Application of multivariate geostatistics in the investigation of heavy metal contamination of roadside dusts from selected highways of the Greater Toronto Area, Canada

A good understanding of roadside soil contamination and the location of pollution sources is important for addressing many environmental problems. The results are reported here of an analysis of the content of metals in roadside dust samples of four major highways in the Greater Toronto area (GTA) in Ontario, Canada. The metals analyzed are Pb, Zn, Cd, Ni, Cr, Cu, Mn, and Fe. Multivariate geostatistical analysis [correlation analysis (CA), principal component analysis (PCA), and hierarchical cluster analysis (HCA)] were used to estimate soil chemical content variability. The correlation coefficient shows a positive correlation between Cr–Cd, Mn–Fe, and Fe–Cu, while negatively between Zn–Cd, Mn–Cd, Zn-Cr, Pb–Zn, and Ni–Zn. PCA shows that the three eigenvalues are less than one, and suggests that the contamination sources are processing industries and traffic. HCA classifies heavy metals in two major groups. The cluster has two larger subgroups: the first contains only the variables Fe, Mn, Cu, Cr, Ni, and Pb, and the second includes Cd and Zn. The geostatistical analysis allows geological and anthropogenic causes of variations in the contents of roadside dust heavy metals to be separated and common pollution sources to be identified. The study shows that the high concentration of traffic flows, the parent material mineralogical and chemical composition, and land use are the main sources for the heavy metal concentration in the analyzed samples.     

The influence of physicochemical parameters on bioavailability and bioaccessibility of heavy metals in sediments of the intertidal zone of Asaluyeh region,Persian Gulf,Iran

In this research, we have worked on the evaluation of heavy metal contamination in the sediments taken from the intertidal zone of Asaluyeh region using Modified Community Bureau of Reference sequential extraction method (mBCR), the simplified bioaccessibility extraction test (SBET), and calculated enrichment factor (EF). Also, potential influencing factors including sediment characteristics that may affect the heavy metals bioavailability and bioaccessibility were investigated. mBCR extraction analysis indicated that among the metals, Mn, Zn, V, Cu, and Cd exhibit relatively higher mobility, while Ti, Pb, Cr, and Ni occur mainly in the residual fractions. Based on the mean values, the bioaccessibility of metals decreased in the order: Mn (50.01%)>Cd (46.26%)>Zn (14.61%)>V (13.97%)>Pb (10.88%)>Ni (9.2%)>Ti (8.43%)>Cr (6.66%)>Cu (6.23%). The obtained results from the principal component analysis (PCA), EF and mBCR extraction showed that most anthropogenic-derived metals with higher solubility are more bioaccessible compared to those of natural origin. Multiple linear regression analysis demonstrated that the main physicochemical variables of the sediment influencing the bioaccessibility of metals include cation exchange capacity (CEC), pH, and particle size fraction.     

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.     

Heavy metals in freshly deposited sediments of the Gomati River (a tributary of the Ganga River): effects of human activities

 The concentrations of various metals (Cr, Cu, Co, Fe, Mn, Ni, Pb, Zn, and Cd) were determined in recently deposited surface sediments of the Gomati River in the Lucknow urban area. Markedly elevated concentrations (milligrams per kilogram) of some of the metals, Cd (0.26–3.62), Cu (33–147), Ni (45–86), Pb (25–77), and Zn (90–389) were observed. Profiles of these metals across the Lucknow urban stretch show a progressive downstream increase due to additions from 4 major drainage networks discharging the urban effluents into the river. The degree of metal contamination is compared with the local background and global standards. The geoaccumulation index order for the river sediments is Cd>Zn>Cu>Cr>Pb. Significant correlations were observed between Cr and Zn, Cr and Cu, Cu and Zn and total sediment carbon with Cr and Zn. This study reveals that the urbanization process is associated with higher concentrations of heavy metals such as Cd, Cu, Cr, Pb, and Zn in the Gomati River sediments. To keep the river clean for the future, it is strongly recommended that urban effluents should not be overlooked before their discharge into the river. Received: 16 February 1996 · Accepted: 29 February 1996     

