Heavy metal contamination of soils in Northern Slovakia

Environmental damages like forest decline in Northern Slovakia could be a result of long-distance transport of pollutants with the dominating north-west winds. On 10 sites, primarily in the northbound upper slopes of west-east oriented mountain ranges in Northern Slovakia, the extent of the heavy metal contamination in soils along a north-south transect was examined. Oi, Oe, Oa, A, and B horizons were sampled and the total concentrations of Al, Cd, Cr, Cu, Fe, Mn, Ni, Pb, and Zn were determined. The ranges of heavy metal concentrations in the forest floor were higher than reported for comparable samples from Bavarian soils except for Zn (Cd: 0.65–1.77; Cr: 12–40; Cu: 19–41; Ni: 8–24; Pb: 70–187; Zn: 31–92 mg kg^?1), in the mineral soil the concentrations were lower. The depth distribution of the metal concentrations indicated a contamination with Cd, Cr, Cu, Ni, Pb, and Zn. The concentration differences between forest floor and mineral soil tended to be higher at the northern than at the southern sites for Cu, Ni, Pb, and Zn, indicating a long-distance transport from the north. Correlation and principal component analyses of the total metal concentrations revealed three groups: Cu, Pb, and Zn inputs mainly seemed to result from long-distance transport from the north, Cr and Ni inputs additionally from local sources. Cd probably had its origin mainly in local sources. This result was further confirmed by the grouping of the sites when clustered.     

Plant uptake of metals,transfer factors and prediction model for two contaminated regions of Kosovo

The bioavailability and plant uptake of heavy metals (HM), as well as finding the most reliable methods for the prediction of availability, continues to be one of the most crucial problems in agricultural and environmental studies. In agricultural soils from two regions in Kosovo, known for its metal pollution, we collected 60 soil and plant samples (wheat, corn, potatoes, and grass). Heavy metals were extracted from soil with aqua regia (pseudototal concentration), NH₄OAc‐EDTA (potential bioavailable), and NH₄NO₃ (mobile fraction), plant samples were digested with HNO₃/H₂O₂ (microwave assisted extraction). The pseudo total content of Cd, Pb, and Zn showed high value in Mitrovice (mean: Cd–2.92, Pb–570.15, and Zn–522.86 mg kg^?1), whereas in Drenas region Ni and Cr showed high value with a mean 258.54 and 203.22 mg kg^?1. Also, the potential bioavailability and mobile form of these metals were increased in Mitrovice (mean: Cd–1.59, Pb–217.05, Zn–522.86 mg kg^?1, respectively Cd–0.17, Pb–0.64, and Zn–15.45 mg kg^?1), compared to Drenas. Cd and Pb were elevated in potato tubers (mean Cd–0.48 and Pb–0.85 mg kg^?1). The TF was higher for micronutrients (Zn and Cu) than for non‐essential metals (Cd and Pb). Multiple regression analysis showed a good model for prediction of Cd, Pb and Zn content in plant with significance 99.9%, whereas this model was not significant for Cu, Cr, and Ni. Soil pH played a significant role in the content of Cd and Zn in wheat and potato plants. Clay content also showed significance in Cd concentration in wheat and potato plants, while carbon content was significant for Cd in grass plants, as well as for Zn in wheat and grass plants.     

The transfer of heavy metals to barley plants from soils amended with sewage sludge with different heavy metal burdens

Purpose

Our main aim objective was to evaluate the transfer of Cd, Cr, Cu, Ni, Pb and Zn to barley (Hordeum vulgare) grown in various soils previously amended with two sewage sludges containing different concentrations of heavy metals. This allowed us to examine the transfer of heavv metals to barley roots and shoots and the occurrence of restriction mechanisms as function of soil type and for different heavy metal concentration scenarios.

Material and methods

A greenhouse experiment was performed to evaluate the transfer of heavy metals to barley grown in 36 agricultural soils from different parts of Spain previously amended with a single dose (equivalent to 50 t dry weight ha^?1) of two sewage sludges with contrasting levels of heavy metals (common and spiked sludge: CS and SS).

