铅、锌、钴、镍、镉、锶、钡、钒、锰后,加碘化钾-甲基异丁基甲酮萃取分离,火焰原子吸收光谱法测定银、镉。银、镉的相对标准偏差(RSD,n=12)分别为6.5%、4.7%。与现行分析方法相比,建立的方法灵敏度和精密度高、准确度好,降低了生产成本,缩短了检测时间,尤其适合大量化探样品的测定。     

Selective chemical extraction of heavy metals in tailings and soils contaminated by mining activity: Environmental implications

Total concentrations of chemical elements in soils may not be enough to understand the mobility and bioavailability of the elements. It is important to characterise the degree of association of chemical elements in different physical and chemical phases of soil. Another geochemical characterisation methodology is to apply sequential selective chemical extraction techniques. A seven-step sequential extraction procedure was used to investigate the mobility and retention behaviour of Al, Fe, Mn, Cu, Zn, Pb, Cr, Co, Ni, Mo, Cd, Bi, Sn, W, Ag, As and U in specific physical–chemical and mineral phases in mine tailings and soils in the surroundings of the abandoned Ervedosa mine. The soil geochemical data show anomalies associated with mineralised veins or influenced by mining. Beyond the tailings, the highest recorded concentrations for most elements are in soils situated in mineralised areas or under the influence of tailings. The application of principal components analysis allowed recognition of (a) element associations according to their geochemical behaviour and (b) distinction between samples representing local geochemical background and samples representing contamination. Some metal cations (Mn, Cd, Cu, Zn, Co, Cr, Ni) showed important enrichment in the most mobilisable and bioavailable (i.e., water-soluble and exchangeable) fractions due likely to the acidic conditions in the area. In contrast, oxy-anions such as Mo and As showed lower mobility because of adsorption to Fe oxy-hydroxides. The residual fraction comprised largest proportions of Sn and Al and to a lesser extent Zn, Pb, Ni, Cr, Bi, W, and Ag, which are also present at low concentrations in the bioavailable fractions. The elements in secondary mineral phases (mainly Fe, Mn, Cu, Zn, Cd, Pb, W, Bi, Mo, Cr, Ni, Co, As and U) as well as in organic matter and sulphides are temporarily withheld, suggesting that they may be released to the environment by changes in physico-chemical conditions.     

Geochemical features of heavy metals in core sediments of northwestern Taihu Lake, China

Sequential core sediments from northwestern Taihu Lake in China were analyzed for grain size, organic carbon and heavy metal content. The sediments are composed of organic-poor clayey-fine silts. The chemical speciations of Cu, Fe, Mn, Ni, Pb, and Zn were also analyzed using the BCR sequential extraction procedure. Cu, Fe, Ni, and Zn are mainly associated with the residue fraction; Mn is concentrated mainly in exchangeable/carbonate fraction and residue fraction; and Pb mainly in Fe/Mn oxide fraction and organic/sulfide fraction. The exchangeable/carbonate fractions of Cu, Fe, Ni, Zn and Pb are lower. The fractions of Ni, Pb and Zn bound to the Fe/Mn oxide have significant correlations with reducible Mn; the organic/sulfide fractions of Cu, Mn, Ni, Pb, and Zn have significant correlations with TOC. The extractable fractions of Cu, Mn, Ni, Pb, and Zn are high at the top 4 cm of the core sediments as compared to those in the deeper layers, showing the anthropogenic input of heavy metals is due to rapid industrial development. The heavy metal pollution history of the sediments has been recorded since the late 1970s, determined by the result of ^137Cs dating.