包头市典型工业区表层土壤中重金属污染状况及其潜在生态风险研究

为了解包头市典型工业企业对其所在地土壤中重金属含量的影响及污染现状,利用相关性系数对其表层土壤中7种重金属(Cu、Zn、Pb、Cr、Cd、Mn、Ni)来源进行研究,并采用内梅罗综合污染指数法和潜在生态危害指数对其污染状况进行评价。结果表明,7种重金属含量平均值均高于内蒙古土壤背景值,其中Cd、Mn、Ni超标率已达100%,而Cu、Pb、Zn的超标率分别为97%、93%和93%,只有Cr超标率较低(53%),污染程度依次为CdPbCuNiZnMnCr,其中Pb和Cd为重度污染,Cu、Zn、Ni为中度污染,Cr、Mn为轻度污染;Cu、Zn、Cr、Mn、Ni可能同时来自工业生产和交通运输两个源,而Pb和Cd除上述来源外,燃煤烟气的排放有较大贡献。潜在生态危害依次为CdPbCuNiCrZnMn,其中Cd的潜在生态风险最大,应予以高度重视,其他金属的风险均为轻微。     

固体聚合膜电解浓集法测量天然水中低含量氚的化学淬灭效应研究

固体聚合膜电解浓集法是浓缩氚含量较低(1 Bq/m~3)的天然水样的常用方法,但因水样自身含有杂质离子或电解装置聚合膜带入杂质进入浓集液,使浓集液偏酸性,在测量过程中易产生化学淬灭效应,导致氚的测量值偏低。本文研究了水样自身存在的杂质离子和聚合膜上残留的杂质离子、样品溶液的pH值及其电导率所产生的化学淬灭效应的影响,实验表明,为减少化学淬灭效应,提高测量低含量氚的准确性,需保证水样溶液呈中性,电导率≤1μS/cm,同时避免杂质沉积在聚合膜上。如果水样溶液的pH值偏酸性、电导率大于1μS/cm,可采用酸碱混合型离子交换树脂去除水样中自身的杂质;对于聚合膜引入的杂质,可在电解后的水样中加入微量氨水将其pH值调节至中性。     

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.     

Heavy metal pollution in freshly deposited sediments of the Yamuna River (the Ganges River tributary): a case study from Delhi and Agra urban centres, India

 The Yamuna River sediments, collected from Delhi and Agra urban centres, were analysed for concentration and distribution of nine heavy metals by means of atomic adsorption spectrometry. Total metal contents varied in the following ranges (in mg/kg): Cr (157–817), Mn (515–1015), Fe (28,700–45,300), Co(11.7–28.4), Ni (40–538), Cu (40–1204), Zn (107–1974), Pb (22–856) and Cd (0.50–114.8). The degree of metal enrichment was compared with the average shale concentration and shows exceptionally high values for Cr, Ni, Cu, Zn, Pb and Cd in both urban centres. In the total heavy metal concentration, anthropogenic input contains 70% Cr, 74% Cu, 59% Zn, 46% Pb, 90% Cd in Delhi and 61% Cr, 23% Ni, 71% Cu, 72% Zn, 63% Pb, 94% Cd in Agra. A significant correlation was observed between increasing Cr, Ni, Zn, and Cu concentrations with increasing total sediment carbon and total sediment sulfur content. Based on the Müller's geoaccumulation index, the quality of the river sediments can be regarded as being moderately polluted to very highly polluted with Cr, Ni, Cu, Zn, Pb and Cd in the Delhi and Agra urban centres. The present sediment analysis, therefore, plays an important role in environmental measures for the Yamuna River and the planning of these city centres. Received: 21 June 1999 · Accepted: 1 October 1999     

Assessment of heavy metal pollution in surface water

A total of 96 surface water samples collected from river Ganga in West Bengal during 2004–05 was analyzed for pH, EC, Fe, Mn, Zn, Cu, Cd, Cr, Pb and Ni. The pH was found in the alkaline range (7.21–8.32), while conductance was obtained in the range of 0.225–0.615 mmhos/cm. Fe, Mn, Zn, Ni, Cr and Pb were detected in more than 92% of the samples in the range of 0.025–5.49, 0.025–2.72, 0.012–0.370, 0.012–0.375, 0.001–0.044 and 0.001–0.250 mg/L, respectively, whereas Cd and Cu were detected only in 20 and 36 samples (0.001–0.003 and 0.003–0.032 mg/L). Overall seasonal variation was significant for Fe, Mn, Cd and Cr. The maximum mean concentration of Fe (1.520 mg/L) was observed in summer, Mn (0.423 mg/L) in monsoon but Cd (0.003 mg/L) and Cr (0.020 mg/L) exhibited their maximum during the winter season. Fe, Mn and Cd concentration also varied with the change of sampling locations. The highest mean concentrations (mg/L) of Fe (1.485), Zn (0.085) and Cu (0.006) were observed at Palta, those for Mn (0.420) and Ni (0.054) at Berhampore, whereas the maximum of Pb (0.024 mg/L) and Cr (0.018 mg/L) was obtained at the downstream station, Uluberia. All in all, the dominance of various heavy metals in the surface water of the river Ganga followed the sequence: Fe > Mn > Ni > Cr > Pb > Zn > Cu > Cd. A significant positive correlation was exhibited for conductivity with Cd and Cr of water but Mn exhibited a negative correlation with conductivity.     