Results and discussion

In soils amended with CS, heavy metals were transferred to roots in the order (mean values of the bio-concentration ratio in roots, BCF_Roots, in brackets): Cu (2.4)?~?Ni (2.3)?>?Cd (2.1)?>?Zn (1.8)?>?Cr (0.7)?~?Pb (0.6); similar values were found for the soils amended with SS. The mean values of the soil-to-shoot ratio were: Cd (0.44)?~?Zn (0.39)?~?Cu (0.39)?>?Cr (0.20)?>?Ni (0.09)?>?Pb (0.01) for CS-amended soils; Zn (0.24)?>?Cu (0.15)?~?Cd (0.14)?>?Ni (0.05)?~?Cr (0.03)?>?Pb (0.006) for SS-amended soils. Heavy metals were transferred from roots to shoots in the following order (mean values of the ratio concentration of heavy metals in shoots to roots in brackets): Cr (0.33)?>?Zn (0.24)?~?Cd (0.22)?>?Cu (0.19)?>?Ni (0.04)?>?Pb (0.02) for CS-amended soils; Zn (0.14)?>?Cd (0.09)?~?Cu (0.08)?>?Cr (0.05)?>?Ni (0.02)?~?Pb (0.010) for SS-amended soils.

Conclusions

Soils weakly restricted the mobility of heavy metals to roots, plant physiology restricted the transfer of heavy metals from roots to shoots, observing further restriction at high heavy metal loadings, and the transfer of Cd, Cu and Zn from soils to shoots was greater than for Cr, Ni and Pb. Stepwise multiple linear regressions revealed that soils with high sand content allowed greater soil-plant transfer of Cr, Cu, Pb and Zn. For Cd and Ni, soils with low pH and soil organic C, respectively, posed the highest risk.     

Heavy‐Metal Contamination of Soil and Vegetables in Wastewater‐Irrigated Agricultural Soil in a Suburban Area of Hanoi,Vietnam

The To Lich and Kim Nguu Rivers, laden with untreated waste from industrial sources, serve as sources of water for irrigating vegetable farms. The purposes of this study were to identify the impact of wastewater irrigation on the level of heavy metals in the soils and vegetables and to predict their potential mobility and bioavailability. Soil samples were collected from different distances from the canal. The average concentrations of the heavy metals in the soil were in the order zinc (Zn; 204 mg kg^?1) > copper (Cu; 196 mg kg^?1) > chromium (Cr; 175 mg kg^?1) > lead (Pb; 131 mg kg^?1) > nickel (Ni; 60 mg kg^?1) > cadmium (Cd; 4 mg kg^?1). The concentrations of all heavy metals in the study site were much greater than the background level in that area and exceeded the permissible levels of the Vietnamese standards for Cd, Cu, and Pb. The concentrations of Zn, Ni, and Pb in the surface soil decreased with distance from the canal. The results of selective sequential extraction indicated that dominant fractions were oxide, organic, and residual for Ni, Pb, and Zn; organic and oxide for Cr; oxide for Cd; and organic for Cu. Leaching tests for water and acid indicated that the ratio of leached metal concentration to total metal concentration in the soil decreased in the order of Cd > Ni > Cr > Pb > Cu > Zn and in the order of Cd > Ni > Cr > Zn > Cu > Pb for the ethylenediaminetetraaceitc acid (EDTA) treatment. The EDTA treatment gave greater leachability than other treatments for most metal types. By leaching with water and acid, all heavy metals were fully released from the exchangeable fraction, and some heavy metals were fully released from carbonate and oxide fractions. The concentrations of Cd, Cr, Cu, Ni, Pb, and Zn in the vegetables exceeded the Vietnamese standards. The transfer coefficients for the metals were in the order of Zn > Ni > Cu > Cd = Cr > Pb.     

Heavy Metals in Freshly Deposited Stream Sediments of Rivers Associated with Urbanisation of the Ganga Plain,India

Freshly deposited stream sediments from six urban centres of the Ganga Plain were collected and analysed for heavy metals to obtain a general scenery of sediment quality. The concentrations of heavy metals varied within a wide range for Cr (115–817), Mn (440–1 750), Fe (28 700–61 100), Co (11.7–29.0), Ni (35–538), Cu (33–1 204), Zn (90–1 974), Pb (14–856) and Cd (0.14–114.8) in mg kg^-1. Metal enrichment factors for the stream sediments were <1.5 for Mn, Fe and Co; 1.5–4.1 for Cr, Ni, Cu, Zn and Pb; and 34 for Cd. The anthropogenic source in metals concentrations contributes to 59% Cr, 49% Cu, 52% Zn, 51% Pb and 77% Cd. High positive correlation between concentrations of Cr/Ni, Cr/Cu, Cr/Zn, Ni/Zn, Ni/Cu, Cu/Zn, Cu/Cd, Cu/Pb, Fe/Co, Mn/Co, Zn/Cd, Zn/Pb and Cd/Pb indicate either their common urban origin or their common sink in the stream sediments. The binding capacity of selected metals to sediment carbon and sulphur decreases in order of Zn > Cu > Cr > Ni and Cu > Zn > Cr > Ni, respectively. Stream sediments from Lucknow, Kanpur, Delhi and Agra urban centres have been classified by the proposed Sediment Pollution Index as highly polluted to dangerous sediments. Heavy metal analysis in the <20-μm-fraction of stream sediments appears to be an adequate method for the environmental assessment of urbanisation activities on alluvial rivers. The present study reveals that urban centres act as sources of Cr, Ni, Cu, Zn, Pb and Cd and cause metallic sediment pollution in rivers of the Ganga Plain.     

