Environmental contamination of trace elements in the vicinity of Okpara coal mine, Enugu, Southeastern Nigeria

Water, sediment, and mine spoil samples were collected within the vicinity of the Okpara coal mine in Enugu, Southeastern Nigeria, and analyzed for trace elements using ICP-MS to assess the level of environmental contamination by these elements. The results obtained show that the mine spoils and sediments are relatively enriched in Fe, with mean values of 1,307.8(mg/kg) for mine spoils and 94.15% for sediments. As, Cd, Cr, Mn,Ni, Pb, and Zn in the sediments were found to be enriched relative to the mean values obtained from the study area, showing contamination by these elements. The mean values of Fe, Mn, Cu, and Cr in the mine spoils and mean values of Fe, Cu, Pb, Zn, Ni, Cr, and Mn in sediments, respectively, are above the background values obtained from coal and shale in the study area, indicating enrichment with these elements. The water and sediments are moderately acidic, with mean pH values of 4.22?±?1.06 and 4.66?±?1.35, respectively. With the exception of Fe, Mn, and Ni, all other elements are within the Nigerian water quality standard and WHO limits for drinking water and other domestic purposes. The strong to moderate positive correlation between Fe and Cu (r?=?0.72), Fe and Zn (r?=?0.88), and Fe and As (r?=?0.60) at p?<?0.05 as obtained for the sediments depict the scavenging effect of Fe on these mobile elements. As also shows a strong positive correlation with Mn (r?=?≥ 0.70, p?<?0.05), indicating that Mn plays a major role in scavenging elements that are not co-precipitated with Fe. In water, the strong positive correlation observed between Cr and Cd (r?=?1.00), Cu and Ni (r?=?0.94), Pb and Cu (r?=?0.87) and Zn and Cu (r?=?0.99); Ni and Pb (r?=?0.83) and Zn and Ni (r?=?0.97); and between Pb and Zn (0.84) at p?<?0.05 may indicate similar element–water reaction control on the system due to similarities in chemical properties as well as a common source. Elevated levels of heavy metals in sediments relative to surface water probably imply that sorption and co-precipitation on Al and Fe oxides are more effective in the mobilization and attenuation of heavy metals in the mine area than acid-induced dissolution. The level of concentration of trace elements for the mine spoils will serve as baseline data for future reference in the study area.     

Citywide distribution of lead and other element in soils and indoor dusts in Syracuse,NY

Associations between Pb, Zn, Fe and Mn in soils and indoor dusts in urban Syracuse, NY have been investigated at different levels of spatial aggregation. The concentrations of these elements of interest (EOI) in 3566 soil samples were mapped across the city to investigate variations in concentration potentially associated with specific city locations. Indoor floor dust loadings for the EOI determined at 433 residences were mapped in a similar fashion. Pearson product correlation coefficients at different levels of soil sample aggregation (individual sampling points, block group averages, and census tract (CT) averages), consistently demonstrated a strong correlation between soil Pb and Zn concentrations. Correlations between Pb and both Fe and Mn soil concentrations were also significant. However, the correlation between the Fe and Mn floor dust loadings was much stronger than that for soil, as were the correlations between the Pb and both the Fe and Mn dust loadings. The correlation between the Fe and Zn floor dust loadings was far less significant. Surprisingly, most of the correlations between the paired EOI in the dusts and soils at the individual homes were mostly not statistically significant. The two correlations of any significance, and these were between the Pb in soil and the Pb in the dust, and between Pb in dust and Zn in soil.     

Differences in uptake and distribution patterns between zinc and cadmium in <Emphasis Type="Italic">Vicia villosa</Emphasis>

Vicia villosa is an annual legume plant. Field-growing experiments were performed on six plots under different soil conditions. Variations in the concentrations of Zn and Cd in tissues were investigated. Differences in distribution patterns between Zn and Cd appeared during growing: the concentrations of Zn in roots in sandstone-derived soils were relatively higher than those in limestone-derived soils, and the uptake patterns of Zn by roots should be similar to those of iron (Fe). However, the concentrations of Cd in roots in limestone-derived soils were higher than those in sandstone-derived soils, and the uptake patterns of Cd by roots should be similar to those of manganese (Mn). On the contrast, the distribution patterns of Zn were similar to those of Mn, while the distribution patterns of Cd were similar to those of Fe in tissues, indicating that the uptake patterns of Zn and Cd were different from distribution patterns.     

