Modeling Sorption of Cd,Hg and Pb in Soils by the NICA-Donnan Model

Metal adsorption is an important process at the soil-solution interface that controls metal bioavailability and toxicity. In this study, batch adsorption experiments were conducted to investigate the binding of Cd, Hg and Pb in soils collected from around metal smelters in Quebec and Ontario, Canada. It was found that soil organic matter enhanced the retention of Cd, Hg and Pb. Assuming that the surfaces of soil particles behaved similarly to organic matter, we used the Non-Ideal Competitive Adsorption (NICA)-Donnan model to derive the parameters for surface complexation of the three metals. The shape of the Cd, Hg and Pb adsorption isotherms are briefly discussed with respect to the results of the experimental measurements and the model predictions. The average values of the NICA-Donnan model parameters could be used to give reasonable predictions of metal sorption in the soils of this study.     

Instances of Soil and Crop Heavy Metal Contamination in China

Both general and specific investigations of soil and crop heavy metal contamination were carried out across China. The former was focused mainly on Cd, Hg, As, Pb, and Cr in soils and vegetables in suburbs of four large cities; the latter investigated Cd levels in both soils and rice or wheat in contaminated areas throughout 15 provinces of the country. The results indicated that levels of Cd, Hg, and Pb in soils and some in crops were greater than the Governmental Standards (Chinese government limits for soil and crop heavy metal contents). Soil Cd ranged from 0.46 to 1.04?mg kg^?1, on average, in the four cities and was as high as 145?mg kg^?1 in soil and 7?mg kg^?1 in rice in the wide area of the country. Among different species, tuberous vegetables seemed to accumulate a larger portion of heavy metals than leafy and fruit vegetables, except celery. For both rice and wheat, two staple food crops, the latter seemed to have much higher concentrations of Cd and Pb than the former grown in the same area. Furthermore, the endosperm of both wheat and rice crops had the highest portion of Cd and Cr. Rice endosperm and wheat chaff accumulated the highest Pb, although the concentrations of all three metals were variable in different parts of the grains. For example, 8.3, 6.9, 1.4, and 0.6?mg kg^?1 of Pb were found in chaff, cortex, embryo, and endosperm of wheat compared with 0.11, 0.65, 0.71, and 0.19?mg kg^?1 in the same parts of rice, respectively. Untreated sewage water irrigation was the major cause of increasing soil and crop metals. Short periods of the sewage water irrigation increased individual metals in soils by 2 to 80% and increased metals in crops by 14 to 209%. Atmospheric deposition, industrial or municipal wastes, sewage sludge improperly used as fertilizers, and metal-containing phosphate fertilizers played an important role as well in some specific areas.     

Simultaneous extraction of soil phytoavailable cadmium,copper, and lead by chelating resin membrane

Cadmium, copper, and lead were extracted from suspensions of contaminated soils using metal chelating exchange resin membranes. Nine soils with widely varying properties and Cd, Cu and Pb levels were tested. Soil suspensions made up with 4 g in 40 mL deionized water were equilibrated with 5 cm² Ca-saturated Chelex exchange resin membrane which was retained inside a polypropylene bag and shaken at 150 rpm for 24 hrs. Resin membrane extractable Cd, Cu and Pb of the soils were correlated with Cd, Cu, and Pb uptake by young wheat seedlings grown in these soils and compared with soil Cd, Cu, and Pb extracted by 0.1 M HCl, 0.01 M CaCl₂, and 0.005 M Diethylenetriamine pentaacetic acid (DTPA). The amounts of Cd, Cu and Pb extracted by the Ca-saturated Chelex membrane from all tested soils correlated well with those absorbed by young wheat seedlings. The Ca-saturated Chelex membrane extractable Cd, Cu and Pb of the soil had the strongest correlation with plant uptake Cd, Cu and Pb among the extraction methods we tested. It was demonstrated that the Ca-saturated Chelex membrane extraction is an appropriate method in simultaneously estimating Cd, Cu and Pb phytoavailability of soil and is applicable to a wide range of soils.     