Long-term changes in soil and plant metal concentrations in an acidic dredge disposal site receiving sewage sludge

A long-term experiment was conducted to determine the distribution of sludge-borne metals applied to a revegetated acidic dredge spoil disposal site. The initial soil was infertile and highly acidic (pH 2.4). Sewage sludge and lime were applied in 1974 at the rates of 100 and 23 mt ha^?1, respectively, and tilled into the soil to a depth of 20 cm. In 1974 an adjacent site was also revegetated with topsoil and lime but without sludge. Soil and plants were sampled 2, 4 and 16 yr following seeding. After 16 yr the total and DTPA-extractable Cu, Zn, Cr, Pb, Ni and Cd decreased in soils to nearly the levels of the control soils. Concentrations of metals in plants also decreased. Decreases in tissue concentrations ranged from 40 to 70% for Cu, Cr, Pb, Ni and Cd and up to 90% for Zn. The results showed that a single 100 mt ha^?1 application of sewage sludge containing high concentrations of metals was a cost-effective method for improving plant growing conditions on highly acidic soils.

     

Fractionation of Cu, Pb, Cr, and Zn in a Soil Column Amended with an Anaerobic Municipal Sewage Sludge

The objective of this study was to investigate the changes in the chemical partitioning of Cu, Pb, Cr and Zn within a column of soil incubated with an anaerobic sewage sludge (ANSS) for 2.5 months. The soil was irrigated during the incubation period. A sequential extraction method was used to fractionate these metals into exchangeable, weakly adsorbed, organic, Al oxide, Fe–Mn oxide, and residual, respectively. ANSS was applied at a loading rate of 69 Mg ha^?1. The soil is a Dystric Cambisol with low pH (<3.8), low CEC [<10 cmol(+) kg^?1 below the first 4 cm depth], and low base saturation (<7%). The addition of the ANSS caused a decrease in concentrations of Cu, Pb, and Cr in the A1 horizon, and an increase in the concentrations with depth. Below the A1 horizon, concentrations of Cu increased uniformly (~1 mg cm^?1), and the greatest increases were observed in the residual, Fe–Mn oxides, and weakly adsorbed fractions. Maximum increases in Pb occurred at 4–9 cm of depth (1.6 mg cm^?1), and mainly affected the weakly adsorbed fraction. Chromium essentially accumulated at the limit between the A2 and the Bw horizons (1.1–1.5 mg cm^?1) as residual and organic bound forms, probably through particulate transport. Zinc mainly accumulated in the A1 horizon (2.9 mg cm^?1) as exchangeable Zn. At depth, Zn increments were predominantly observed in the residual fraction. The results of this study thus demonstrate the redistribution of contaminants into different chemical pools and soil layers after sludge amendment.     

Relationships of Heavy Metals in Natural Lake Waters with Physico-chemical Characteristics of Waters and Different Chemical Fractions of Metals in Sediments

The relationships between heavy metal concentrations and physico-chemical properties of natural lake waters and also with chemical fractions of these metals in lake sediments were investigated in seven natural lakes of Kumaun region of Uttarakhand Province of India during 2003–2004 and 2004–2005. The concentrations of Cr, Mn, Fe, Ni, Cu, Zn, Cd and Pb in waters of different lakes ranged from 0.29–2.39, 10.3–38.3, 431–1407, 1.0–6.6, 5.3–12.1, 12.6–166.3, 0.7–2.7 and 3.9–27.1 μg l^?1 and in sediments 14.3–21.5, 90.1–197.5, 5,265–6,428, 17.7–45.9, 13.4–32.0, 40.0–149.2, 11.1–14.6 and 88.9–167.4 μg g^?1, respectively. The concentrations of all metals except Fe in waters were found well below the notified toxic limits. The concentrations of Cr, Mn, Ni, Cu, Zn, Cd and Pb were positively correlated with pH, electrical conductivity, biological oxygen demand, chemical oxygen demand and alkalinity of waters, but negatively correlated with dissolved oxygen. The concentrations of Cr, Ni, Zn, Cd and Pb in waters were positively correlated with water soluble + exchangeable fraction of these metals in lake sediments. The concentrations of Zn, Cd and Pb in waters were positively correlated with carbonate bound fraction of these metals in lake sediments. Except for Ni, Zn and Cd, the concentrations of rest of the heavy metals in waters were positively correlated with organically bound fraction of these metals in lake sediments. The concentrations of Cr, Mn, Ni, Cu and Zn in waters were positively correlated with reducible fraction of these metals in lake sediments. Except for Cd, the concentrations of rest of the metals in waters were positively correlated with residual fraction and total content of these heavy metals in lake sediments.     

