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.     

Pilot-scale counter-current acid leaching process for Cu,Pb, Sb,and Zn from small-arms shooting range soil

Purpose

The main objective of this study was to evaluate the potential of a counter-current leaching process (CCLP) on 14 cycles with leachate treatment at the pilot scale for Pb, Cu, Sb, and Zn removal from the soil of a Canadian small-arms shooting range.

Materials and methods

The metal concentrations in the contaminated soil were 904?±?112 mg Cu kg^–1, 8,550?±?940 mg Pb kg^–1, 370?±?26 mg Sb kg^–1, and 169?±?14 mg Zn kg^–1. The CCLP includes three acid leaching steps (0.125 M H₂SO₄?+?4 M NaCl, pulp density (PD)?=?10 %, t?=?1 h, T?=?20 °C, total volume?=?20 L). The leachate treatment was performed using metal precipitation with a 5-M NaOH solution. The treated effluent was reused for the next metal leaching steps.

Results and discussion

The average metal removal yields were 80.9?±?2.3 % of Cu, 94.5?±?0.7 % of Pb, 51.1?±?4.8 % of Sb, and 43.9?±?3.9 % of Zn. Compared to a conventional leaching process, the CCLP allows a significant economy of water (24,500 L water per ton of soil), sulfuric acid (133 L H₂SO₄ t^–1), NaCl (6,310 kg NaCl t^–1), and NaOH (225 kg NaOH t^–1). This corresponds to 82 %, 65 %, 90 %, and 75 % of reduction, respectively. The Toxicity Characteristic Leaching Procedure test, which was applied on the remediated soil, demonstrated a large decrease of the lead availability (0.8 mg Pb L^–1) in comparison to the untreated soil (142 mg Pb L^–1). The estimated total cost of this soil remediation process is 267 US$ t^–1.

Conclusions

The CCLP process allows high removal yields for Pb and Cu and a significant reduction in water and chemical consumption. Further work should examine the extraction of Sb from small-arms shooting range.     

Heavy Metal Content in Lettuce Plants Grown in Biosolids Compost

The objective of this work was to evaluate the affects of the application of composted biosolids on the accumulation of heavy metals (Cd, Cu, Ni, Pb and Zn) in lettuce leaves. Pots containing different proportions (0 to 100%) of composted biosolids were used to grow lettuce plants under greenhouse conditions. Dry and fresh weight, leaf area and Cd, Cu, Ni, Pb and Zn uptake were determined after harvest. It was found that the dry and fresh matter productions of the plants were significantly lower in the control treatment. The addition of composted biosolids caused a 20 and 40% increase in biomass accumulation. Cd and Pb concentrations in leaves were below detection limits (0.05 mg kg^?1) in all treatments. Zn concentration in leaves increases as compost proportion decreases, ranging from 57.2 to 80.4 mg kg^?1. Composted biosolids application increased the Cu and Ni plant concentrations, ranging from 5.1 to 9.8 mg Cu kg^?1 and 2.3 to 3.7 mg Ni kg^?1. In all treatments the proportions of heavy metals in plants were below the international standards of toxicity. The results allow us to suggest that, in short-term applications, composted biosolids could be used as soil amendment for lettuce production, without toxic effects in the chemical composition of the plant.     

Avian Urine: Its Potential as a Non-Invasive Biomonitor of Environmental Metal Exposure in Birds