Geogenic and anthropogenic zinc in epiphytic and terricolous lichens in Finland

At 31 sites in Finland the Zn content was determined of the epiphytic lichen Hypogymnia physodes (L.) Nyl. growing on pine and birch, the terricolous lichen Cladina spp. in pine bark, and the inner part of birch bark. The anomalous contents of Zn in H. physodes on pine and Cladina spp. in soil appeared to be strongly related to sulphide ore deposits. Anthropogenic Zn correlated closely with S and Fe in H. physodes on pine and with Fe in Cladina spp. The binding of geogenic Zn was related to iron hydroxides, and was attributed to the different uptake mechanism of S in these lichens. Elevated values of Zn in H. physodes on birch were due to both geogenic and anthropogenic sources. Zinc in pine bark increased with the Zn content in H. physodes and reached a limiting value.     

Impact of the past mining activity in Roşia Montană (Romania) on soil and vegetation

The paper presents the results of a combined soil and vegetation survey in Ro?ia Montan? mining area (western Romania), famous for its gold and silver deposits, extensively exploited over the last 2,000 years. As the ore extraction has ceased in 2006 and new operations could be initiated in the future, the study contributes to the definition of the environmental baseline. Samples of topsoil and leaves of the tree species Betula pendula and Carpinus betulus have been collected from the inside and outside of the mining area, on a total surface of more than 60 km². The pH and heavy metal concentrations (Cd, Cr, Cu, Ni, Pb, and Zn) have been measured on 262 soils/sediments samples, revealing the predominantly acidic character of soils and the generally low contents of heavy metals. Stronger acidity and higher contents of heavy metals have been noticed in the proximity of the mining site, on the tailings and waste rock dumps, and along the streams with acid water. More than 100 leaf samples have been analysed for the same heavy metals as soils and also for chlorophyll fluorescence and pigment concentrations. B. pendula has shown a particular ability to concentrate Zn in leaves, at levels that may greatly exceed the Zn content in the corresponding soil samples. The correlation between the heavy metal contents in leaves and in soils, in most of the cases, is not very strong, presumably in relation to the low concentrations in soils. The chlorophyll concentration in leaves of B. pendula slightly diminishes on soils with low pH.     

Risk of metal mobility in soils from a Pb/Zn depleted mine (Lugo,Spain)

The risk of Pb, Zn and Cd mobility is evaluated in soils from a depleted mine at Rubiais (Lugo, Spain). This area is under special protection because of its outstanding natural value. Soils from nine different areas were selected: at the mining zone (R1, R2, R3), at minespoils (R4, R5, R6) and soils developed on the settling pond (R7, R8, R9). A control soil (RC) was sampled outside the mine. The objectives are (i) to study the characteristics of soils with high influence on metal retention, (ii) to determine the content of Pb, Zn and Cd comparing it with the generic reference levels, and (iii) to evaluate the distribution and the interactions between the metals and the soil geochemical phases by means of sequential chemical extraction, X-ray diffraction, field emission scanning electron microscopy/energy-dispersive X-ray spectroscopy (FE-SEM/EDS) and time of flight secondary ion mass spectrometry (TOF–SIMS). The concentration of Pb, Zn and Cd ranges 850–6,761, 1,754–32,287 and 1.8–43.7 mg kg^?1, respectively, and the highest proportion is in the residual fraction. The Mn oxides highly influence the retention of Cd while Pb retention is mainly influenced by Fe oxides. Zn is uniformly distributed amongst the residual fraction and the Fe and Mn oxides. TOF–SIMS and SEM/EDS techniques confirm the fractionation results, showing how Pb and Zn are as sulphide and associated with Fe and Mn oxides. Nevertheless, care should be taken since oxides and sulphides could suffer sulphide oxidation processes or alteration of the oxides causing leaching and the contamination of the protected ecosystem.     