Spatial distribution of soil heavy metal concentrations as indicator of pollution sources at Mount Križna (Great Fatra,central Slovakia)

The objective of this study was to test the suitability of a simple approach to identify the direction from where airborne heavy metals reach the study area as indication of their sources. We examined the distribution of heavy metals in soil profiles and along differently exposed transects. Samples were taken from 10 soils derived from the same parent material along N-, S-, and SE-exposed transects at 0—10, 10—20, and 20—40 cm depth and analyzed for total Al, Cd, Cr, Cu, Fe, Mn, Ni, Pb, and Zn concentrations. The heavy metal concentrations at 0—10 cm were larger than background concentrations in German arable soils except for Cr (Cd: 0.6—1.8 mg kg^—1; Cr: 39—67; Cu: 40—77; Ni: 87—156; Pb: 48—94; Zn: 71—129; Fe: 26—34 g kg^—1; Mn: 1.1—2.4). Decreasing Cd, Cu, Mn, and Pb concentrations with increasing soil depth pointed at atmospheric inputs. Aluminum and Ni concentrations increased with soil depth. Those of Fe, Cr, and Zn did not change with depth indicating that inputs at most equalled leaching losses. The Pb accumulation in the surface layer (i.e. the ratio between the Pb concentrations at 0—10 to those at 20—40 cm depth) was most pronounced at N-exposed sites; Pb obviously reached Mount Križna mainly by long-range transport from N where several industrial agglomerations are located. Substantial Cd, Cu, and Mn accumulations at the S- and SE-exposed sites indicated local sources such as mining near to the study area which probably are also the reason for slight Cr and Zn accumulations in the SE-exposed soils. Based on a principal component analysis of the total concentrations in the topsoils four metal groups may be distinguished: 1. Cr, Ni, Zn; 2. Mn, Cd; 3. Pb (positive loading), Cu (negative loading); 4. Al, Fe, indicating common sources and distribution patterns. The results demonstrate that the spatial distribution of soil heavy metal concentrations can be used as indication of the location of pollution sources.     

Retention of Metals in Agricultural Soils After Amending with MSW and MSW-Biosolids Compost

The goal of this study was to measure the As, Cu, Fe, Pb and Zn contents of soils amended with municipal solid waste (MSW) and MSW-biosolids compost and to determine the long-term transport of these metals to lower soil horizons. Lead, Cu, Cd and Zn contents in the composts were 3–20 times more concentrated in the compost compared to the soil at the Calverton, NY, U.S.A. farm. As a result, Pb, Cd, Cu and Zn were elevated in the upper 5 cm soil layer following compost application and the metal enrichment was proportional to the amount of compost applied (21–62 Mg ha^-1). In addition, Pb, As and Cu contents of the non-compost amended Calverton soils were enriched above the tillage depth (20–25 cm). Cu, Pb and As enrichment was attributed to the historical use of sodium arsenite, lead arsenate and copper sulfate insecticides and fungicides. Results of the metal analyses of soil cores collected 16 and 52 months following compost application showed that Cu, Zn and Pb remained confined to the upper 5 cm soil layer. The low water extractable fraction of these metals in MSW and MSW-biosolids compost was a major factor limiting the transport of these metals to lower soil horizons. In contrast, Cd leaching from the upper 0–5 and 5–10 cm soil layers was continuous over the 52 month study period and was attributed primarily to the presence of soluble Cd in phosphate fertilizer initially applied to the Calverton farm soil.     

Glutamic acid decomposition as a sensitive measure of heavy metal pollution in soil

The effect of added heavy metals (Cd, Cr, Cu, Ni, Pb and Zn) on the rate of decomposition of glutamic acid was studied in four Dutch soil types in order to determine if such measurements would serve as sensitive indicators of heavy metal pollution in soil. The time required to reach the maximum respiration rate (referred to as the decomposition time) with glutamic acid was linearly related to increasing concentrations of Ni in a sandy loam soil.Changes in decomposition time were measured 18 months after addition of 55, 400 or 1000 mg kg^? of Cd, Cr, Cu, Ni, Pb or Zn respectively to sand, silty loam, clay and sandy peat soils. A significant increase in the decomposition time occurred with a concentration of 55 mg kg^?1 of Cd, Cu or Zn in the sand soil. At 400mgkg^?1 adverse effects in the various soils are distinct. The sensitivity of the decomposition time of glutamic acid as a method to measure soil pollution is discussed.     