Current non-invasive biomonitoring techniques to measure heavy metal exposure in free ranging birds using eggs, feathers and guano are problematic because essential metals copper (Cu) and zinc (Zn) deposited in eggs and feathers are under physiological control, feathers accumulate metals from surface contamination and guano may contain faecal metals of mixed bioavailability. This paper reports a new technique of measuring lead (Pb), Cu and Zn in avian urate spheres (AUS), the solid component of avian urine. These metal levels in AUS (theoretically representing the level of metal taken into the bloodstream, i.e. bioavailable to birds) were compared with levels in eggs (yolk and shell), feathers and whole guano from chickens (Gallus gallus domesticus) exposed to a heavy metal-contaminated soil (an allotment soil containing Pb 555?mg?kg^?1 dry mass (dm), Cu 273?mg?kg^?1?dm and Zn 827?mg?kg^?1?dm). The median metal levels (n?=?2) in AUS from chickens exposed to this contaminated soil were Pb 208???g?g^?1 uric acid, Cu 66???g?g^?1 uric acid and Zn: 526???g?g^?1 uric acid. Lead concentrations in egg yolk and shell samples (n?=?3) were below the limit of detection (<2?mg?kg^?1), while Cu and Zn were only consistently detected in the yolk, with median values of 3 and 70?mg?kg^?1 (dm), respectively, restricting the usefulness of eggs as a biomonitor. Feathers (n?=?4) had median Pb, Cu and Zn levels respectively of 15, 10 and 140?mg?kg^?1 (dm), while whole guano samples (n?=?6) were 140, 70 and 230?mg?kg^?1 (dm). Control samples were collected from another chicken flock; however, because they had no access to soil and their diet was significantly higher in Cu and Zn, no meaningful comparison was possible. Six months after site remediation, by top soil replacement, the exposed chickens had median Pb, Cu and Zn levels respectively in whole guano (n?=?6) of 30, 20 and 103?mg?kg^?1 (dm) and in AUS (n?=?4) of 147, 16 and 85???g?g^?1 uric acid. We suggest the persistent high Pb level in AUS was a consequence of bone mobilised for egg production, releasing chronically sequestered Pb deposits into the bloodstream. In contrast, AUS levels of Cu and Zn (metals under homeostatic control and sparingly stored) had declined, reflecting the lower current exposure. However because pre- and post-remediation samples were measured using different methods carried out at different laboratories, such comparisons should be guarded. The present study showed that metals can be measured in AUS, but no assessment could be made of availability or uptake to the birds because tissue and blood samples were not concomitantly analysed. A major short coming of the study was the inappropriate control group, having no access to uncontaminated soil and being fed a different diet to the exposed birds. Furthermore guano and urine analysis should have been carried out on samples from individual birds, so biological (rather than just technical) variation of metal levels could have been determined. Future studies into using AUS for biomonitoring environmental heavy metals must resolve such experimental design issues.     

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.     

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.     

Leaching Behavior of Heavy Metals In Biosolids Amended Sandy Soils

Use of biosolids in agriculture to improve crop production and soil quality have created concerns due to content of heavy metals that may affect surface or ground water quality. A column leaching study was conducted to evaluate the leaching potential of copper (Cu), lead (Pb), zinc (Zn), cdmium (Cd), cobalt (Co), chromium (Cr), and nickel (Ni) from two typical agricultural sandy soils in South Florida (Spodosol and Alfisol) with increasing application of pelletized biosolids (called PB) at the rates of 0, 1.25, 5.0, 10.0 g kg^?1, respectively together with chemical fertilizer (CF). Elevated PB rate resulted in reduced leaching loss of Cu, Pb, Zn, Cd, Co, Ni from Spodosol, but resulted in increased loss of Pb, Zn, Cd, and Co from Alfisol. Significant reduction in Cu loss occurred in both soils, which can be attributed to the strong binding of Cu with organic matter from the applied PB. Percentage of Cd loss as of total Cd was 13% – 41%, the highest in all the heavy metals, whereas loss of Pb as of total Pb was less than 6.6%, though the concentrations of Pb, Cd, Co, and Ni in leachate were mostly above the limits of U.S. EPA drinking water standards or the national secondary drinking water standards. These results indicate that soil properties, PB application rates, and chemical behavior of elements jointly influence the leachate total loads of heavy metals in sandy soils applied with biosolids. Application of CF together with BP at a rate higher than 10.0 g kg^?1 for sandy soils may pose potential threats to water quality due to enhanced leachate loads of Cr and Ni in Spodosol and Pb, Zn, Cd, Co and Ni in Alfisol.     