Engelmann Spruce (Picea engelmannii) as a biological monitor of changes in soil metal loading related to past mining activity

Engelmann spruce (Picea engelmannii) is the dominant tree species in many abandoned mine areas of the Rocky Mountains. It is long-lived, and therefore, may act as a long term biological monitor of changes in soil chemistry caused by past mining activity. In this study, laser ablation inductively coupled mass spectrometry (LA-ICPMS) was used to analyze individual tree rings of Engelmann spruce for Fe, Zn, Cu, Cd, Mn, Pb and Sr concentrations. Cores were obtained from trees growing in tailings-impacted and control (non-tailings impacted) sites near the Waldorf mine (Waldorf, CO, USA). Zinc, Cu, Fe, Cd, Pb and Sr concentrations remained low and consistent over time in the control tree rings. However, in the tailings impacted cores, concentrations of Zn, Cu, Fe and Cd increase significantly in post-mining rings. In addition, Zn, Cu, Fe, and Cd concentrations in pre-mining rings of both the control and tailings impacted cores are similar, indicating that present day soil concentrations of these elements in the control area are a reasonable estimation of background for this area. Lead and Sr concentrations in control and tailings-impacted rings remained similar and relatively constant through time and are not useful in determining changes in soil chemistry due to past mining activity.     

Partitioning of manganese,iron, copper,zinc, lead,cobalt, and nickel in black coatings on stream boulders in the vicinity of the Magruder mine,Lincoln Co., Georgia

Sequential digestions of Fe-Mn oxide coated boulders collected upstream and downstream from the Magruder mine, Lincoln Co., Georgia, indicate probable partitioning relationships for Zn, Cu, Pb, Co, and Ni with respect to Mn and Fe. Initial digestion with 0.1M hydroxylamine hydrochloride (Hxl) in 0.01M HNO₃ selectively dissolyes Mn oxides, whereas subsequent digestion with 1:4 HCl dissolves remaining Fe oxides.The results indicate that partitioning is not constant, but varies systematically with respect to the location of metal-rich waters derived from sulfide mineralization. Upstream from the mineralized zone Zn and Ni are distinctly partitioned to the Fe oxide component and Co and Cu are partitioned to the Mn oxide component. Immediately downstream from the mineralized zone, Mn oxides become relatively more enriched in Zn, whereas Fe oxides are relatively more enriched in Cu, Co, and Ni. Analytical precision for Pb is poor, but available data suggests it is more closely associated with Fe oxides.For routine geochemical surveys utilizing coated surfaces, a one-step digestion method is probably adequate. Parameters useful for detecting sulfide mineralization are metal concentrations normalized to surface area or various ratios (e.g. Zn/(Mn + Fe), Cu/Mn, Pb/Fe). Ratios can be obtained much faster, and at lower analytical costs than conventional analysis of stream sediment.     

A possible base-metal indicator plant from mamandur,south india

Sixty-five samples of rocks, soils, plants and well waters in the Mamandur area have been analysed for Cu, Zn, Pb, Sr, K, Na, and Mn by atomic absorption spectrophotometry. Among the plants, Waltheria indica Sterculiaceae is confined to mineralised ground in the area. This plant is characterised by maximum concentration of Zn, Cu, Mn, Rb, Sr, Na and K, and is to that extent, a valuable (though not an infallible) indicator of base-metal mineralisation. It is shown that there is considerable difference in the intake of elements by plants in relation to the concentration of the same elements in the soils and well waters of the area.     