Contents and chemical forms of heavy metals in school and roadside topsoils and road-surface dust of Beijing

Purpose

The concentration of human activities in urban systems generally leads to urban environmental contamination. Beijing is one of ancient and biggest cities on the world. However, information is limited on Beijing’s soil contamination, especially for roadside and campus soils. Thus, the aims of this study were to investigate the contents and chemical forms of toxic heavy metals Cd, Cr, Cu, Ni, Pb, and Zn in the road-surface dust, roadside soils, and school campus soils of Beijing. In addition, enrichment and spatial variation of these toxic heavy metals in the soils and dust were assessed.

Materials and methods

Topsoil samples were collected from the schools and roadside adjacent to main ring roads, and dust samples were collected from the surface of the main ring roads of Beijing. These samples were analyzed for total contents and chemical forms of Cd, Cr, Cu, Ni, Pb, Sc, Zn, Al, and Fe. Enrichment factors (EFs, relative to the background content) were calculated to evaluate the effect of human activities on the toxic heavy metals in soils.

Results and discussion

Heavy metal contents in the road dust ranged from 0.16 to 0.80, 52.2 to 180.7, 18.4 to 182.8, 11.9 to 47.4, 23.0 to 268.3, and 85.7 to 980.9 mg kg^?1 for Cd, Cr, Cu, Ni, Pb, and Zn, respectively. In the roadside soil and school soil, Cd, Cr, Cu, Ni, Pb, and Zn contents ranged from 0.13 to 0.42, 46.1 to 82.4, 22.7 to 71.6, 20.7 to 29.2, 23.2 to 180.7, and 64.5 to 217.3 mg kg^?1, respectively. The average EF values of these metals were significantly higher in the dust than in the soils. In addition, the average EF values of Cd, Cu, Pb, and Zn in the soils near second ring road were significantly higher than those near third, fourth, and fifth ring roads. Anthropogenic Cd, Pb, and Zn were mainly bound to the carbonates and soil organic matter, while anthropogenic Cu was mainly bound to oxides. The mobility and bioavailability of these metals in the urban soils of Beijing generally decreased in the following order: Cd?>?Zn?>?Pb?>?Cu?>?Ni?>?Cr; while in the dust, they decreased in the following order: Zn, Cu, and Cd?>?Pb?>?Ni?>?Cr.

Conclusions

Both EF and chemical forms documented that Cr and Ni in the soils and dust mainly originated from native sources, while Cd, Cu, Pb, and Zn partially originated from anthropogenic sources. In overall, Beijing’s road dust was significantly contaminated by Cd and Cu and moderately contaminated by Cr, Pb, and Zn, while Beijing’s roadside soil and school soil were moderately contaminated by Cd and Pb. However, the maximal hazard quotients (HQs) for individual Cd, Cr, Cu, Ni, Pb, and Zn and comprehensive hazard index (HI) of these metals in the dust and soil were less than 1, indicating that the heavy metals in the dust and soil generally do not pose potential health effects to children, sensitive population.     

Sequential fractionation and plant availability of heavy metals as affected by sewage sludge applications to soil

Abstract

The effect of sewage sludge applications on extractability and uptake by chard and lettuce of soil cadmium (Cd), chromium (Cr), copper (Cu), nickel (Ni), leaf (Pb), and zinc (Zn) was investigated. Ten different treatments (0, 150, 300, and 500 kg N ha^‐1) as mineral fertilizer, and 400, 800, and 1,200 kg N ha^‐1 of aerobically and anaerobically‐digested sewage sludges were applied annually to a sandy‐loam soil since 1984. Seven years after the start of the treatments, higher levels of heavy metals were detected in the soil, depending on the type of metal, depth of sampling, type of sludge used, and, especially, rate of application. Following a sequential extraction procedure incorporating 0.1M CaCl₂, 0.5M NaOH, and 0.05M Na₂EDTA, most of the heavy metals in soil were detected in the Na₂EDTA solution and the residual fractions. Large amounts of Cd appeared to be extracted by CaCl₂, whereas substantial amounts of Cu and Ni were isolated by NaOH. The effect of treatments on the percentages of the metals found in each fraction depended on the type of metal, sampling depth, sludge used, and application rate. No significant increases were found in the heavy metal contents of chard and lettuce leaves, but some of the treatments resulted in a significant decrease of Cd and Cr levels in lettuce leaves.     