Accumulation of potentially toxic elements in sediments in Budi Lagoon,Araucania Region,Chile

The concentrations of Cd, Cu, Mn, Ni, Pb, Fe and Zn were determined in superficial sediments extracted from nine zones of Budi Lagoon, located in the Araucanía Region (Chile). The concentrations of these metals were determined by flame atomic absorption spectroscopy and the method was validated using certified reference material (marine sediment). The concentration ranges found for the trace elements were: Pb < 0.5; Cd < 0.2–3.9; Cu 21.8–61.9; Ni 31.2–59.4; Zn 54.5–94.8 mgkg^?1 (dry weight). The elements that registered the highest concentrations were Mn 285.4–989.8 mgkg^?1 and Fe 4.8–10.6 %. The lagoon cluster analysis of the stations was divided into three groups (Temo station with high Cu and low Mn concentrations, Bolleco, Comué, Allipén and Deume 3 stations presented highest Cd concentration, and another group Botapulli, Río Budi, Deume 2 and Deume 1 stations presented low levels of Cd). The textural characteristics of the sediment were determined (gravel, sand and mud) and the results were correlated with the concentrations of the metals in the various study zones. The sediments of Budi Lagoon presented high levels of Fe and Mn, which are of natural origin and exceed the maximum values recorded by many authors. With respect to the recorded concentrations for Cd, Cu, Ni and Zn, are within the ranges published by other authors in similar works. The Pb element was not detected. The results were subjected to statistical analysis to evaluate the correlations between the content of the elements and obtain the site of sediment.     

Multivariate analysis of heavy metals in surface sediments from lower reaches of the Xiangjiang River, southern China

The concentrations of heavy metals (Cr, Mn, Co, Ni, Cu, Zn, Cd, and Pb) in 16 samples collected from the lower reach (Changsha–Xiangtan–Zhuzhou section) of the Xiangjiang River in southern China were determined by high-resolution inductively coupled plasma mass spectroscopy (HR-ICPMS). Multivariate analysis, such as principal component analysis and cluster analysis, coupled with correlation coefficient analysis, was used to analyze the analytical data and to identify possible pollution sources of heavy metals. The results showed that the eight studied heavy metals accumulated in the sediments from the lower Xiangjiang River, especially Mn, Cu, Zn, Pb and Cd, which were 2.0–2.6, 1.7–2.6, 3.5–3.8, 3.2–3.6 and 189.5–152.8 times the soil trace element background for Hunan Province and UCC background values, respectively. Principal component analysis and cluster analysis, coupled with correlation coefficient analysis, revealed that the sediments from lower Xiangjiang River were mainly influenced by two sources: Cr, Co, Ni, Cu, Zn, Cd and Pb mainly originated from industrial sources, whereas Mn was derived from both industrial and natural sources, but mainly from natural sources due to weathering and erosion.     

Heavy metals pollution of aquatic ecosystems in the vicinity of a recently closed underground lead-zinc mine (Basque Country, Spain)

A presentation is made of the study of an underground polymetallic sulphide mine and the pollution caused by this in the adjoining aquatic ecosystems. Troya Mine is in the Basque Cantabrian region (northern Spain). The annual production of the ore deposit of over 3.7 million tons of Pb (0.9%), Zn (11.2%) and Cu (0.2%) was 300,000 t. It was open and producing from 1986-1993. The mineralization was made up of pyrite, marcasite, sphalerite, galena, chalcopyrite and arsenopyrite. Only the Zn and the Pb were mined. We studied the distribution and behaviour of the heavy metals Zn, Pb, Fe, Mn, Cu, Cr and Cd in the water column, dissolved and suspended fractions, and in the sediments of Estanda Stream and of Gezala Creek. Zn, Cd and Mn tend to be found in the water; Fe, Pb, Cu and Cr appear as an adsorbed fractionin the solid phases. Those of the second group are significantly linked to the fluvial sediments and present very high levels. The concentrations of the metals are conditioned by the waters from the mine galleries, by the leached waste, by the surface runoff, and by overflow from the spillway of the tailings pond. Our observations provide knowledge on the extent of the polluting power of the metals, the physico-chemical effects in play and the subsequent chances of recovering these highly affected environments.     