Bioleaching of high pyrite carbon-rich sphalerite preflotation tailings

In this work, zinc extraction was investigated using bioleaching process. The used samples were carbon-rich preflotation tailings prepared from a lead–zinc mineral processing plant, located in Yazd province, Iran. Two samples were obtained with high amount of pyrite, while the first sample contained high arsenic (As) substitution in the pyrite crystal lattice, and it was about 4–5 times more than that of the second sample. The organic matter in both samples has presented a signature of poorly crystalline carbon. Bioleaching experiments were designed and carried out by a mixed culture of Acidithiobacillus ferrooxidans, Acidithiobacillus thiooxidans and Leptospirillum ferrooxidans in shake flasks. The results showed that in the optimum point of experiments (pH 1.94–2, pulp density 10 %, without initial Fe⁺²), about 95 % of Zn would be extracted within 14 days, while with no use of bacteria, merely 35 % of Zn content was dissolved (under the same condition). Because of the characteristics of the prepared samples, the bacterial medium (9K) was removed in the optimum condition of bioleaching tests. Results showed that even in the absence of 9K medium, bacteria had proper growth too, such that more than 93 % of Zn content was extracted. In fact, the same results were achieved in the absence and presence of 9K medium. Comparison of the obtained results in bioleaching tests under the optimum condition indicated that Zn extraction was the same for both high and low As samples, while Fe extraction from low As content sample was nearly 4 times higher than that of the other sample.     

Spatial distribution and geochemical baselines of major/trace elements in soils of Medak district,Andhra Pradesh,India

Regional-scale variations in soil geochemistry were investigated with special reference to differences among soil groups and lithology in an area of 9,699 km² in Medak district, Andhra Pradesh, India. The concentrations of 29 elements (major: Si, Al, Fe, Mn, Mg, Ca, Na, K, Ti, P and trace: As, Ba, Cd, Co, Cr, Cu, F, Mo, Ni, Pb, Rb, Se, Sr, Th, U, V, Y, Zn, Zr) in 878 soil samples collected (557-topsoil, 321-subsoil) at a sampling density of 1 site/17 km² from 557 sites representative of all the soil types present in studied area were determined, and their elemental composition are discussed. The baseline levels of these elements in soils are determined over different lithological units for the identification of anomalous values relative to these. For the first time, geochemical maps for Medak district are prepared on 1:50,000 scale and the lithogeochemical database generated provides information on the lateral and vertical distribution of elements in soil. The spatial variations in the distribution of elements reflect underlying geologic characteristics. Box-plots reveal that the concentration of most of the elements in soils were not strongly dependent on the soil group but the soil-geochemistry abruptly changes with the change in the soil parent materials indicating that the distribution of elements is mostly influenced by the bedrock lithology and other natural processes acting on them. For instance, the concentrations of Co, Cu, Fe, Mn, Ti, V and Zn are high in soils developed on basaltic terrain while the soils developed on granitic and gneissic terrain exhibit high elemental concentrations of K, Pb, Rb, Si, Th and Y. Alfisols had relatively high contents of elements while entisols had lower concentrations of most of the elements. The database can be used in the chemical characterisation of different geological units as well as applications in various environmental and agricultural fields. The results indicate that regional geology is an important determinant of soil geochemical baselines for soil pollution assessment and further emphasizes the importance of determining background levels locally. The defined baselines can be used to establish background values for future soil surveys.     

Distribution of thallium and accompanying metals in tree rings of Scots pine (Pinus sylvestris L.) from a smelter-affected area

Distribution of Tl, Zn, Cd, Pb, K, Ca, Mg and Mn and Pb isotopic composition in tree rings of Scots pine (Pinus sylvestris L.) from an area affected by primary Zn smelting (Olkusz, southern Poland) were investigated. Elevated concentrations of Tl (up to 0.8 mg kg⁻¹) in pine trees imply that conifers tend to accumulate this metal to some extent. A generally positive relationship between soil and tree-ring Tl levels was identified. The Tl patterns in stem wood did not correspond to changes in Tl deposition; the lateral translocation of Tl in the sapwood and its accumulation at the sapwood-heartwood boundary (i.e., in the inner sapwood) is suggested. It is probable that the specific behavior of Tl in trees results from its biogeochemical analogy with K. In contrast, tree-ring patterns of Zn and Cd significantly correlated with their deposition; nevertheless, a partial shift of these metals towards the stem center cannot be excluded. The isotopic composition of Pb (²⁰⁶Pb/²⁰⁷Pb ~ 1.172–1.184) in trees and underlying soils revealed the predominant influence of smelter emissions (²⁰⁶Pb/²⁰⁷Pb ~ 1.17) on Pb contamination. Analysis of main nutrients (Ca, Mg and Mn) in wood reflected environmental changes related to acid deposition.     