Characterization of Bacteria in the Rhizosphere Soils of Polygonum Pubescens and Their Potential in Promoting Growth and Cd,Pb, Zn Uptake by Brassica napus

Microbe-enhanced phytoremediation has been considered as a promising measure for the remediation of metal-contaminated soils. In this study, two bacterial strains JYX7 and JYX10 were isolated from rhizosphere soils of Polygonum pubescens grown in metal-polluted soil and identified as of Enterobacter sp. and Klebsiella sp. based on 16S rDNA sequences, respectively. JYX7 and JYX10 showed high Cd, Pb and Zn tolerance and increased water-soluble Cd, Pb and Zn concentrations in culture solution and metal-added soils. Two isolates produced plant growth-promoting substances such as indole acetic acid, siderophore, 1-aminocyclopropane-1-carboxylic deaminase, and solubilized inorganic phosphate. Based upon their ability in metal tolerance and solubilization, two isolates were further studied for their effects on growth and accumulation of Cd, Pb, and Zn in Brassica napus (rape) by pot experiments. Rapes inoculated with JYX7 and JYX10 had significantly higher dry weights, concentrations and uptakes of Cd, Pb, Zn in both above-ground and root tissues than those without inoculation grown in soils amended with Cd (25 mg kg^?1), Pb (200 mg kg^?1) or Zn (200 mg kg^?1). The present results demonstrated that JYX7 and JYX10 are valuable microorganism, which can improve the efficiency of phytoremediation in soils polluted by Cd, Pb, and Zn.     

Characterization of Aqueous Pb(II) and Cd(II) Biosorption on Native and Chemically Modified Alstonia macrophylla Saw Dust

This study was conducted in order to understand the mechanism of Cd and Pb adsorption in aqueous solutions by raw and modified saw dust (SD) of Alstonia macrophylla. The biosorbent was characterized by Boehm titration, specific surface area, scanning electron microscopy (SEM), X-ray energy dispersion (EDAX), and Fourier transform infrared (FTIR) analyses. SD was treated using organic acids and bases. Batch studies were conducted for raw and modified SD to determine the effect of initial concentration, pH, ionic strength, and contact time on metal adsorption. The specific surface area and total basic and acidic groups of SD were 77 m²/g and 1521 and 2312 μmol/g, respectively. The adsorption of both metals onto SD was pH dependent. No ionic strength dependency was observed in adsorption of Cd and Pb at pH >6, indicating inner sphere surface complexation. Monolayer adsorption is dominant in both metal sorptions by SD. Furthermore, there is no competition between metals on adsorption and raw SD was found to be suitable for removal of Cd and Pb as compared to organic acid– or base-treated SD. Maximum adsorption capacity of SD for Cd and Pb were 30.6 and 204.2 mg/g, respectively. Results indicate that the A. macrophylla SD can be considered as a potential material for metal ion removal from wastewater.     

Concentration and Distribution of Six Trace Metals in Northern Kentucky Soils

Concentration and distribution of cadmium (Cd), chromium (Cr), copper (Cu), nickel (Ni), lead (Pb), and zinc (Zn) were determined in 26 soil profiles (n = 78) of northern Kentucky in response to environmental concerns about increasing anthropogenic inputs in a fast-paced urbanizing area. The selected sites represent alluvial, glacial till or residual soils that have not received any biosolid- or industrial-waste applications. Mean concentrations of Zn (53.8 mg kg^?1) and Ni (25.9 mg kg^?1) were the highest in the soil profile, whereas Cd (0.21 mg kg^?1) was present only in trace amounts. All metals were within the low to middle range of baseline concentrations reported for US soils, suggesting minimal anthropogenic inputs. The distribution of Cu, Cr, Ni, and Zn increased with soil depth, whereas Cd and Pb concentrations were unaffected throughout the soil profile. Alluvial soils had the highest overall metal accumulations, particularly in surface soil horizons, indicating potential metal enrichment through depositional processes. The presence of a fragipan horizon or depth to bedrock did not significantly affect metal retention. Single correlation and multiple regression analyses indicated OM and pH as the most influential soil parameters for metal retention, followed by cation exchange capacity (CEC) and CEC/clay. Single correlations among metals suggested strong covariance of Zn with most metals throughout the soil profile, but weaker for Pb and Ni.     