Immobilization of heavy metals in soils using inorganic amendments in a greenhouse study

The effect of red mud (10 g kg^–1), a by‐product of the alumina industry, zeolite (20 g kg^–1), a naturally‐occurring hydrous aluminosilicate, and lime (3 g kg^–1) on metal lability in soil and uptake by fescue (Festuca rubra L.) (FEST) and amaranthus (Amaranthus hybridus L.) (AMA) was investigated in four different soils from Austria. The soil collection locations were Untertiefenbach (UNT), Weyersdorf (WEY), Reisenberg (REI), and Arnoldstein (ARN). The latter was collected in the vicinity of a former Pb‐Zn smelter and was highly polluted with Pb (12300 mg kg^–1), Zn (2713 mg kg^–1), and Cd (19.7 mg kg^–1) by long‐term deposition. The other soils were spiked with Zn (700 mg kg^–1), Cu (250 mg kg^–1), Ni (100 mg kg^–1), V (100 mg kg^–1), and Cd (7 mg kg^–1) salts in 1987. The two plant species were cultivated for 15 months. Ammonium nitrate (1 M) extraction was used in a soil : solution ratio of 1:2.5 to assess the influence of the amendments on the labile metal pools. The reduction of metal extractability due to red mud was 70 % (Cd), 89 % (Zn), and 74 % (Ni) in the sandy soil (WEY). Plant uptake in this treatment was reduced by 38 to 87 % (Cd), 50 to 81 % (Zn), and 66 to 87 % (Ni) when compared to the control. Sequential extraction revealed relative enrichments of Fe‐oxide‐associated metal fractions at the expense of exchangeable metal fractions. Red mud was the only amendment that decreased lability in soil and plant uptake of Zn, Cd, and Ni consistently. Possible drawbacks of red mud application (e.g., As and Cr concentration) remain to be evaluated.     

Heavy metal distribution in different soil aggregate size classes from restored brackish marsh,oil exploitation zone,and tidal mud flat of the Yellow River Delta

Purpose

Heavy metal distribution in soils is affected by soil aggregate fractionation. This study aimed to demons trate the aggregate-associated heavy metal concentrations and fractionations in “sandy,” “normal,” and “mud” soils from the restored brackish tidal marsh, oil exploitation zone, and tidal mudflat of the Yellow River Delta (YRD), China.

Materials and methods

Soil samples were sieved into the aggregates of >2, 0.25–2, 0.053–0.25, and <0.053 mm to determine the concentrations of exchangeable (F1), carbonate-bound (F2), reducible (F3), organic-bound (F4), and residual fraction (F5) of Cd, Cr, Cu, Ni, Pb, and Zn.

Results and discussion

The 0.25–2 mm aggregates presented the highest concentrations but the lowest mass loadings (4.23–12.18 %) for most metal fractions due to low percentages of 0.25–2 mm aggregates (1.85–3.12 %) in soils. Aggregates <0.053 mm took majority mass loadings of metals in sandy and normal soils (62.04–86.95 %). Most soil aggregates had residual Cr, Cu, Ni, Zn, and reducible Cd, Pb dominated in the total Cd, Cr, Cu, Ni, Pb, and Zn concentrations. Sandy soil contained relatively high F4, especially of Cu (F4) in 0.25–2 mm aggregates (10.22 mg kg^?1), which may relate to significantly high organic carbon contents (23.92 g kg^?1, P?<?0.05). Normal soil had the highest total concentrations of metals, especially of Cu, Ni, and Pb, which was attributed to the high F3 and F5 in the <0.053 mm aggregates. Although mud soil showed low total concentrations of heavy metals, the relatively high concentrations of bioavailable Cd and Cu resulted from the relatively high Cd (F2) and Cu (F2) in the >2 mm aggregates indicated contribution of carbonates to soil aggregation and metal adsorption in tidal mud flat.

Conclusions

Soil type and aggregate distribution were important factors controlling heavy metal concentration and fractionation in YRD wetland soil. Compared with mud soil, normal soil contained increased concentrations of F5 and F3 of metals in the 0.053–0.25 mm aggregate, and sandy soil contained increased concentrations of bioavailable and total Cr, Ni, and Zn with great contribution of mass loadings in the <0.053 mm aggregate. The results of this study suggested that oil exploitation and wetland restoration activities may influence the retention characteristics of heavy metals in tidal soils through variation of soil type and aggregate fractions.