The species of Silene compacta Fischer as indicator of zinc,iron and copper mineralization

The possibility of using the species Silene compacta Fischer (Caryophyllaceae) as a plant indicator for Zn, Fe and Cu is discussed in this paper. Rock and plant samples were collected from an area near Essimi, north-eastern Greece, which is known for its Cu–Pb–Zn mineralization and analyzed for their content in 14 elements (Fe, Mn, Ag, As, Cd, Co, Cu, Mo, Ni, Pb, Sb, Sn, Zn and V). The data illustrate positive linear correlation between the concentrations of Zn, Fe and Cu in plant ash and rock samples. In particular, these correlations are 0.99 for Zn, 0.97 for Fe and 0.97 for Cu and are significant at the 99.9% confidence level. Therefore, S. compacta could be used as a plant indicator for Zn, Fe and Cu mineralization.     

Comparison between non-residual Al,Co, Cu,Fe, Mn,Ni, Pb and Zn released by a three-step sequential extraction procedure and a dilute hydrochloric acid leach for soil and road deposited sediment

Surprisingly little is known about the relationship between the labile phases removed by sequential extraction procedures and those liberated by single leaches that minimally impact the alumino-silicate matrix of solids. This investigation examines the relationship between the summed concentrations of Al, Co, Cu, Fe, Mn, Ni, Pb and Zn released by an optimized 3-step standardized sequential extraction procedure and those released by a single 0.5 M HCl leach. Thirty-nine representative soil and road deposited sediment samples were examined from an urban watershed, in Honolulu, Hawaii, which has been shown to have a high degree of traffic-associated pollution. Properties of samples analyzed varied widely and exhibited a range in cation exchange capacities from 7 to 59 cmol_c/kg, pH values from 3.5 to 7.9, and organic C contents from 1 to 29%. Results indicate that the dilute HCl leach was slightly more aggressive than the sequential procedure as it removed significantly more Al, Cu, Fe, Mn and Ni; though no significant differences were observed between Co, Pb and Zn concentrations liberated by the two approaches. Both approaches showed limited dissolution of the crystal lattice with ⩽9% of the total Al liberated. Regardless of approach, element mobility was the same with the order being: Pb>Mn>Zn>Co≈Cu>Ni>Fe ∼ Al. Regression analysis indicated highly significant (P<0.0001) logarithmic relationships between the two digestion procedures, with coefficients of determination (r²) ⩾92% for all elements except Fe (54%) and Ni (64%). Further support for the strong relationships between elements liberated by both digestions was gained from geochemical contrasts between anomalous and background levels and concentration enrichment ratios. This was particularly true for Pb and Zn, the most anthropogenically enhanced trace metals in the watershed. All data indicated that a dilute HCl leach was a valuable, rapid, and cost-effective analytical tool in contamination assessment.     

Heavy metal distribution in surface sediments of the Tirumalairajan river estuary and the surrounding coastal area, east coast of India

Surface sediments collected at the Tirumalairajan river estuary and their surrounding coastal areas were analyzed for the bulk metal concentration. The sediments were collected from post- and premonsoon seasons. Dominances of heavy metals are in the following order: Fe > Mn > Zn > Pb > Cu in both seasons from estuary and coastal area. The results reveal that Fe, Mn, Cu, Pb, and Zn demonstrated an increased pattern from the estuary when compared to the coastal area. The heavy metal pattern of the sediments of the Tirumalairajan river estuary and its surrounding coastal area offered strong evidence that the coastal area was a major source of heavy metals to the estuarine region. For various metals, the contamination factor and geoaccumulation index (I _geo) have been calculated to assess the degree of pollution in sediments. The contamination factor and geoaccumulation index show that Zn, Pb, and Cu unpolluted to moderately pollute the sediments in estuarine part. This study shows the major sources of metal contamination in catchment and anthropogenic ones, such as agriculture runoff, discharge of industrial wastewater, and municipal sewage through the estuary and adjoining coastal area.     