Heavy Metal Pollution in Soils Around the Abandoned Mine Sites of the Iberian Pyrite Belt (Southwest Spain)

This paper investigates the pollution load of selected trace elements in 32 soil samples collected around 21 different mining areas of the Iberian Pyrite Belt (Southwest Spain), integrating chemical data with soil parameters to help understand the partitioning and mobility of pollutants. The minesoils are depleted in acid neutralising minerals and show limiting physicochemical properties, including low pH values and very high anomalies of potentially hazardous metals. The total concentrations of As (up to 1,560 mg kg^?1) and certain heavy metals (up to 2,874 mg kg^?1 Cu, 6,500 mg kg^?1 Pb, 6,890 mg kg^?1 Zn, 62 mg kg^?1 Hg and 22 mg kg^?1 Cd) are two orders of magnitude above the soil background values. The close association of Cd and Zn with the carbonate content in lime-amended minesoils suggests metal immobilisation through adsorption and/or co-precipitation mechanisms, after acid neutralisation, whereas As and Pb are similarly partitioned into the soil and mostly associated with iron oxy-hydroxides.     

Heavy‐Metal Inhibition of Nitrification in Selected Iowa Soils Treated with Stay‐N 2000

Abstract

Heavy‐metal inhibition of nitrification in soils treated with reformulated nitrapyrin was investigated. Clarion and Okoboji soils were treated with ammonium sulfate [(NH₄)₂SO₄] and a nitrification inhibitor. Copper(II) (Cu), Zinc(II) (Zn), Cadmium(II) (Cd), or Lead(II) (Pb) were added to each soil. A first‐order equation was used to calculate the maximum nitrification rate (K _max), duration of lag period (t′), period of maximum nitrification (Δt), and the termination period of nitrification (t _s). In the Clarion soil, the K _max decreased from 12 mg kg^?1 d^?1 without the nitrification inhibitor to 4, 0.25, 0.86, and 0.27 mg kg^?1 d^?1, respectively, when the inhibitor and Cu, Zn, Pb, or Cd were applied. In the Okoboji soil, K _max decreased from 22 mg kg^?1 d^?1 with no inhibitor to 6, 3, 4, and 2 mg kg^?1 d^?1, respectively, when an inhibitor and Cu, Zn, Pb, or Cd were added. The t′ varied from 8 to 25 d in the Clarion soil and from 5 to 25 d in the Okoboji soil, due to addition of Cu, Zn, Pb, or Cd and the inhibitor.     

Effects of Soil Amended with Cadmium and Lead on Growth,Yield, and Metal Accumulation and Distribution in Parsley

A greenhouse experiment was designed to determine the cadmium (Cd) and lead (Pb) distribution and accumulation in parsley plants grown on soil amended with Cd and Pb. The soil was amended with 0, 5, 10 20, 40, 60, 80, and 100 mg Cd kg^?1 in the form of cadmium nitrate [Cd(NO₃)₂] and 0, 5, 10, 50 and 100 mg Pb kg^?1 in the form of lead nitrate [Pb(NO₃)₂]. The main soil properties; concentrations of the diethylenetriaminepentaacetic acid (DTPA)–extractable metals lead (Pb), Cd, copper (Cu), iron (Fe), zinc (Zn), and manganese (Mn) in soil; plant growth; and total contents of metals in shoots and roots were measured. The DTPA-extractable Cd was increased significantly by the addition of Cd. Despite the fact that Pb was not applied, its availability was significantly greater in treatments 40–100 mg Cd kg^?1 compared with the control. Fresh biomass was increased significantly in treatments of 5 and 10 mg Cd kg^?1 as compared to the control. Further addition of Cd reduced fresh weight but not significantly, although Cd concentration in shoots reached 26.5 mg kg^?1. Although Pb was not applied with Cd, its concentration in parsley increased significantly in treatments with 60, 80, and 100 mg Cd g^?1 compared with the others. Available soil Pb was increased significantly with Pb levels; nevertheless, the increase was small compared to the additions of Pb to soil. There were no significant differences in shoot and root fresh weights between treatments, although metal contents reached 20.0 mg Pb kg^?1 and 16.4 mg Pb kg^?1 respectively. Lead accumulation was enhanced by Pb treatments, but the positive effect on its uptake was not relative to the increase of Pb rates. Cadmium was not applied, and yet considerable uptake of Cd by control plants was evident. The interactive effects of Pb and Cd on their availability in soil and plants and their relation to other metals are also discussed.     

