Metal contamination and solid phase partitioning of metals in urban roadside sediments

This study was undertaken to assess the anthropogenic impact on metal concentrations of urban roadside sediments (N = 633) in Seoul city, Korea and to estimate the potential mobility of selected metals (Zn, Cu, Pb, Cr, Ni, and Cd) using sequential extraction. Comparison of metal concentrations in roadside sediments with mean background values in sediments collected from first- or second-order streams in Korea shows that Zn, Cu and Pb are most affected by anthropogenic inputs. The 206Pb/207Pb ratios of roadside sediments (range = 1.1419-1.1681; mean 1.1576 +/- 0.0068) suggest that Pb is mainly derived from industrial sources rather than from leaded gasoline. A five-step sequential extraction of roadside sediments showed that Zn, Cd and to a lesser degree Ni occur predominantly in the carbonate bound fraction, while Pb is highest in the reducible fraction, Cu in the organic fraction, and Cr in the residual fraction. It was found that the concentrations in the readily available exchangeable fraction were generally low for most metals examined, except for Ni whose exchangeable fraction was appreciable (average 15.2%). Considering the proportion of metals bound to the exchangeable and carbonate fractions, the comparative mobility of metals probably decreases in the order of Zn > Ni > Cd > Pb > Cu > Cr. As potential changes of redox state and pH may remobilize the metals bound to carbonates, reducible, and/or organic matter, and may release and flush them through drain networks into streams, careful monitoring of environmental conditions appears to be very important. With respect to ecotoxicity, it is apparent the Zn and Cu pollution is of particular concern in Seoul city.     

Metal partitioning in river sediments measured by sequential extraction and biomimetic approaches

We quantified the concentrations and distributions of metals (Cd, Cr, Cu, Ni, Pb, and Zn) in the sediments of Tuen Mun River, Hong Kong. The potential bioavailability of metals was assessed with a biomimetic extraction method using the sipunculan gut juices. The sediments were characterized by relatively high concentrations of trace metals. Field collected sediments were highly anoxic and the ratio of simultaneously extractable metal (sigmaSEM) to acid volatile sulfide (AVS) was much less than one in these sediments. The majority (>67%) of Cd, Pb, and Zn were bound to AVS, thus their concentrations in the sediment porewater were low. In contrast, Ni was little bound to AVS due to its lower ratios of SEM-Ni to total Ni concentrations. For Cu, relatively high concentrations in the sediment porewater was found, and total organic carbon, AVS and other resistant sulfide phase were the controlling factors for sedimentary Cu partitioning. Net metal adsorption from gut juices to anoxic sediments was observed in metal extraction experiments, suggesting that AVS determined the bioaccumulation and potential bioavailability of most metals in these sediments. Extraction of metals from the oxidized sediments by the gut juices was mainly attributed to metal redistribution from AVS to other geochemical phases. The gut juices were the most effective solvent or extractant than the simple electrolyte solution [I (NaNO(3)) = 0.01 M] and the natural overlying water. Cd was more easily extracted from the oxidized sediments than Zn that tended to have a stronger binding affinity with Fe-Mn oxide, clay and organic matter. The application of partial removal techniques in metal extraction experiments further demonstrated the differential controls of various sediment geochemical phases in affecting metal bioavailability, with the order of TOC > Fe-Mn oxides > carbonate.     

Heavy metals in coastal wetland sediments of the Pearl River Estuary, China

Sediment quality in coastal wetlands of the Pearl River Estuary was concerned since the wetlands were used for land reclamation, aquaculture and wildlife protection, and meanwhile served as one of the main ultimate sinks for large amount of heavy metals discharged from the rapidly developing Pearl River Delta. Total concentrations of heavy metal, such as Zn, Ni, Cr, Cu, Pb, and Cd, and their chemical speciation were investigated. Results showed that the sediments were significantly contaminated by Cd, Zn and Ni with concentration ranges of 2.79-4.65, 239.4-345.7 and 24.8-122.1mg/kg, respectively. A major portion (34.6-46.8%) of Pb, Cd, and Zn was strongly associated with exchangeable fractions, while Cu, Ni and Cr were predominantly associated with organic fractions, residual, and Fe-Mn oxide. Cd and Zn would be the main potential risk and the sediment quality is no longer meeting the demand of the current wetland utilization strategies.     