松花江哈尔滨段水系沉积物中无机元素环境标准样品的研制

介绍了松花江哈尔滨段水系沉积物环境标准样品的研制方法,对其中21个无机元素进行定值。采集的水系沉积物样品经自然阴干、研磨、筛分、混匀、装瓶和灭菌等加工处理后,分层随机抽取18瓶样品,在0.25 g样品取样量条件下,以铜、铅、锌、砷、汞、铁和铝为代表元素进行均匀性研究,结果表明样品均匀性良好。在室温避光保存条件下,以铜、铅、锌、砷和汞为代表元素,采用线性模型进行稳定性研究,在15个月研制期间样品未观察到不稳定性。由11家协作实验室对水系沉积物标准样品中的21个无机元素进行定值研究,经统计检验分析评定出20个元素的标准值和不确定度,1个元素给出参考值。研制成的标准样品已应用于土壤或水系沉积物样品中无机元素的监测。     

Seasonal variation of gold and arsenic in biogeochemical samples from a disseminated gold deposit in the Northern Cordillera

An orientation survey was conducted over the Quartz Mountain, Oregon, hot-spring type disseminated gold deposit to address three questions critical to successful exploration of the area: What is the relationship between bedrock geology and the trace-element content of trees and soils; do these relationships change seasonally; are these relationships similar in the two tree species which discontinuously blanket the area?Twig, needle and wood samples were collected four times during the year from both ponderosa pine (Pinus ponderosa) and white fir (Abies concolor). Soils were collected once. All samples were analyzed for Au and As and the wood samples were analyzed also for Sb.Arsenic was the best pathfinder element, having little analytical, spatial, or seasonal variation in the twig and needle samples. Anomalous levels were 150 μg/g (ppm) As in pine and 30 μg/g in fir. Gold showed analytical variation of 20–30%, sample duplicate variation up to 90%, spatial changes, and seasonal variation ranging from winter-summer background [10–20 ng/g (ppb) Au] to anomalies of 300–400 ng/g (ppb) Au in pine and 100 μg/g (ppb) Au in fir in the spring and fall. Antimony could not be completely evaluated as a pathfinder element because it was only determined in wood samples.Needles and twigs from both species proved to be viable sample media for exploration of the area. Wood was not a suitable medium because of low, erratic values, perhaps due in part to analytical technique. Needles had 2 to 20 times higher As concentrations than did twigs. Twigs had a slightly higher Au content [25 ng/g (ppb)] than did needles. The pine samples were higher in both elements than were the fir samples. The data, normalized by species, could be treated as one homogeneous data base.The soil Au and As data outlined the mineralization clearly with a central Au anomaly [100 ng/g (ppb) and greater] surrounded by As anomalies [100 μg/g (ppm) and greater] over a distance of 594 m. Neither spring nor fall tree Au anomalies were coincident with the soil Au anomaly. Consistent throughout the year, tree As anomalies coincided with the soil As anomalies, but covered a smaller area. Both the Au and As anomalies in trees appeared to be related to bedrock contact zones rather than to the soil the trees were growing in.     

Spatial distribution,mineralogy, and weathering of heavy metals in soils along zinc-concentrate ground transportation routes: implication for assessing heavy metal sources

We investigated the source of heavy metals in soils at a site in South Korea, where a ground transportation of zinc-concentrates (ZnS, sphalerite) occurs daily. Seventy soil samples were collected at the site and analyzed for residual concentrations of heavy metals, as well as their chemical and mineralogical properties. Enrichment factor was calculated based on local geochemical background level of metals in soils and confirmed the contamination of soils in the area by an anthropogenic source. The concentration data were also subjected to a Pearson correlation analysis to determine the possible influences of anthropogenic sources and identify the primary source. A slight negative correlation between heavy metals and Al, and a weak correlation between heavy metals and Fe implied that the heavy metals originated from anthropogenic inputs rather than a geogenic source. A strong positive linear correlation between Zn and other heavy metals (i.e., As, Cd, Cu, Pb, r ≥ 0.96, p ≤ 0.001) suggested the influence of a single anthropogenic source of zinc-concentrates containing all of these heavy metals. Zinc-concentrate oxidation and leaching experiments, which mimicked physical and chemical weathering in the environment, indicated that zinc-concentrate could be transformed to zinc oxides and release Cd and Pb upon precipitation. The findings in this study provide an insight into the fate of the Zn that the original form of zinc-concentrate would not remain in the soil after long-term weathering, which should be considered when source of heavy metals is identified.     