     

Chemical Changes in Soil and Plants After Successive Amendments of Tunisian MSW Compost

A field study was carried out to evaluate long-term heavy metal (HM) accumulation in the top 20 cm of a Tunisian clayey loam soil amended for (four years) with municipal solid waste compost (MSWC) at three levels (0, 40 and 80 t ha^?1 year^?1). HM uptake and translocation within wheat plants grown on these soils were also investigated. Compared to untreated soils, MSWC-amended soils showed significant increases in the content of all measured HM (Cd, Cr, Cu, Ni, Pb and Zn) in the last three years, especially for the 80 t ha^?1 year^?1 MSWC-amended plots. Wheat plants grown on MSWC-amended soils showed a general increase in metal uptake and translocation, especially for Cr and Ni. This HM uptake was about three fold greater for treatment 80 t h^?1 as compared to plots amended at a rate of 40 t h^?1. At times, the diluting effect resulting from enhanced growth rates of the plants with compost application resulted in lower concentrations in the plants grown (grain part) on treated plots. On the other hand, Cr and Ni were less mobile in the aerial part of wheat plants and were accumulated essentially in root tissues. Plant/soil transfer coefficients for MSWC-amended treatments were higher than threshold range reported in the literature, indicating that there was an important load/transfer of HM ions from soils to wheat plants.     

Influence of pH on the release and chemical fractionation of heavy metals in sediment from a suburban drainage stream in an arid mine-based oasis

Purpose

The objectives of this study were to explore the influences of pH on the release of Cu, Zn, Cd, Pb, Ni, and Cr in sediments derived from the upstream, middle, and downstream reaches of Dongdagou stream in Gansu Province, Northwest China, and to examine the fractionation changes of heavy metals in the sediments after reaching their release equilibrium under different pH conditions.

Materials and methods

Sediment samples were obtained using a stainless steel grab sampler to collect the uppermost 10 cm of sediment from the channel bed. The pH-dependent release experiment was conducted in the solid-to-liquid ratio of 1:20 at different pH values (2, 4, 6, 8, 10, and 12) at room temperature. The total Cu, Zn, Cd, Pb, Ni, and Cr concentrations in the sediments were digested using an acid digestion mixture (HNO₃ + HF + HClO₄) in an open system. Metal fractionation of selected sediments was obtained using the Tessier sequential extraction procedure. Heavy metal concentrations in the samples were determined using atomic absorption spectrophotometry.

Results and discussion

The mean concentrations of heavy metals in sediments decreased in the following order: Zn (1676.67 mg kg^?1) > Pb (528.65 mg kg^?1) > Cu (391.34 mg kg^?1) > Cr (53.48 mg kg^?1) > Ni (34.27 mg kg^?1) > Cd (11.53 mg kg^?1). Overall, the solubility of Cu, Zn, Cd, Pb, and Ni decreased with increasing pH, and they were strongly released at pH 2. Moreover, the solubility of Cr increased with increasing pH, and its release was highest at pH 12. After reaching the release equilibrium of heavy metals under different pH conditions, the percentages of organic Cu, Zn, Cd, and Fe-Mn oxyhydroxide Pb decreased, compared to their initial fractions. The residual fractions of Ni and Cr were dominant, regardless of pH.

Conclusions

The average concentrations of Cu, Zn, Cd, and Pb in sediments were highly elevated compared with the soil background values in Gansu Province, China. The results of this pH-dependent release experiment showed that the release behaviors of Cu, Zn, Pb, and Cr followed an asymmetric V-shaped pattern, whereas Cd and Ni followed an irregular L-shaped pattern. The changes in the release of heavy metals in sediments were related to their redistribution between chemical fractionations.

     

Zeitschrift für Pflanzenernährung und Bodenkunde: Schwermetallgehalt von Wurzel und Sproßorganen der Rebe (Vitis vinifera L.) nach Düngung mit Müll-Klärschlammkompost

Heavy metal content of roots and shoots of vines (Vitis vinifera L.) after fertilization with garbage-sewage-sludge-compost The enrichment of Zn, Cu, Pb, Cd, Co, Ni and Cr from garbage-sewage-sludge-compost in vineyard soils, vines and must was studied in field-and pot-experiments. The following results were obtained: 1. In a field experiment, in which garbage-sewage-sludge-compost was applied, a marked soil enrichment of Zn, Cu, Pb, Cd and Cr was found. It was most evident at the 0–20 cm depth but also obvious at the 40–60 cm depth thus indicating downward migration. The soil was not enriched with Co and Ni. The heavy metal content of leaves, berries and must of riesling vines did not increase on the plots treated with garbage-sewage-sludge-compost. 2. In a pot trial, using an acid and an alkaline soil each mixed with garbage-sewage-sludge-compost, it was observed that only the uptake of Zn and Cu increased into the leaves, tendrils and wood of the riesling cuttings. In relation to the content of the substrate, the heavy metals were detected in the roots percentually in the following order: Cu, Cd > Zn > > Pb, Co, Ni, Cr The root contents were mostly substantially higher than those of the shoot. The migration from root to shoot decreased in the following percentual order: Zn > Cu > Cd, Pb 3. The heavy metal content decreased considerably from the roots to the upper plant organs. This was reflected in low concentrations of heavy metals in the vine must.     