Impact of land use types on the concentrations of metals in soils of urban environment in Nigeria

The concentrations of metals (Cd, Pb, Ni, Cr, Cu, Fe, Mn and Zn) were determined in soils under different land use types in an urban environment in order to study the impact of land uses on the concentrations of metals in the soils. The mean concentration range of metals for all land use types were 42.1 to 410, 11.2 to 118.2, 4388.2 to 31891.1, 9.7 to 65.4, 0.1 to 1.8, 4.7 to 35.2, 2.0 to 16.8 and 77.9 to 881.7 mg/kg, for Mn, Pb, Fe, Cu, Cd, Cr, Ni and Zn, respectively. The computed multiple pollution index (MPI) indicated that 67 % of the examined sites had MPI values between 1 and 20 i.e. at the pollution range, while 33 % of sites had MPI values of zero which indicated that these sites were not polluted with the studied metals. Zinc had the highest impact on the multiple pollution index values. Three main principal components were identified from the principal component analysis which include (i) Cu, Zn, Pb, Cr and Ni originating from both industrial and agricultural sources, and as well as automobile exhausts; (ii) Fe and Mn which originated from both natural and anthropogenic sources; (iii) Cd which its anthropogenic origin is different from components I and II. This study provided information on the sources of metals in the urban environment and extent of contamination associated with each land use, which are useful in the ranking of contaminated sites, environmental quality management, environmental forensic studies and guidance for remediation/redevelopment of contaminated land.     

Assessment of heavy metals contamination in urban topsoil from Changchun City,China

Due to the rapid urbanization and industrialization that has occurred in China over the last few decades, metals have been continuously emitted into the urban environment and now pose a serious threat to human health. Indeed, there is a growing concern over the potential for pollution of urban soils with heavy metals. Therefore, an extensive soil survey was conducted in urban areas of Changchun, China, to evaluate the current status of heavy metal contamination in soils and to evaluate its potential sources. A total of 352 samples of urban soils were collected from urban areas of Changchun using a systematic sampling strategy in which one sample per km² was taken (0 ~ 20 cm). The levels of Cu, Pb, Zn and the major elements (Mn, Al₂O₃, CaO, Fe₂O₃, MgO, SiO₂, K₂O and NaO) were then determined by X-Ray fluorescence spectrometry (XRF), while the level of Cd was determined by graphite furnace atomic absorption spectrometry (GF-AAS), and the Hg and As concentrations were determined by atomic fluorescence spectroscopy (AFS). The results indicated that, when compared with the background values of topsoil in the Changchun region, the topsoil in urban areas were enriched with metals, particularly Cu, Cd, Zn, Pb and Hg. The results of correlation coefficient analysis showed that Hg, As, Cd, Cu, Pb and Zn were significantly positive correlated with each other, while Cr and Mn formed another group. Moreover, significantly positive correlations were observed between pH and Zn, Pb, Cu, Cd, As and Hg, indicating that pH influences the distributions of these metals in urban soils in Changchun. Principal component analysis (PCA) was conducted to identify sources of heavy metals and the results revealed distinctly different associations among the trace metals and the major elements in the urban soils. The concentration of Cr appeared to be controlled by the parent material (natural sources), while Cu, Pb and Zn were mainly from vehicle emissions, with Zn primarily coming from vehicle tires. Additionally, Hg and As primarily originated from coal combustion, while Cd was mainly associated with industrial sources. According to the pollution index (PI) of each metal, the overall levels of metal pollution were not especially high, but there were clearly contaminated sites concentrated in the central and northeast portion of the studied region. The Nemerow integrated pollution index (NIPI) of the seven metals also indicated that urban soils in Changchun city were classified as having low level of pollution.     