Forms of trace metals from inorganic sources in soils and amounts found in spring barley

Barley (Hordeum vulgare L.) was grown on a sandy soil given different doses of cadmium carbonate (salt), copper carbonate (malachite), lead carbonate (cerussite), and zinc carbonate (smithsonite) in a pot experiment conducted in a greenhouse. The element compounds were added to the soil in amounts equivalent to the following levels of the metals: Cd 5, 10, 50 μq ^?1; Cu and Pb 50, 100, 500 μg g^?1; Zn 150, 300, 1500 μg g^?1. Sequential extraction was used for partition these metals into five operationally-defined fractions: exchangeable, bound to carbonates, bound to Fe-Mn oxides, bound to organic matter and residual. The residue was the most abundant fraction in the untreated soil for all the metals studied (43 to 61% of the total contents). The concentration of exchangeable Cd (0.2 μg g^?1), Cu (0.01 μg g^?1), Pb (0.1 μg g^?1), and Zn (1.4 μg g^?1) were relatively low in the untreated soil but increased markedly in the treated soils for Cd (up to 31 μg g^?1) and Zn (up to 83 μg g^?1), whereas only small changes were observed for Cu and Pb. The pot experiment showed a significant increase in the Cd and Zn contents of barley grown on the treated soils, but only small changes in Cu and Pb concentrations.     

Trace Element Concentrations in Saltmarsh Soils Strongly Affected by Wastes from Metal Sulphide Mining Areas

Soil and water samples were analysed for trace metals and As in two watercourses and 14 sampling plots in a salt marsh polluted by mine wastes in SE Spain. Groundwater levels, soil pH and Eh were measured ‘in situ’ for a 12-month period in each sampling plot, and total calcium carbonate was also determined. Low concentrations of soluble metals (maximum Mn 1.089 mg L^?1 and maximum Zn 0.553 mg L^?1) were found in the watercourses. However, total metal contents were extremely high in the soils of a zone of the salt marsh (maximum 1,933 mg kg^?1 of Mn, 62,280 mg kg^?1 of Zn, 16,845 mg kg^?1 of Pb, 77 mg kg^?1 of Cd, 418 mg kg^?1 of Cu and 725 mg kg^?1 of As), and soluble metals in the pore water reached 38.7 mg L^?1 for Zn, 3.15 mg L^?1 for Pb, 48.0 mg L^?1 for Mn, 0.61 mg L^?1 for Cd and 0.29 mg L^?1 for As. Variable concentrations with depth indicate a possible re-mobilisation of the metals, which could be related to spatial and temporal variations of water table level, pH and Eh and to the presence of calcium carbonate. A tendency for the Eh to decrease in the warmest months and to increase in the coldest ones was found, especially, in plots that received water with a high content of dissolved organic carbon. Hence, the existence of nutrient effluent-enriched water may modify the physical–chemical conditions of the soil–water system and influence metal mobility.     

Dissolved Organic Carbon in Association with Water Soluble Nutrients and Metals in Soils from Lake Okeechobee Watershed, South Florida

Water quality of Lake Okeechobee has been a major environmental concern for many years. Transport of dissolved organic matter (DOM) in runoff water from watershed is critical to the increased inputs of nutrients (N and P) and metals (Cu and Zn). In this study, 124 soil samples were collected with varying soil types, land uses, and soil depths in Lake Okeechobee watershed and analyzed for water-extractable C, N, P, and metals to examine the relationship between dissolved organic carbon (DOC) and water soluble nutrients (N and P) and metals in the soils. DOC in the soils was in 27.64?C400 mg kg^?1 (69.30 mg kg^?1 in average) and varied with soil types, land uses, and soil depth. The highest water-extractable DOC was found in soils collected in sugar cane and field crops (277 and 244 mg kg^?1 in average, respectively). Water soluble concentrations of N and P were in the range of 6.46?C129 and 0.02?C60.79 mg kg^?1, respectively. The ratios of water-extractable C/N and C/P in soils were in 0.68?C12.52 (3.23 in average) and 3.19?C2,329 (216 in average), and varied with land uses. The lowest water-extractable C/N was observed in the soils from dairy (1.66), resident (1.79), and coniferous forest (4.49), whereas the lowest water-extractable C/P was with the land uses of dairy (13.1) and citrus (33.7). Therefore, N and P in the soils under these land uses may have high availability and leaching potential. The concentrations of water soluble Co, Cr, Cu, Ni, and Zn were in the ranges of?<?method detection limit (MDL)?C0.33, <MDL?C0.53, 0.04?C2.42, <MDL?C0.71, and 0.09?C1.13 mg kg^?1, with corresponding mean values of 0.02, 0.01, 0.50, 0.07, and 0.37 mg kg^?1, respectively. The highest water soluble Co (0.10 mg kg^?1), Cr (0.26 mg kg^?1), Ni (0.31 mg kg^?1), and Zn (0.80 mg kg^?1) were observed in soils under the land use of sugar cane, whereas the highest Cu (1.50 mg kg^?1) was with field crop. The concentration of DOC was positively correlated with total organic carbon (TOC) (P <0.01), water soluble N (P <0.01), electrical conductivity (EC, P <0.01), and water soluble Co, Cr, Ni, and Zn (P <0.01), and Cu (P <0.05), whereas water soluble N was positively correlated with water soluble P, Cu, and Zn (P <0.01) in soils. These results indicate that the transport of DOC from land to water bodies may correlate with the loss of macro-nutrients (N, P), micro-nutrients (Cu, Zn, and Ni), and contaminants (Cr and Co) as well.     