Fluoro‐mobilization of metals in a Slovak forest soil affected by the emissions of an aluminum smelter

Depositions originating from a central Slovak Al smelter may increase metal solubility in adjacent soils because they contain F (mainly HF). The reason for fluoro‐mobilization of metals may be the formation of soluble fluoro‐metal complexes or the mobilization of organic matter and subsequent formation of organo‐metal complexes. The objectives of our work were (1) to assess the extent of metal mobilization by fluoride in a Slovak Lithic Eutrochrept affected by the emissions of an Al smelter and (2) to model the dissolved metal species with the help of a chemical equilibrium model (MINEQL+). The O (Moder), A, and B horizons were equilibrated with solutions at F concentrations of 0, 0.9, 2.7, and 9.0 mmol l^—1. In the extracts, the concentrations of Al, Ca, Cd, Cr, Cu, Fe, K, Mg, Mn, Ni, Pb, Zn, dissolved organic carbon (DOC), free and complexed F, and the pH and electrical conductivity (EC) were determined. The heavy metal concentrations in the O horizon (Cd: 0.99, Cr: 18.0, Cu: 44, Ni: 26, Pb: 110, and Zn: 84 mg kg^—1) were 2.5 to 9 times larger than those in the A and B horizons. The concentrations of H₂O‐soluble F decreased from the O (261 mg kg^—1) to the A (103 mg kg^—1) and B horizon (92 mg kg^—1). In batch experiments increasing addition of F increased the equilibrium concentrations of Al, Cr, Cu, Fe, Ni, Pb, and DOC in all samples, of Cd in the A, and of K in the B horizon. At the same time the concentrations of complexed F and pH increased whereas EC decreased. Chemical equilibrium modelling indicated that the mobilizing effect of F resulted from the formation of fluoro‐Al complexes and organo‐complexes of all other metals.     

Trace metals in sediments and aquatic plants from the Xiangjiang River, China

Purpose

The metal concentrations and Pb isotopic composition in sediments and plants from the Xiangjiang River, China, were investigated to understand the contamination and potential toxicity of metals in sediments; to determine the accumulation and distribution of metals in plant tissues; and to trace the possible pollution source of Pb in sediments and plants.

Materials and methods

Sediments and plants were collected from 43 sampling sites in the study region. After sediments were air-dried and passed through a 63-??m sieve, they were acid-digested and DTPA-extracted for determination of total and bioavailable metals. The plants were separated into roots, leaves, and stems; dried; cut into pieces; and digested with HNO₃?CH₂O₂. Metals (As, Cd, Cr, Cu, Ni, Pb, and Zn) and Pb isotopic composition were analyzed by inductively coupled plasma-mass spectrometry.

Results and discussion

Maximum As, Cd, Cr, Cu, Ni, Pb, and Zn concentrations in sediments were 47.18, 55.81, 129.5, 161.6, 160.4, 430.7, and 1,098.8?mg?kg^?1, respectively. The bioavailable fractions of As, Cd, Cu, Pb, and Zn had significant linear relationship with their corresponding total contents in sediments while no significant relationship was observed between bioavailable and total contents of Cr and Ni. In general, plant tissues showed higher As, Cd, Cu, Pb, and Zn concentrations and lower Cr and Ni concentrations compared with sediments. The ²⁰⁶Pb/²⁰⁷Pb ratios decreased in the order of total > bioavailable > stems ?? leaves > roots. A strong linear correlation was observed between the ²⁰⁸Pb/²⁰⁶Pb and ²⁰⁶Pb/²⁰⁷Pb ratios of the plant tissues, sediments, and the possible pollution sources of Pb in the Xiangjiang River.

Conclusions

As, Cd, Cu, Pb, and Zn demonstrated higher contamination levels in sediments and plants compared with Cr and Ni. Cd had highest potential ecological risk. The Pb from anthropogenic sources with low ²⁰⁶Pb/²⁰⁷Pb ratios was preferentially associated with the bioavailable fractions in sediments and accumulated in roots. The Pb in plant tissues is mainly derived from the Pb in sediment and is taken up through the sediment-to-root pathway.