Geochemical and statistical analysis of trace metals in atmospheric particulates in Wuhan, central China

The geochemical characteristics of trace metals (As, Cr, Co, Cd, Cu, Mn, Ni, Pb, V and Zn) in PM10 in Wuhan, the biggest metropolitan in central China, as well as their sources and contributions were analyzed. As PM10 has been the principal contaminant of air in Wuhan for years, concentrations of trace metals were measured in PM10 using high-volume samplers at one urban (Hankou) and one industrial (Changqian) site in Wuhan between September 2003 and September 2004. Based on the results, PM10 in Wuhan is characterized by relatively high levels of As, Cd, Mn, Pb and Zn compared with other Asian cities. The time-series of these elements indicated that As, Cu and Zn at both sites have similar trends, whereas Pb levels showed different patterns due to different emission sources. Factor analysis was applied to the datasets focusing on the apportionment of the mass of selected trace metals. Results indicate that Pb, Cd and As have a common source (smelting) at both sites, whereas the sources of Ni vary from coal combustion and steel in Changqian to mineral and traffic in Hankou.     

Speciation of some heavy metals in bottom sediments of the Ob and Yenisei estuarine zones

The speciation of Fe, Mn, Zn, Cu, Co, Ni, Cr, Pb, and Cd was studied in 52 samples of bottom sediments collected during Cruise 49 of the R/V Dmitrii Mendeleev in estuaries of the Ob and Yenisei rivers in the southwestern Kara Sea. Immediately after sampling, the samples were subjected to on-board consecutive extraction to separate metal species according to their modes of occurrence in the sediments: (1) adsorbed, (2) amorphous Fe-Mn hydroxides and related metals, (3) organic + sulfide, and (4) residual, or lithogenic. The atomic absorption spectroscopy of the extracts was carried out at a stationary laboratory. The distribution of Fe, Zn, Cu, Co, Ni, Cr, Pb, and Cd species is characterized by the predominance of lithogenic or geochemically inert modes (70–95% of the bulk content), in which the metals are bound in terrigenous and clastic mineral particles and organic detritus. About half of the total Mn amount and 15–30% Zn and Cu is contained in geochemically mobile modes. The spatiotemporal variations in the proportions of metal species in the surface layer of sediments along the nearly meridional sections and through the vertical sections of bottom sediments cores testify that Mn and, to a lesser extent, Cu are the most sensitive to changes in the sedimentation environment. The role of their geochemically mobile species notably increases under reducing conditions.     

Geochemistry of trace metals and Pb isotopes of sediments from the lowermost Xiangjiang River, Hunan Province (P. R. China): implications on sources of trace metals

This paper reports a geochemical study of trace metals and Pb isotopes of sediments from the lowermost Xiangjiang River, Hunan province (P. R. China). Trace metals Ba, Bi, Sc, V, Cr, Mn, Co, Ni, Cu, Zn, Mo, Cd, Sn, Sb, Pb, Tl, Th, U, Zr, Hf, Nb and Ta were analyzed using ICP-MS, and Pb isotopes of the bulk sediments were measured by MC-ICP-MS. The results show that trace metals Cd, Bi, Sn, Sc, Cr, Mn, Co, Ni, Cu, Zn, Sb, Pb and Tl are enriched in the sediments. Among these metals, Cd, Bi and Sn are extremely highly enriched (EF values >40), metals Zn, Sn, Sb and Pb significantly highly (5 < EF < 20), and metals Sc, Cr, Mn, Co, Ni, Cu and Tl moderately highly (2 < EF < 5) enriched in the river sediments. All these metals, however, are moderately enriched in the lake sediments. Geochemical results of trace metals Th, Sc, Co, Cr, Zr, Hf and La, and Pb isotopes suggest that metals in the river sediments are of multi-sources, including both natural and anthropogenic sources. Metals of the natural sources might be contributed mostly from weathering of the Indosinian granites (GR) and Palaeozoic sandstones (PL), and metals of anthropogenic sources were contributed from Pb–Zn ore deposits distributed in upper river areas. Metals in the lake sediments consist of the anthropogenic proportions, which were contributed from automobile exhausts and coal dusts. Thus, heavy-metal contamination for the river sediments is attributed to the exploitation and utilization (e.g., mining, smelting, and refining) of Pb–Zn ore mineral resources in the upper river areas, and this for the lake sediments was caused by automobile exhausts and coal combustion. Metals Bi, Cd, Pb, Sn and Sb have anthropogenic proportion of higher than 90%, with natural contribution less than 10%. Metals Mn and Zn consist of anthropogenic proportion of 60–85%, with natural proportion higher than 15%. Metals Sc, Cr, Co, Cu, Tl, Th, U and Ta have anthropogenic proportion of 30–70%, with natural contribution higher than 30%. Metals Ba, V and Mo might be contributed mostly from natural process.     