Comparison between fractionation and bioavailability of trace elements in rhizosphere and bulk soils

Rhizosphere is a microbiosphere and has quite different chemical, physical and biological properties from bulk soils. A greenhouse experiment was performed to compare the difference of fractionation and bioavailability of trace elements Cr, Ni, Zn, Cu, Pb and Cd between rhizosphere soil and bulk soil. In the meantime, the influence of air-drying on the fractionation and bioavailability was also investigated by using wet soil sample as a control. Soils in a homemade rhizobox were divided into four zones: rhizosphere, near rhizosphere, near bulk soil and bulk soil zones, which was designated as S1, S2, S3 and S4. Elemental speciations were fractionated to water soluble, exchangeable and carbonate bound (B1), Fe-Mn oxide bound (B2), and organic and sulfide bound (B3) by a sequential extraction procedure. Speciation differences were observed for elements Cr, Ni, Zn, Cu, Pb and Cd between the rhizosphere and bulk soils, and between the air-dried and wet soils as well. The concentrations of all six heavy metals in fraction B1 followed the order of S2 > S3 > S1 > S4 and for B2, the order was S2 > S3 S4 > S1. For B3, the order was S1 > S3 S4 > S2, while for Cd the order was S2 > S3 approximately/= S4 > S1. The air-drying increased elemental concentration in fractions B1 and B2 by 20-50% and decreased in fraction B3 by about 20-100%. Correlation analysis also indicated that the bioavailability correlation coefficient of fraction B1 in rhizosphere wet soil to plants was better than that between either air-dried or nonrhizosphere soils. Therefore, application of rhizosphere wet soils should be recommended in the future study on the speciation analysis of trace elements in soils and bioavailability.     

Use of sequential extraction to assess metal partitioning in soils

The state of heavy metal pollution and the mobility of Cd, Cu, Ni, Cr, Pb and Zn were studied in three texturally different agricultural soil profiles near a Cu-Ni smelter in Harjavalta, Finland. The pseudo-total concentrations were determined by an aqua regia procedure. Metals were also determined after division into four fractions by sequential extraction with (1) acetic acid (exchangeable and specifically adsorbed metals), (2) a reducing agent (bound to Fe/Mn hydroxides), (3) an oxidizing agent (bound to soil organic matter) and (4) aqua regia (bound to mineral structures). Fallout from the smelter has increased the concentrations of Cd, Cu and Ni in the topsoil, where 75-90% of Cd, 49-72% of Cu and 22-52% of Ni occurred in the first two fractions. Slight Pb and Zn pollution was evident as well. High proportions of mobile Cd, Cu and Ni also deeper in the sandy soil, closest to the smelter, indicated some downward movement of metals. The hydroxide-bound fraction of Pb dominated in almost all soils and horizons, while Ni, Cr and Zn mostly occurred in mineral structures. Aqua regia extraction is usefully supplemented with sequential extraction, particularly in less polluted soils and in soils that exhibit substantial textural differences within the profiles.     

Bioaccessibility and health risk of arsenic, mercury and other metals in urban street dusts from a mega-city, Nanjing, China

The oral bioaccessibility and the human health risks of As, Hg and other metals (Cu, Pb, Zn, Ni, Co, Cd, Cr, Mn, V and Fe) in urban street dusts from different land use districts in Nanjing (a mega-city), China were investigated. Both the total contents and the oral bioaccessibility estimated by the Simple Bioaccessibility Extraction Test (SBET) of the studied elements varied with street dusts from different land use districts. Cd, Zn, Mn, Pb, Hg and As showed high bioaccessibility. SBET-extractable contents of elements were significantly correlated with their total contents and the dust properties (pH, organic matter contents). The carcinogenic risk probability for As and Cr to children and adults were under the acceptable level (<1 × 10⁻⁴). Hazard Quotient values for single elements and Hazard Index values for all studied elements suggested potential non-carcinogenic health risk to children, but not to adults.     