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.     

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.     

Anthropogenic Heavy Metal Pollution in the Surficial Sediments of the Keratsini Harbor, Saronikos Gulf, Greece

The contents of ten elements [Cd, Pb, W, Zn, Mn, As, Se, Cr, Cu, and organic carbon (C_org)] have been determined in the surficial sediments of Keratsini harbor, Saronikos Gulf, Greece. The contamination of the sediments was assessed on the basis of geoaccumulation index and to corresponding sediment quality guidelines (SQGs) effects range low/effects range median. The results revealed highly elevated Cd, Pb, W, Zn, As, Se, Cr, Cu, and C_org values (Cd, 190–1,763 mg kg^?1; Pb, 521–1,263 mg kg^?1; W, 38–100 mg kg^?1; Zn, 409–6,725 mg kg^?1; Mn, 95–1,101 mg kg^?1; As, not detectable–1,813 mg kg^?1; Se, not detectable–58 mg kg^?1; Cr, 264–860 mg kg^?1; Cu, 195–518 mg kg^?1; and C_org, 0.69–4.41%). The enrichment of metals in the sediments results from the contribution of the central Athens sewage outfall through which the waste of the Attica basin ends up in Keratsini harbor as well as from industrial and ship contaminants.     

Chemical characterization of heavy-metal contaminated soil in southeast Kansas

A tri-state mining region, including parts of Missouri, Oklahoma, and Kansas, was the site of intense lead and zinc mining and smelting activity until the 1950's. A study was initiated to characterize the heavy-metal contamination of soils in this area. Water-soluble, an index of plantavailable, total, and sequentially extractable metals; organic, and total carbon; and saturated paste pH were determined for mine tailings and soil samples. Mine tailings contained 81 to 89 mg kg^?1 total Cd, 1 150 to 1 370 mg kg^?1 total Pb, and 11 400 to 13 700 mg kg^?1 total Zn. Total concentrations in soil samples were 15 to 86 mg kg^?1 Cd, 35 to 1 620 mg kg^?1 Pb, and 99 to 18 500 mg kg^?1 Zn; and, DTPA extractable concentrations ranged from 0.6 to 10 mg kg^?1 Cd, 7.8 to 68 mg kg^?1 Pb, and 33 to 715 mg kg^?1 Zn. Samples were sequentially extracted to approximate the proportions of the metals in the sulfide, carbonate, organic, sorbed, and exchangeable fractions. For Zn and Cd, concentrations were greatest in the sulfide fraction followed by carbonate, organic, sorbed, and exchangeable. Lead followed the same pattern, except higher concentrations were observed in the sorbed than the organic fractions.     