Acacia nilotica L. Bark Removes Toxic Elements from Solution: Corroboration from Toxicity Bioassay Using Salix viminalis L. in Hydroponic System

The present investigation deals with the advantages and potential of the Acacia nilotica bark as an adsorbent of toxic metals. Bark (1 g) when added to 100 ml of aqueous solution containing 10 μg ml^-1 metal solution exhibited different metal adsorption values for different metals. The order of metal adsorption being Cr ≥ Ni > Cu > Cd > As > Pb. A similar trend of metal adsorption was observed when the bark is reused (1^st recycle) Cr> Ni > Cu > Cd > Pb and also in the column sorption. In order to verify the metal removal property of A. nilotica bark, toxicity bioassay with Salix viminalis stem cuttings in hydroponic system augmented with Cd, Cr, and Pb together with A. nilotica bark powder was carried out. The results of toxicity bioassay confirmed the metal adsorption property of the bark powder. The functions of toxicity studies include leaf area, root length and number of new root primordia produced per stump. The leaf area, root length, and the number of new root primordia increased considerably in the presence of A. nilotica bark. The order of metal toxicity for leaf area and new root primordial is Cd > Cr > Pb. However, for root length the order of metal toxicity is Cr > Cd > Pb. The metal budgets of the leaf and root confirmed that the bark powder had adsorbed substantial amount of toxic metals and thus alleviates the toxicity imposed by the various tested elements. Hence, the utility of A. nilotica bark in developing and designing innovative technology for the clean up of toxic elements in aqueous solutions and possible scope for its use in phytoremediation are discussed.     

The effect of soil type and degree of metal contamination upon uptake of Cd,Pb and Cu in bush beans (Phaseolus vulgaris L.)

Summary Five soils of increasing specific surface area (SSA) were loaded to five levels of contamination with Cd, Pb and Cu, and bean plants (Phaseolus vulgaris L.) were grown on the soils for 30 days. A linear correlation was found between the concentration of Cd in the soil solutions and the amount absorbed by the plant per gram root material for four out of the five soils, and, in the case of Cu, for all five soils. Quantitatively, there was insufficient Cd or Cu in the soil solution to account for plant uptake of these metals. The amount of Cd absorbed by plants could also be related to the adsorption density (concentration/SSA soil) of the metal in four of the five soils, whereas the Cu content of plants could be related to the adsorption density of all five soils. It is thought that the metals were removed from the soil solution by root absorption and replenished by metal cations adsorbed onto surface sites in the soil. Consideration of the adsorption density of these metals in the soil may be a useful means to determine the permissible limits for heavy metal application for a wide range of soils. Lead uptake was significantly correlated to total Pb in soils, but not to the adsorption density or soil solution concentrations. The possible interpretation of the results are discussed.     

Sources and Ecological Risk Assessment of Heavy Metal(loid)s in Agricultural Soils of Huzhou,China

To identify sources of heavy metal(loid) (HM) contamination in agricultural soils of Huzhou, surface soil samples were sampled from 89 different agricultural regions in 2012. Concentrations of heavy metal(loid)s, along with pH, total phosphorus (TP), total nitrogen (TN), and soil organic matter (SOM), were determined. Ecological risk was then assessed using a modified Hakanson ecological risk index, and the sources of contamination were determined using principal component analysis (PCA). Mean concentrations of heavy metal(loid)s were 10.26, 23.21, 83.75, 22.81, 0.25, 61.86, 33.03, and 0.15 mg kg^?1 for As, Cu, Zn, Ni, Cd, Cr, Pb, and Hg, respectively. Cu, Zn, Ni, Cr, Cd, Hg, and Pb were correlated positively with TP and there were obvious positive correlations among Cu, Zn, Ni, Cr, and Cd. Risk index (RI) values varied from 39 to 1246 with a mean value of 137. Enrichment of Pb, Zn, Cu, and especially Cd can be attributed to excessive use of nitrogen and phosphorus fertilizers containing heavy metals, as well to surface irrigation and natural soil formation. While the ecological risk of most agricultural soils in Huzhou is low, it is recommended that the use of phosphate and nitrogen fertilizers be restricted and production technology be improved to reduce the heavy metal(loid) concentrations. Results suggest that the Chinese environmental quality standard for soil should be revised to better address heavy metal(loid) contamination.     

