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.     

根瘤菌对土壤铜、锌和镉形态分配的影响

以湖南郴州红壤和河北巩义褐土为供试土壤。制备Cu、Zn、Cd污染土壤。接种大豆根瘤菌(Rhi-zobium fredii)HN01,用连续提取法浸提土壤中不同形态的重金属．结果表明。褐土接种根瘤菌后固相结合态Zn总量降低10％。专性吸附态、氧化锰结合态和有机结合态Zn减少达9％～26％．红壤中结合态Zn的总量变化不显著,但专性吸附态和氧化锰结合态Zn含量显著减少。交换态Zn含量显著增加．褐土中接种根瘤菌抑制了Cu向土壤溶液的释放,固相结合态Cu总量增加18％,可交换态、专性吸附态、氧化锰结合态和有机结合态的Cu增加20％～54％．接种根瘤菌对土壤中Cd的溶解没有明显的抑制或促进作用,但改变了红壤中各形态Cd的含量高低顺序．Cd污染红壤中可交换态和有机结合态Cd含量分别增加22％和11％,专性吸附态和氧化锰结合态Cd分别减少14％和29％．根瘤菌对不同类型重金属及不同土壤中重金属形态影响的差异主要与土壤pH降低有关．     

Preliminary study on heavy metals contamination of soil using solid phase speciation and the influence on groundwater in Bozanta–Baia Mare Area,Romania

Abstract

A preliminary study on soil contamination with heavy metals and As based on solid phase speciation according to the Tessier scheme and the influence on groundwater in an area under anthropogenic influence (Bozanta-Baia Mare, Romania) was conducted. The partitioning of Al, As, Cd, Cu, Fe, Mn, Pb and Zn in five fractions is discussed in relation to soil characteristics, pH, organic matter content, mineralogical composition and distribution of the same elements in airborne particulate matter. The airborne particulate matter contains high quantities of As, Cd, Cu, Pb and Zn as exchangeable fraction. The sequential extraction carried out on soil samples revealed the main role of Fe-Mn oxides surface in the immobilization of metals. Organic matter has a specific role in complexation of Cu, Pb, As and Al, since high contents of these metals were recovered in the oxidizable fraction. Cadmium has a high selectivity for carbonate minerals. The amendment of soil with natural fertilizer increases the exchangeable fraction of metals with the highest toxicity. The available fraction for plants (exchangeable + carbonate-bound species) exceeded the alert values in soil, therefore the continuous monitoring of the area is necessary. The soil is unsuitable for agricultural use due to high contamination on surface with toxic elements resulted from anthropogenic activities. Groundwater is contaminated with very toxic elements (As, Cd and Pb) but also with Cu, Mn and Zn and is unsuitable as supply for drinking water.     

Relationship of Soil Properties to Fractionation of Pb and Zn in Soil and Their Uptake into Plantago lanceolata

Soil samples (0 to 5?cm) from 30 locations in the Celje region, Slovenia, an area that has been subjected to severe industrial emissions of Pb and Zn, were analyzed for selected soil properties and subjected to a six-step sequential extraction of Pb and Zn. Phyto-available forms of heavy metals: soluble in soil solution and exchangeable from soil colloids to soil solution together accounted for 0 to 1.68% of Pb and 0 to 40.8% of total soil Zn. Most of the Pb and Zn was found to reside in less labile forms bound to carbonate (2.04 to 43.5% Pb, 3.9 to 35.1% Zn), bound to Fe and Mn oxides (0 to 16.1% Pb, 1.4 to 25.4% Zn), bound to organic matter (35.8 to 71.1% Pb, 14.8 to 56.2% Zn), and in the residual fraction (10.4 to 53.4% Pb, 14.2 to 75.3% Zn). Factor analysis and stepwise multiple regression revealed that the concentration of Pb in the proposed indicator plant, narrow leaf plantain (Plantago lanceolata) did not correlate with the measured soil properties, Pb fractionation in soil, and total soil Pb. Plant uptake of Zn, however, significantly correlated with soil pH and with the share of phyto-available forms of Zn in the soil (R² = 86.9). A statistically significant correlation (P<0.01) was found between the fractions of Pb and Zn carbonates and soil organic matter content (R² = 90.6 and 90.9, respectively); the fraction of Pb bound to organic matter and soil organic matter content (R² = 90.6); the residual fraction of Pb and total Pb content in soil (R² = 95.7); the fraction of Zn bound to Fe an Mn oxides, the fraction of Zn bound to organic matter, the residual fraction of Zn and total Zn content in soil (R² = 75.9, 93.2, and 87.4, respectively). Soil texture, pH, and cation exchange capacity did not affect the relative proportions of Pb and Zn forms in soil.     

Assessment of a heavy metals‐contaminated site using sequential extraction,TCLP, and risk assessment techniques

The mobility of selected heavy metals in contaminated soil at a previous industrial site in Brisbane, Australia, was assessed using a sequential extraction technique. Copper, Pb, Zn, Cr, Fe, and Mn were extracted from the soil solution/exchangeable, carbonate, Fe and Mn oxides, and organic matter fractions. The amounts of metals adsorbed by these fractions were used as an indicator of each metal's mobility in the soil. Copper and Pb were largely adsorbed by the organic and oxide fractions, while a significant amount of Zn was extracted from the carbonate fraction. The potential mobility and biological availability of the metals in these soils is Zn > Cr = Cu ≈ Pb. Soils were also analyzed using the toxicity characteristic leaching procedure (TCLP) to determine whether the contaminated soil could be disposed of by landfilling. The leachability of all metals from the soils was very low, with metal concentrations below the allowable limits. The TCLP also showed that Zn was the most mobile metal in these soils. An environmental and health risk assessment was undertaken, and it was concluded that the site did not represent a risk despite the “total”; concentrations of some metals being up to 40 times the investigation threshold value adopted in Australia.     