Heavy Metals in Mycorrhizal Rhizospheres Contaminated By Zn–Pb Mining and Smelting Around Olkusz in Southern Poland

Soils in areas of mining and smelting of Pb–Zn ores in Southern Poland are strongly enriched in heavy metals (Zn, Pb, Fe, Cd, Tl, As). The highest concentrations of Zn (<55,506 mg kg^?1), Pb (<8,262 mg kg^?1), Cd (<220 mg kg^?1) and Tl (<67 mg kg^?1) are linked to the fine fractions of upper soil layers in sites contaminated by past exploitation and processing of ores. The high stress of metals, and the negative influence of acid waste drainage has limited the development of flora and fauna in these areas. The increasing ability of plants to grow is due to the positive symbiotic action of fungi and bacteria. The mycorrhizal communities were identified in rhizospheres rich in unstable Zn–Pb–Fe sulphides such as sphalerite, galena, pyrite and marcasite and carbonates of Zn (smithsonite) and Pb (cerussite). They occur in associations with sulphates, e.g., gypsum. In parts of fungi, secondary mineral phases containing Zn, Pb, Fe and Mn occur. Metal-bearing aggregates formed during symbiotic action between myccorhiza and bacteria connected with them. They enhance the binding of bio-available ions of Zn, Pb and Mn in the most unstable phases. Metal contents in the mycorrhizal parts of the rhizospheric soils were determined by Atomic Absorption Spectroscopy. Mineralogical investigations involved X-ray diffraction, scanning electron microscopy with energy dispersive spectrometry.     

Fraction Distributions of Lead,Cadmium, Copper,and Zinc in Metal‐Contaminated Soil before and after Extraction with Disodium Ethylenediaminetetraacetic Acid

Abstract: The fraction distributions of heavy metals have attracted more attention because of the relationship between the toxicity and their speciation. Heavy‐metal fraction distributions in soil contaminated with mine tailings (soil A) and in soil irrigated with mine wastewater (soil B), before and after treatment with disodium ethylenediaminetetraacetic acid (EDTA), were analyzed with Tessier's sequential extraction procedures. The total contents of lead (Pb), cadmium (Cd), copper (Cu), and zinc (Zn) exceeded the maximum permissible levels by 5.1, 33.3, 3.1, and 8.0 times in soil A and by 2.6, 12.0, 0.2, and 1.9 times in soil B, respectively. The results showed that both soils had high levels of heavy‐metal pollution. Although the fractions were found in different distribution before extraction, the residual fraction was found to be the predominant fraction of the four heavy metals. There was a small amount of exchangeable fraction of heavy metals in both contaminated soils. Furthermore, in this study, the extraction efficiencies of Pb, Cd, and Cu were higher than those of Zn. After extraction, the concentrations of exchangeable Pb, Cd, Cu, and Zn increased 84.7 mg·kg^?1, 0.3 mg·kg^?1, 4.1 mg·kg^?1, and 39.9 mg·kg^?1 in soil A and 48.7 mg·kg^?1, 0.6 mg·kg^?1, 2.7 mg·kg^?1, and 44.1 mg·kg^?1 in soil B, respectively. The concentrations of carbonate, iron and manganese oxides, organic matter, and residue of heavy metals decreased. This implies that EDTA increased metal mobility and bioavailability and may lead to groundwater contamination.     

EDTA Leaching of Cu Contaminated Soils Using Ozone/UV for Treatment and Reuse of Washing Solution in a Closed Loop

Ozone and UV irradiation were used for oxidative decomposition of EDTA-Cu complexes in washing solution obtained during multi-step leaching of Cu (344,1?±?36.5 mg kg^?1) contaminated vineyard soil with EDTA as a chelant. The released Cu was absorbed from the washing solution on a commercial mixture of metal absorbing minerals, and the treated washing solution then reused for removal of soil residual Cu-EDTA complexes in a closed-loop process. Six consecutive leaching steps (6?×?2.5 mmol kg^?1 of EDTA) removed 38.8 % of Cu from soils, and reduced Cu soil mobility, determined using the toxicity characteristic leaching test (TCLP), by 28.5%. The final washing solution obtained after soil remediation was colourless, with a pH close to neutral (7.5?±?0.2) and with low concentrations of Cu and EDTA (0.51?±?0.22 mg L^?1 and 0.083 mM, respectively). The proposed remediation method has therefore potential not just to recycle and save process water, but also not to produce toxic wastewaters. Soil treatment did not substantially alter the soil properties determined by pedological analysis, and had relatively little impact on soil hydraulic conductivity and soil water sorption capacity.