Vertical and Horizontal Distributions of Zn,Cd, Pb,Cu, and Hg in Uncultivated Soil in the Vicinity of a Zinc Smelter at Odda,Norway

In the present work the extent and variation of Zn, Cd, Pb, Cu, and Hg loading in undisturbed surface soil (0–5 cm) and the vertical transport of the metals in soil profiles are studied in the vicinity of a zinc smelter in Norway. Three major controlling factors on the metal concentrations in soil have been assessed: 1) distance from the anthropogenic point source; 2) organic matter content (O.M.); and 3) the prevailing wind directions. Moreover metal distributions in proximal soil profiles in 1972 and 2003 are compared. Current concentrations of Zn, Cd, Pb, Cu, and Hg in surface soil reach 14000, 60, 980, 430, and 7.0 mg·kg ^{? 1} , respectively, near the smelter and decrease regularly with distance in the northerly direction according to the regression model (y = ax^{? b} ). The Zn concentrations are significantly different from the background range up to 30 km from the smelter, whereas the other metals approach background at only 10 km distance. Subsurface concentration peaks of Pb, Cu, and Hg are found at greater depth in soil profiles than peaks of Zn and Cd. Levels of Zn, Cd, and Pb in surface soil seem to have decreased from 1972 to 2003, whereas for Cu the levels appear not to be significantly different.     

Effect of Immobilizing Substances and Salinity on Heavy Metals Availability to Wheat Grown on Sewage Sludge-Contaminated Soil

The objective of the investigation was to evaluate the effect of immobilizing substances and NaCl salinity on the availability of heavy metals: Zn, Cd, Cu, Ni, and Pb to wheat (Triticum aestivum L.). In greenhouse pot experiment, a sewage sludge amended soil was treated with the following immobilizing substances: three clay minerals (Na-bentonite, Ca-bentonite and zeolite), iron oxides (goethite and hematite), and phosphate fertilizers (superphosphate and Novaphos). The pots were planted with wheat and were irrigated either with deionized or saline water containing 1600 mg L^?1 NaCl. Wheat was harvested two times for shoot metal concentrations and biomass measurements. Metal species in soil solution were estimated using the software MINEQL+.

The addition of metal immobilizing substances to the soil significantly decreased metal availability to wheat. The largest reduction in metal bioavailability was found for bentonites. The irrigation with saline water (1600 mg L^?1 NaCl) resulted in a significant increase in metal chloride species (MCl⁺ and MCl₂ ⁰). The highest metal complexation with Cl occurred for Cd, which was about 53% of its total soil solution concentration. The total concentration of Cd (Cd_T) in soil solution increased by 1.6–2.8-fold due to saline water. The NaCl salinity caused a significant increase in uptake and shoot concentration of Cd for two harvests and small but significant increase in shoot Pb concentration for the second harvest. It was concluded that the use of bentonites is the most promising for the reduction of heavy metal availability to plants. Saline water containing 1600 mg L^{? 1} NaCl increased the availability of Cd and Pb to wheat and decreased the efficiency of bentonites to immobilize soluble Cd.     

Copper,Lead, Cadmium,and Zinc Sorption By Waterlogged and Air-Dry Soil

Competitive sorption of copper (Cu), lead (Pb), cadmium (Cd), and zinc (Zn) was studied in three soils of contrasting chemical and physical properties under air-dry and waterlogged conditions. Competitive sorption was determined using the standard batch technique using six solutions, each with Cu, Pb, Cd, and Zn concentrations of approximately 0, 2.5, 5, 10, 20, and 50?mg L^?1Waterlogged soils tended to sorb higher amounts of added Cu, Pb, Zn and Cd relative to soils in the air-dry condition; however, this increase in sorption was generally not statistically (p<0.05) significant. The magnitude of sorption under both waterlogged and air-dry conditions was affected by the type and amount of soil materials involved in metal sorption processes, and competition between other metals for the sorption sites. Metal sorption was closely correlated with soil properties such as cation exchange capacity, organic carbon, and Fe and Mn hydrous oxides. Exchangeable Al may have markedly reduced metal sorption due to its strong affinity for the sorption sites, while increases in exchangeable Mn may have enhanced Zn and Cd sorption. Heavy metal sorption was best described as a combination of both specific and nonspecific interactions. The extractability of Cu, Pb, Cd, and Zn under waterlogged and air-dry conditions was also studied. Three solutions containing these metals were mixed with each soil to achieve a final concentration of 0, 50, and 500?mg kg^?1. Each soil was extracted every 7 days using 1?M MgCl₂ (pH 7) to determine metal extractability. Metal extractability initially decreased then increased due to waterlogging. The increased extractability of added metals was closely related to increased solubility of Fe and Mn suggesting that dissolution of Fe and Mn, oxides under reducing conditions caused a release of previously sorbed Cu, Pb, Cd, and Zn.     