Geochemistry of trace metals associated with reduced sulfur in freshwater sediments

Porewater concentration profiles were determined for Fe, trace elements (As, Cd, Co, Cu, Mn, Ni, Pb, Zn), sulfide, SO₄ and pH in two Canadian Shield lakes (Chevreuil and Clearwater). Profiles of pyrite, sedimentary trace elements associated with pyrite and AVS were also obtained at the same sites. Thermodynamic calculations are used, for the anoxic porewaters where sulfide was measured, to characterize diagenetic processes involving sulfide and trace elements and to illustrate the importance of sulfide, and possibly polysulfides and thiols, in binding trace elements. The ion activity products (IAP) of Fe sulfide agree with the solubility products (K_s) of greigite or mackinawite. For Co, Ni and Zn, IAP values are close to the K_S values of their sulfide precipitates; for Cu and Pb, IAP/K_s indicate large oversaturations, which can be explained by the presence of other ligands (not measured) such as polysulfides (Cu) and thiols (Pb). Cobalt, Cu, Ni and Zn porewater profiles generally display a decrease in concentration with increasing ΣH₂S, as expected for transition metals, whereas Cd, Pb and Zn show an increase (mobilisation). The results suggest that removal of trace elements from anoxic porewaters occurs by coprecipitation (As and Mn) with FeS(s) and/or adsorption (As and Mn) on FeS(s), and by formation of discrete solid sulfides (Cd, Cu, Ni, Pb, Zn and Co). Reactive Fe is extensively sulfidized (51–65%) in both lakes, mostly as pyrite, but also as AVS. Similarities between As, Co, Cu and Ni to Fe ratios in pyrite and their corresponding mean diffusive flux ratios suggest that pyrite is an important sink at depth for these trace elements. High molar ratios of trace elements to Fe in pyrite from Clearwater Lake correspond chronologically to the onset of smelting activities. AVS can be an important reservoir of reactive As, Cd and Ni and, to a lesser extent, of Co, Cu and Pb. Overall, the trace elements most extensively sulfidized were Ni, Cd and As (maximum of 100%, 81% and 49% of the reactive fraction, respectively), whereas Co, Cu, Mn, Pb and Zn were only moderately sulfidized (11–16%).     

Evidences for heavy metal contamination in surface sediments of seagrass ecosystem of Lakshadweep archipelago, India

Surface sediments of nine islands of Lakshadweep were evaluated for their heavy metal concentration (Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb and Zn). Sediments of thirteen seagrass and seven non seagrass sites were collected randomly and analysed for heavy metal concentration using Inductively Coupled Plasma Optical Emission Spectrometer. Heavy metals like Cu, Ni and Zn were found in higher concentrations in the seagrass sediments, whereas other heavy metals such as Cd, Co, Cr, Fe, Mn and Pb were higher in non seagrass sediments. Different pollution indices were calculated to evaluate contamination level of all heavy metals in the sediments. Cadmium recorded higher contamination factor (1.733–21.067), enrichment factor (276.10–12,270) and Geo-accumulation Index (0.208–3.811) both in seagrass and nonseagrass sediments. Multivariate statistical analysis such as principal component analysis and cluster analysis coupled together with correlation co-efficient was used to identify the possible sources of heavy metal pollution in the region. Average concentrations of Cd in Lakshadweep islands were slightly higher than effective range, low but still below effective range medium. All other metals were still below these ranges indicating fairly uncontaminated sediment in the region.     

The spatial distribution pattern of heavy metal concentrations in urban soils — a study of anthropogenic effects in Berehove,Ukraine

In the present study we examined the Ba, Cd, Cr, Cu, Fe, Mn, Ni, Pb and Zn contamination levels of the soils of Berehove, a small city in West-Ukraine. As a first step we determined the spatial distribution of the heavy metal contents of the urban soils; then, by studying the land use structure of the city and by statistical analysis we identified the major sources of contamination; we established a matrix of correlations between the heavy metal contents of the soils and the different types of land use; and finally, we drew a conclusion regarding the possible origin(s) of these heavy metals. By means of multivariate statistical analysis we established that of the investigated metals, Ba, Cd, Cu, Pb and Zn accumulated in the city’s soils primarily as a result of anthropogenic activity. In the most polluted urban areas (i.e. in the industrial zones and along the roads and highways with heavy traffic), in the case of several metals (Ba, Cd, Cu, Pb, Zn) we measured concentration levels even two or three times higher than the threshold limit values. Furthermore, Cr, Fe and Ni are primarily of lithogenic origin; therefore, the soil concentrations of these heavy metals depend mainly on the chemical composition of the soil-forming rocks.