The use of a sequential leaching procedure for heavy metal fractionation in green liquor dregs from a causticizing process at a pulp mill

A five-stage sequential leaching procedure was used to fractionate heavy metals (Cd, Cu, Pb, Cr, Zn, Fe, Mn, Ni, Co, As, V, Ba and Ti) in green liquor dregs into the following fractions: (1) water-soluble fraction (H2O), (2) exchangeable fraction (CH3COOH), (3) easily reduced fraction (HONH3Cl), (4) oxidizable fraction (H2O2 + CH3COONH4), and (5) residual fraction (HF + HNO3 + HCl). The green liquor dregs were derived from a causticizing process at a pulp mill at Kemi, Northern Finland. According to the leaching studies, the leachability of heavy metals in the water-soluble fraction varied between 0.5 and 2 mg kg(-1) expressed on a dry weight (d.w.) basis, indicating relatively low bioavailability of the metals. However, the concentration of Mn (2065 mg kg(-1); d.w.) showed a strong and of Zn (17.6 mg kg(-1); d.w.), Ni (39.7 mg kg(-1); d.w.) and Ba (32.0 mg kg(-1); d.w.) slightly tendency to be extracted in the exchangeable fraction. In addition, Zn, Mn, Ni, Co, V and Ba showed clear leachability in the easily reduced fraction, as well as Cd, Cu, Cr, Zn, Mn, As and Ba in the oxidizable fraction. For Cd, Cu, Cr, Zn, Mn, Ni, Co, Ba and Ti, the sum of leachable heavy metal concentrations in fractions 1-5 agreed relatively well with the "total" heavy metal concentrations. Recoveries of the sum of fractions 1-5 were 84-56% of those obtained by the US EPA method 3052 (i.e. concentrations obtained after microwave oven digestion with a mixture of HF and HNO3).     

Heavy metal distribution in marine sediments from the southwest coast of Spain

The latest version (1999) of the BCR-sequential extraction technique was used to determine the distribution of metals (Cu, Zn, Cd, Pb, Fe, Ni, Cr, and Mn) with major sedimentary phases (acid-soluble, reducible, oxidisable and residual) in samples from the southwest coast of Spain. The total metal content was also determined. The results showed that an extensive area along the coast (35 km long), near the joint mouth of the Tinto and Odiel Rivers, contains sediments with high concentrations of metals, with maximums of 649 mg/kg of Zn, 336 mg/kg of Cu, 197 mg/kg of Pb and 2.5 mg/kg of Cd. The values found for Cr, Ni and Mn are comparable to those in unpolluted areas. Based on the chemical distribution of metals, we found that Zn is the most mobile (i.e., it can pass easily into the water under changing environmental conditions). This metal showed the highest percentages in the acid-soluble fraction (the most labile), especially in the central coastal area, where the samples contained over 50% of this element associated with this fraction. This area close to the Tinto and Odiel river mouths also shows a significant increase in the mobility of Cd and Cu. In both cases the amount present in the residual fraction is lower, and the acid-soluble fraction is increased for Cd and the oxidisable fraction for Cu. However, the highest percentages of Fe, Cr and Ni are found in the residual fraction (84%, 89% and 75%, respectively), which implies that these metals are strongly bound to the sediments.     

Isotherms and sequential extraction procedures for evaluating sorption and distribution of heavy metals in soils

Heavy metals are potentially toxic to human life and the environment. Their contaminating effect in soils depends on chemical associations. Hence, determining the chemical form of a metal in soils is important to evaluate its mobility and bioavailability. We utilized a sequential extraction procedure and sorption isotherms (monometal and competitive) to evaluate the mobility and distribution of Cd, Cu, Ni, Pb, and Zn in four soils differing in their physicochemical properties: Calcixerollic Xerochrepts (Cx1 and Cx2), Paralithic Xerorthent (Px) and Lithic Haplumbrept (Lh). Most of the metals retained under point B conditions of sorption isotherms were extracted from the more mobile fractions: exchangeable and carbonates, in contrast with the profiles of the original soils where metals were preferently associated with the residual fraction. In soils having carbonate concentration under 6% (Cx1 and Lh), the exchangeable fraction was predominant, whereas in calcareous soils (Cx2 and Px) metals extracted from carbonates predominated. Partitioning profiles were in accordance with the affinity sequences deduced from the initial slope of isotherms and showed that the soils had a greater number of surface sites and higher affinity for Pb and Cu than for Cd, Ni, or Zn. In general, the simultaneous presence of the cations under study increased the percentages of metals released in the exchangeable fraction. The tendency towards less specific forms was more noticeable in Cx2 and Px soils and for Ni, Zn, and Cd. The affinity of inorganic surfaces was larger for Zn than for Cd or Ni, but the affinity of organic surfaces was larger for Cd or Ni than for Zn.     