浙江油茶产地土壤和果实金属元素含量特征

为探讨油茶(Camellia oleifera)产地土壤和油茶果实中金属元素分布和富集特征,在油茶果实成熟期,对浙江5个油茶产地土壤及油茶果实中金属元素进行污染分析和富集能力评价.结果表明,浙江油茶产地土壤中Pb、Cr、Cd、As、Hg、Ni、Cu和Zn含量低于农用地土壤污染风险筛选值,综合污染等级为安全.个别产区常山...     

Leaching of Zinc,Cadmium, and Lead in a Sandy Soil Due to Application of Poultry Litter

Dissolved organic matter in poultry litter could contribute organic ligands to form complexes with heavy metals in soil. The soluble complexes with heavy metals can be transported downward and possibly deteriorate groundwater quality. To better understand metal mobilization by soluble organic ligands in poultry litter, soil columns were employed to investigate the movement of zinc (Zn), cadmium (Cd), and lead (Pb). Uncontaminated soil was amended with Zn, Cd, and Pb at rates of 400, 8, and 200 mg kg ^{? 1} soil, respectively. Glass tubes, 4.9-cm-diameter and 40-cm-long, were packed with either natural or metal-amended soil. The resulting 20-cm-long column of soils had bulk density of about 1.58 g cm ^{? 3} . Columns repacked with natural or amended soil were leached with distilled water, 0.01 M EDTA, 0.01 M CaCl ₂ , or poultry litter extract (PLE) solutions. Low amounts of Zn, Cd, and Pb were leached from natural soil with the solutions. Leaching of Zn, Cd, or Pb was negligible with distilled water. In the metal-amended soil, EDTA solubilized more Zn, Cd, and Pb than CaCl ₂ and PLE. The breakthrough curves of Zn and Pb in the PLE and CaCl ₂ were similar, indicating they have similar ability to displace Zn and Pb from soils. Compared with Zn and Cd the PLE had a small ability to solubilize Pb from metal-amended soil. Thus, the application of poultry litter on metal-contaminated soils might enhance the mobility of Zn and Cd.     

Adsorption isotherms of lanthanum to soil constituents and effects of pH,EDTA and fulvic acid on adsorption of lanthanum onto goethite and humic acid

Abstract

La³⁺ adsorption isotherms to five soil constituents (quartz, feldspar, kaolinite, goethite and humic acid) are studied. EDTA, fulvic acid and pH effects are also investigated on the adsorption of lanthanum by goethite and humic acid because of their relative importance in affecting metal environmental behavior. Adsorption isotherms of La³⁺ to five constituents show differences in adsorption capacity and in shape in the studied range of La³⁺. These constituents can be classified according to their adsorption capacity: humic acid > goethite ≈ kaolinite > feldspar ≈ quartz. pH increase could promote humic acid and goethite adsorption of La³⁺ while EDTA could reduce the adsorption by these two adsorbents. Fulvic acid can reduce humic acid adsorption but has less effect on adsorption by goethite.     

X-ray Fluorescence (XRF) Analysis of Soil Heavy Metal Pollution from an Industrial Area in Kumasi,Ghana