Impact of parent rock and topography aspect on the distribution of soil trace metals in natural ecosystems

The concentration and dynamic of soil trace metals in natural ecosystems, in particularly, is dependent on the lithology of parent rock as well as topography and geopedological processes. To ascertain more knowledge for this dependency, soils on three parent rocks involving peridotite, pegmatite, and dolerite in two contrasting topography aspects were investigated. The total values of Fe, Mn, Zn, Cu, and Ni were determined and compared for different soil pedons. The concentration of Fe, Mn, and Ni were highest in soils developed from peridotite (127, 1.8 g kg^?1, and 218 mg kg^?1, respectively), intermediate in soils derived from dolerite (81, 1.3 g kg^?1, and 166 mg kg^?1, respectively), and least in soil developed from pegmatite (50, 0.23 g kg^?1, and 20 mg kg^?1, respectively). The values of Zn and Cu, originated from different parent rocks, were in order of dolerite (78 mg kg^?1) > peridotite (77 mg kg^?1) > pegmatite (28 mg kg^?1) and pegmatite (121 mg kg^?1) > peridotite (111 mg kg^?1) > dolerite (28 mg kg^?1), respectively. For most of the studied pedons, profile metals distribution differed among the soils: The values of Fe, Cu, and Ni were enriched in the cambic horizons mainly as result of release, mobilization, and redistribution of the studied metals during geopedological processes, whereas those of Zn and Mn were concentrated in the surface horizons. Probably due to greater weathering rate of trace metal-bearing rocks on north-facing slope, the content of the trace metals along with the geoaccumulation index (I _geo) and the degree of soil contamination (C _d) were higher than on south-facing slope. Based on assessment of soil pollution indices, the soils were categorized as unpolluted [I _geo ≤ 0 (class 0)], unpolluted to moderately polluted levels [0 < I _geo < 1 (class 1)], and very low [C _d < 1.5 (class 0)] to low degree of contamination [1.5 < C _d < 2 (class 1)].     

Effects of in situ remediation on the speciation and bioavailability of zinc in a smelter contaminated soil

We report results from an extensive study on the speciation of zinc (Zn) and its relation to the mobility and bioavailablity of this element in a smelter contaminated soil and an in situ remediated area of this soil 12 yr after the application of cyclonic ash and compost. Emphasis was placed on the role of neoformed precipitates in controlling Zn speciation, mobility and bioavailability under different environmental conditions. Twelve years after remediation, the pH of the treated and non-treated soil differed by only 0.5 pH unit. Using state-of-the-art electron and X-ray microscopies in combination with micro-focused extended X-ray absorption fine structure (μ-EXAFS) spectroscopy, no major differences in Zn speciation were found between samples of the treated and non-treated soil. In both soils, 30% to 50% of Zn was present in smelter related minerals (willemite, hemimorphite or gahnite), while 50% to 70% of Zn was incorporated into newly formed Zn precipitates. Contrary to the non-treated soil, the treated soil did not contain gahnite or sphalerite; it is possible that these minerals were dissolved under the higher pH conditions at the time of treatment. Desorption experiments, using a stirred flow technique with a 0.1 mol/L CaCl₂ (pH 6.5) and a HNO₃ (pH 4.0) solution were employed to determine the exchangeable Zn fraction and the Zn fraction which will be mobilized under more extreme weathering conditions, respectively. No significant differences were found in desorption behavior between the treated vs. non-treated soil. Bioavailability tests, using the R. metallidurans AE1433 biosensor showed that ∼8% of total Zn was bioavailable in both the treated and non-treated soils. It was concluded that the incorporation of Zn into newly formed precipitates in both the treated and non treated soils leads to a significant natural attenuation of the exchangeable/bioavailable Zn fraction at near neutral pH conditions. At lower pHs, conditions not favorable to the formation of Zn precipitates, the pool of Zn associated with the secondary Zn precipitates is potentially more bioavailable.