Speciation of heavy metals in marine sediments vs their bioaccumulation by mussels.

Total contents and speciation of selected heavy metals, including Al, Fe, Co, Ni, Pb, Zn, Cu, Cr, were measured in sediment samples and mussels Mya arenaria and Astarte borealis collected in the Horsund Fjord off Spitsbergen (Norwegian Sea) and the Bay of Gdansk (Baltic Sea). The investigation aimed at revealing differences in the accumulation pattern of heavy metals in mussels inhabiting sediments characterized by varying metal bioavailability. The contents of metals adsorbed to sediments and associated with iron and manganese hydroxides, which were obtained by sequential extraction, were utilized as a measure of metal bioavailability. The contents of Cd, Pb, Zn, Cu and Cr in mussels collected off Spitsbergen were generally lower than those in mussels from the Baltic Sea. In sediments collected off Spitsbergen the bioavailable fraction represented a small proportion (0-3.7% adsorbed metals and 0-11% associated with metals hydroxides) of total heavy metal contents. In sediments from the Baltic Sea the percentages of metals adsorbed and bound to hydroxides were 1-46% and 1-13%, respectively. The differences in bioavailable metal contents measured in sediments were utilized to explain the different contents of metals in mussels collected in the corresponding sites.     

Partitioning and mobility behavior of metals in road dusts from national-scale industrial areas in Korea

In this study, we investigated the characteristics of heavy metal contamination in road dusts collected from industrial areas in Korea. A total of 12 sampling sites, including nine sites in three different industrial complexes (ICs), two IC vicinity areas and one background area, were selected for this study. The collected road dusts were divided into four categories. The heavy metals (Cd, Cu, Pb, Zn, and Ni) were extracted from the road dust by an aqua regia extraction method and analyzed by atomic absorption spectrometry. The highest concentrations of Cd, Cu, and Pb were identified in road dusts from areas near the non-ferrous metal IC, followed by those from the petrochemical IC. The petrochemical IC and the mechanical/shipbuilding IC showed the highest concentrations of Ni and Zn in their road dusts, respectively. The concentration of heavy metals in the road dusts collected from the IC vicinity areas, even those located in a rural environment, were very high. The concentration of heavy metals increased with decreasing particle size of the road dusts. This study also analyzed the mobility of the heavy metals in the road dusts using partial sequential extraction with the Tessier procedure. The order of mobility identified, based on exchangeable and carbonate fractions of the heavy metals, was Cd > Zn > Pb > Cu > Ni.     

Potentially toxic metal contamination of urban soils and roadside dust in Shanghai, China

A detailed investigation was conducted to understand the contamination characteristics of a selected set of potentially toxic metals in Shanghai. The amount of Pb, Zn, Cu, Cr, Cd and Ni were determined from 273 soil/dust samples collected within urban area. The results indicated that concentration of all metals except Ni in soils was significant, and metal pollution was even severer in roadside dust. A series of metal spatial distribution maps were created through geostatistical analysis, and the pollution hotspots tended to associate with city core area, major road junctions, and the regions close to industrial zones. In attempt of identifying the source of metals through geostatistical and multivariate statistical analyses, it was concluded as follows: Pb, Zn and Cu mainly originated from traffic contaminants; soil Ni was associated with natural concentration; Cd largely came from point-sourced industrial pollution; and Cr, Ni in dust were mainly related to atmospheric deposition.     