Knowledge of soil heavy metal concentration is very important for assessing the purity and quality of the soil in an environment. The concentrations of nine heavy metals (NHM), Zn, Pb, Cr, Cu, Co, Ni, Cd, Hg, and As, from the near-surface soils (～ 0–15 cm) from an industrial cluster in Kumasi, Ghana, were qualitatively and quantitatively measured and analyzed using X-ray fluorescence (XRF) spectroscopy analysis. The sources of these NHM were mainly anthropogenic as a result of the indiscriminate industrial waste disposal. In all, a total of about 100 soil samples were taken from six sampling sites, four of which were industrial and the remaining two residential. Forty soil samples out of the total number were carefully selected for elemental analyses and the mean heavy metal concentrations were calculated using statistical methods. The results from locations of high industrial impact showed that the mean concentrations of the NHM present in the soil were in the order of Zn (189.2?908.6 mgkg^?1), Pb (133.7?571.3 mgkg^?1), Cr (91.3?545.8 mgkg^?1), Cu (62.9?334.6 mgkg^?1), Co (38.6?81.9 mgkg^?1), Ni (12.4?30.9 mgkg^?1), Cd (6.9?13.2 mgkg^?1), Hg (5.5?10.4 mg kg^?1), and As (2.3?18.6 mgkg^?1). Apart from Ni and As, all the heavy metals recorded concentrations that ranged from 10?900% higher than their respective threshold limit values (TLVs). Heavy metal concentrations from the residential sites were comparatively far lower with only Cr, Cd, and Hg registering concentrations between 65?250% above their TLVs. The cluster with its residential communities is at a serious risk of soil heavy metal toxicity and awareness to this needs to be created as such.     

成都平原北部水稻土重金属含量状况及其潜在生态风险评价

为了解成都平原水稻土重金属含量状况和潜在的生态风险,选取成都平原北部水稻土典型区域为研究对象,采集了158个表层土壤样品,分析了土壤中pH值和Cd、Cu、As、Hg、Pb、Cr、Ni 7种重金属元素含量,以20世纪80年代测定的成都平原土壤重金属元素背景值为评价标准,采用Hakanson潜在生态危害指数法对研究区域的重金属潜在生态风险进行了评价。结果表明:研究区域水稻土Cd、Hg、Ni、Cu、Pb、Cr和As平均含量分别为0.709、0.187、32.08、34.12、31.52、82.13 mg/kg和7.25 mg/kg;Cd、Ni、Cu和Hg 4种重金属超过《土壤环境质量标准》(GB15618-1995) Ⅱ级标准值样本比例分别为87.34%、8.23%、3.80%和3.80%,Cd含量超标严重。7种重金属元素变异系数幅度为18.35%-49.03%,由大到小依次为Cd、Hg、Cu、As、Ni、Cr、Pb。75.32%的样本达到中度或较强重金属潜在生态风险,区域整体表现为中度潜在生态风险(RI平均值为198.65),Cd和Hg为高生态风险元素,对潜在生态风险贡献率分别为62.27%和20.78%,As、Pb、Cu、Ni、Cr为低生态风险元素;风险概率图显示城区周边和绵远河沿线的潜在生态风险等级较高。因此,成都平原水稻土农业生产中应采取一定的措施防控农产品Cd和Hg污染。     

Fractionation,mobility and multivariate statistical evaluation of metals in marine sediments of Cape Town Harbour,South Africa

Abstract

Distribution of possible chemical forms of Al, Si, Sn, Pb, Zn, Fe, Hg, Cd and Cu in marine sediments of Cape Town harbour was investigated using a modified Tessier’s sequential extraction procedure and ICP-MS and ICP-AES for heavy metals determination. The mean fractions for all metals at all locations were: 1.5–7196 mg kg^-1 for Si, 7.79–7266 mg kg^-1 for Al, 161-639 mg kg^-1 for Cu, 19–41978 mg kg^-1 for Fe, 2.83–5864 mg kg^-1 for Zn, 1.45–13.26 mg kg^-1for Cd, 9.87–223 mg kg^-1 for Sn, 11.98-979 mg kg^-1 for Pb and 0.13–5.93 mg kg^-1 for Hg. Si, Al and Zn were mostly associated with Fe–Mn oxides, whereas Sn and Hg were mainly bound to residual and organic matter. Pb existed mainly in the residual and iron/manganese oxide phases while Cd was evenly distributed in all the five phases. The loading plots of heavy metals bound to the various chemical forms, as well as Pearson correlation coefficients, enabled the determination binding relationship. Pb, Sn and Hg exhibited similar binding behaviour which indicated an anthropogenic point source from wastes from the ship maintenance workshop, and the presence of Sn in the organic phase can be identified with the use of anti-fouling paints at the harbour, whereas Al, Fe, Si, Cu and Zn would probably be of natural origin. Lastly Cd probably came from a diffuse pollution sources in the harbour due to its unique binding characteristic. The mobility of heavy metals varied depending on location and the heavy metal type. The mobility of metals followed the order: Si > Zn > Fe > Cu> Al> Cd> Pb > Sn > Hg. The high percentage of Cd and Pb in the bioavailable forms suggested the need to keep close surveillance on these metals because of their high toxicity.     