Speciation of metals in contaminated sediments from Oskarshamn Harbor,Oskarshamn, Sweden

Bottom sediments in coastal regions have been considered the ultimate sink for a number of contaminants, e.g., toxic metals. In this current study, speciation of metals in contaminated sediments of Oskarshamn harbor in the southeast of Sweden was performed in order to evaluate metal contents and their potential mobility and bioavailability. Sediment speciation was carried out by the sequential extraction BCR procedure for As, Cd, Cr, Cu, Hg, Ni, Pb, and Zn and the exchangeable (F1), reducible (F2), oxidizable (F3), and residual (R) fractions were determined. The results have shown that Zn and Cd were highly associated with the exchangeable fraction (F1) with 42–58 % and 43–46 %, respectively, of their total concentrations in the mobile phase. The assessment of sediment contamination on the basis of quality guidelines established by the Swedish Environmental Protection Agency (SEPA) and the Italian Ministry of Environment (Venice protocol for dredged sediments) has shown that sediments from Oskarshamn harbor are highly contaminated with toxic metals, especially Cu, Cd, Pb, Hg, As, and Zn posing potential ecological risks. Therefore, it is of crucial importance the implementation of adequate strategies to tackle contaminated sediments in coastal regions all over the world.     

Atmospheric deposition of metallic pollutants over the Ligurian Sea: labile and residual inputs

Atmospheric fluxes of six trace metals (Cd, Cr, Cu, Ni, Pb and Zn) with Al as a crustal reference were measured at Cap Ferrat (French Riviera) between February 1997 and July 1998. An original sampling protocol enabled the separation of labile (seawater at pH 2) and residual fractions in the total atmospheric input. Median acid-labile fractions were 91%, 69%, 83%, 84%, 97% and 98% of the total for Cd, Cr, Cu, Ni, Pb and Zn, respectively. Under the conditions used, lability of individual metals is related to the anthropogenic component of the samples. Enrichment factors and anthropogenic fraction are estimated for each metal. Some interannual changes are investigated (Pb, Zn). The observed increase of Zn inputs may be linked to local input from the Nice district waste plant (commissioned in 1988), 6.5 km away.     

Relationship between heavy metals concentrations in egret species,their environment and food chain differences from two Headworks of Pakistan

Concentration of ten metals (Cd, Cr, Co, Cu, Fe, Li, Mn, Ni, Pb and Zn) were analyzed in the egg contents, prey and soil samples of little egret (Egretta garzetta) and cattle egret (Bubulcus ibis) from two Headworks to determine habitat and species-specific differences; to assess the importance of prey and habitat contamination as an exposure source for heavy metals. Concentration of Cu, Mn, Cr and Pb in egg contents, Fe, Co, Cu, Mn, Zn in prey and Fe, Co, Cu, Ni, Li in surface soils were significantly different (P < 0.05). Mean metal concentrations of Cr, Pb and Cd were relatively higher in little egret whereas Cu and Mn were higher in the egg contents of cattle egret. The mean concentrations of Cu, Mn and Zn were higher in prey samples of cattle egrets and Cr, Cd and Pb in prey samples of little egrets. In soil samples collected from little egret heronries metal concentrations were higher except Cu and Ni. Correlation Analysis and Hierarchical Agglomerative Cluster Analysis (HACA) identified relatively similar associations of metals and their source identification. Metals such as Fe, Cu, Mn, and Li were related with geochemical origin from parent rock material as well as anthropogenic input whereas Cr, Cd, Pb, Ni, Co and Zn were associated mostly with anthropogenic activities. The study suggested that eggs are useful bio-monitor of local heavy metal contamination.     

北运河沉积物/水界面上重金属迁移转化规律

分析测定了6种元素(Cr、Co、Mn、Cu、Pb、Zn)在北运河水系10个采样点水体和表层沉积物中的含量和形态分布,利用SPSS 19.0统计软件对重金属在不同形态中的含量进行相关性分析。结果显示,北运河下游重金属污染程度高于上游;Cr、Cu、Pb、Zn在底泥可提取态中所占比例相当高,多数采样点都超过10.0%。所研究的重金属多数在底泥Fe-Mn结合态与悬浮物、可交换态、硫化物和有机质结合态均存在相关性;Mn是北运河地化循环中最为活跃的元素。     

巢湖表层沉积物中重金属的分布特征及其污染评价

以巢湖表层沉积物为研究对象,利用BCR连续提取法研究了沉积物中Cr、Co、Ni、Cu、Cd、Zn、V和Pb等8种重金属元素的分布特征,同时运用潜在风险指数法和地累积指数法综合评价了巢湖沉积物中重金属的生态风险。结果表明,巢湖沉积物中的重金属含量在空间上表现出东西高、中间低的分布特征。巢湖表层沉积物中Cr、Co、Ni、V和Cu 5种重金属都主要以残渣态为主,Zn和Cd主要以弱酸提取态为主,Pb以可还原态为主,同时,Co和Cu 2种元素的可交换态及可还原态含量占有较高比例,具有潜在危害性。相关性分析显示,Cr、Cu、Pb、Ni、Zn和Cd 6种重金属元素的来源和分布可能具有相似性,Co和V 2种重金属元素具有相似的地球化学行为且其主要来源可能与其他几种重金属不同。潜在生态风险指数评价结果表明,巢湖表层沉积物中8种重金属元素构成的生态危害顺序为:Cd>Pb>Co>Cu>Ni>Zn>V>Cr,Cd具有高的生态危害等级,其他7种重金属元素均为低生态危害等级。地累积指数法评价结果表明:巢湖沉积物重金属元素的富集程度为Cd>Zn>Pb>Co>Cu>V>Ni>Cr,Cr属于清洁级别,Co、Cu、V和Ni处于轻度污染水平,Zn和Pb处于偏中度污染,Cd达到了重污染水平。     

Evolution of heavy metal speciation during the aerobic composting process of sewage sludge

The contents of heavy metals and their bioavailability to the soil-plant system were the major limitation to the application of sewage sludge compost in soil. This study was conducted to determine the evolution of heavy metal speciation in the course of an aerobic composting, and investigate the influence of changes of composting process parameters including pH, temperature and organic matter (OM) content on distribution of heavy metal speciation in composted sludge. The sequential extraction procedure developed by Tessier et al. was used in sludge compost to determine the heavy metal speciation. Results showed that, during composting, (1) the contents of the residue fraction for Pb, Zn and Cd were decreased but those for Ni and Cr were increased; the Cu residue fraction was almost constant; (2) the contents of the total mobile fractions (including fractions 1-4) for Zn and Pb were significantly increased, but the increase of those for Cu and Ni were not so remarkable; (3) there were significant degrees of correlation between heavy metal fractions and changes of some selected parameters (for example, pH, composting temperature, and OM content). Only the content of the total mobile fractions for Cu could be predictable from its total content. For the prediction of the total mobile fractions of Zn, Ni, Cd and Cr, the R(2) value was significantly increased by the inclusion of other variables such as pH, temperature and OM content.     

Spatial distribution of heavy metals in urban soils of Naples city (Italy)

Concentrations of surface and sub-surface soil Cu, Cr, Pb and Zn in the Naples city urban area were measured in 1999. Contourmaps were constructed to describe the metals spatial distribution. In the most contaminated soil samples, metals were speciated by means of the European Commission sequential extraction procedure. At twelve sites, Cu, Pb and Zn levels in soil were compared with those from a 1974 sampling. Many surface soils from the urban area as well as from the eastern industrial district contained levels of Cu, Pb and Zn that largely exceeded the limits (120, 100 and 150 mg kg(-l) for Cu, Pb and Zn, respectively) set for soils of public, residential and private areas by the Italian Ministry of Environment. Chromium values were never above regulatory limits(120 mg kg(-1)). Copper apparently accumulates in soils contiguous to railway lines and tramway. Cu and Cr existed in soil mainly inorganic forms (-68%), whereas Pb occurs essentially as residual mineral phases (77%). The considerable presence of Zn in the soluble, exchangeable and carbonate bound fraction (23%) suggests this element has high potential bioavailability and leachability through the soil. Concentrations of Cu, Pb and Zn have greatly increased since the 1974 sampling, with higher accumulation in soils from roadside fields.