A mass-balance study on chloride fluxes in a large central European catchment during 1900–2010

Using data on long-term monitoring of water quality, mass budgets, and empirical models, we quantified chloride (Cl) leaching from major diffuse and point sources in a large central European catchment (upper Vltava river, Czech Republic) over a 110-year period (1900–2010), with the major aim to evaluate the influence of historical changes in land use and management practices on Cl leaching from agricultural land. The Cl input to farmland in synthetic fertilizers, livestock feed, and atmospheric deposition tripled in the 1950s–1980s (from 23 to 64 kg ha^?1 year^?1 on average), and then abruptly decreased to ~14 kg ha^?1 year^?1 during 1990–2010. The proportion of drained agricultural land rapidly increased from 4 % in the 1950s to its maximum of 43 % in the 1990s. Until the 1950s, the Cl leaching from agricultural land followed a simple dose–response function. Then, agricultural soils retained on average 16 ± 4 kg ha^?1 year^?1 of Cl during 1959–1985, when the most important changes in land use and management practices occurred, and subsequently became a net Cl source of 11 ± 3 kg ha^?1 year^?1 on average during 1986–2010, when Cl input to soils declined and drainage of new land ceased. Our data suggest that the temporal changes in the Cl storage in agricultural land are associated with changes in Cl concentrations in both permanent soil water and soils. Physico-chemical conditions in freshly drained soils, namely elevated aeration and high concentrations of soil organic matter (SOM), and high Cl inputs probably resulted in a Cl immobilization in soils by formation of organic chlorine (Cl_org) and adsorption that was higher than the Cl production from Cl_org mineralization and desorption. In contrast, Cl_org mineralization and Cl desorption exceeded the Cl retention during the consecutive period of low Cl inputs and decreasing SOM concentrations in agricultural soils. Our study implies that changes in land use and agricultural management can significantly affect dose–response functions even for Cl, which is traditionally considered and modelled as a conservative ion.     

Mobility and Distribution of Zinc,Cadmium and Lead in Calcareous Soils Receiving Spiked Sewage Sludge

Leaching column experiments were conducted to determine the degree of mobility and the distribution of zinc (Zn), cadmium (Cd), and lead (Pb) because of an application of spiked sewage sludge in calcareous soils. A total of 20 leaching columns were set up for four calcareous soils. Each column was leached with one of these inflows: sewage sludge (only for two soils), spiked sewage sludge, or artificial well water (control). The columns were irrigated with spiked sewage sludge containing 8.5 mg Zn l^?1, 8.5 mg Cd l^?1, and 170 mg Pb l^?1 and then allowed to equilibrate for 30 days. At the end of leaching experiments, soil samples from each column were divided into 18 layers, each being 1 cm down to 6 cm and 2 cm below that, and analyzed for total and extractable Zn, Cd and Pb. The fractionation of the heavy metals in the top three layers of the surface soil samples was investigated by the sequential extraction method. Spiked sewage sludge had little effect on metal mobility. In all soils, the surface soil layers (0-1 cm) of the columns receiving spiked sewage sludge had significantly higher concentrations of total Zn, Cd and Pb than control soils. Concentration of the heavy metals declined significantly with depth. The mobility of Zn was usually greater than Cd and Pb. The proportion of exchangeable heavy metals in soils receiving spiked sewage sludge was significantly higher than that found in the control columns. Sequential extraction results showed that in native soils the major proportion of Zn and Pb was associated with residual (RES) and organic matter (OM) fractions and major proportion of Cd was associated with carbonate (CARB) fraction, whereas after leaching with spiked sewage sludge, the major proportion of Zn and Pb was associated with Fe-oxcide (FEO), RES, and CARB fractions and major proportion of Cd was associated with CARB, RES and exchangeable (EXCH) fractions. Based on relative percent, Cd in the EXCH fraction was higher than Zn and Pb in soils leached with spiked sewage sludge.