Effects of soil acidification on the chemical extractability of Fe,Mn, Zn and Cu and the growth and micronutrient uptake of highbush blueberry plants

Summary The effects of soil acidification and micronutrient addition on levels of extractable Fe, Mn, Zn and Cu in a soil, and on the growth and micronutrient uptake of young highbush blueberry plants (Vaccinium corymbosum L. cv. Blueray) was investigated in a greenhouse study.Levels of 0.05M CaCl₂-extractable Fe, Mn, Zn and Cu increased as the pH was lowered from 7.0 to 3.8. However, the solubility (CaCl₂-extractability) of Fe and Cu was considerably less pH-dependent than that of Mn and Zn. With the exception of HCl-and DTPA-extractable Mn, micronutrients extractable with 0.1M HCl, 0.005M DTPA and 0.04M EDTA were unaffected or raised only slightly as the pH was lowered from 6.0 to 3.8. Quantities of Mn and Zn extractable with CaCl₂ were similar in magnitude to those extractable with HCl, DTPA and EDTA whilst, in contrast, the latter reagents extracted considerably more Cu and Fe than did CaCl₂. A fractionation of soil Zn and Cu revealed that soil acidification resulted in an increase in the CaCl₂- and pyrophosphate-extractable fractions and a smaller decrease in the oxalate-extractable fraction.Plant dry matter production increased consistently when the soil pH was lowered from 7.0 to 4.6 but there was a slight decline in dry matter as the pH was lowered to 3.8. Micronutrient additions had no influence on plant biomass although plant uptake was increased. As the pH was lowered, concentrations of plant Fe first decreased and then increased whilst those of Mn, and to a lesser extent Zn and Cu, increased markedly.     

Suspended particulate oxides and organic matter interactions in trace metal sorption reactions in a small urban river

The relative scavenging abilities of suspended particulate oxides (SPOX), and organic matter (SPOM) for Cd, Zn and Cu were evaluated in a small, anthropogenically influenced river. In addition, the factor most important in influencing the sorption density (A_d: metal concentration associated with a given phase divided by the concentration of that geochemical phase in the suspended particulate pool) of each metal to SPOX and SPOM were identified through multiple linear regression analyses from the suite of: pH, temperature, dissolved metal concentration, and the concentration of the other particulate fraction. Results indicate that SPOX-SPOM interactions do occur in trace metal complexation reactions; and interactions are both phase and cation specific. Fe oxides are able to outcompete discrete organic binding sites for Cu and Zn as a relative decrease in the amount of these two cations sorbed to organic matter was observed with increasing particulate Fe oxides. SPOM concentration was identified as being most important in influencing Cu sorption densities associated with the SPOX fraction. Organic matter — oxide complexes are postulated to occur that enhance oxide sorption of Cu such that relatively more Cu is sorbed to particulate oxides with increasing particulate organic matter concentrations. Dissolved concentrations of Cd and Zn were found to be most important in influencing the sorption densities for these two metals associated with the oxides fraction. The sorption behaviour appears to follow Freundlich isotherm behaviour where the amount sorbed is a function of the dissolved concentration.     

Phytotoxicity and distribution of copper in tropical soil amended with sewage sludge and copper sulfate

Abstract

A greenhouse experiment was conducted to evaluate phytotoxicity and distribution of Cu in a tropical soil amended with sewage sludge (Sw) and copper sulfate (CuSO₄.5H₂O). Samples of a clay soil from the State of Paraná, Brazil were collected at depth of 0–20; 20–40 and 40–60 cm, and brought to the laboratory to be properly accommodated in experimental units (PVC tubes). The Cu treatments were performed by the application of Sw (10 t ha-¹) amended with Cu (SB-T), and by CuSO₄. H₂O (WB-T). Lettuce plants were cultivated in the amended soil in order to predict the toxicity of the Cu. The experiment was conducted for 70 days, and then the lettuce plants and soil samples were collected for analysis. A sequential method was used to separate soil Cu into following fractions: exchangeable, amorphous iron oxide bound, crystalline iron oxide bound, organic matter bound and residual bound. The experimental results showed that Fe, Zn, K, P, Cu and organic matter amounts of the soil increased with the treatment SB-T. The toxic phyto-available Cu content in the soil for the lettuce plants was 80.00 mg kg^-1. A percolation study showed that the Cu contents were larger for the first 20 cm of depth, indicating that the metal was not transported down the soil profile. The Cu content of different fractions declined in an order residual > amorphous iron oxide > crystalline iron oxide > organic matter > exchangeable, regardless of treatment performed. Additionally, the Cu contents added from treatments were determined mainly in amorphous iron oxide fraction.     

Effect of annual variation in soil pH on available soil nutrients in pear orchards

Soil pH is an important factor affecting the availability of soil nutrients that impact plant growth. Given the susceptibility of soil pH to excessive fertilization and the widespread use of manures, it is essential to examine the influence of soil pH on the distribution and availability of soil nutrients. We sampled and analyzed brown soils from pear orchards in thirteen towns in Wendeng county. Samples were obtained from areas along or between rows of trees at specified distances and depths. The results showed that the soil pH fluctuated from 4.06 to 6.59 in October 2008 and from 4.24 to 7.57 in April 2009. The quantity of soil samples with pH below 5.50 increased by 34.6%. Analysis of the soil pH for samples obtained along the rows of trees showed that the pH decreased as the depth increased (except for the range 5.5 to 6.0); soil pH in the samples obtained between the rows of trees demonstrated different trends. The average organic matter (O.M.) content as well as the N (NH₄⁺) and available P, K, Cu, Zn, Fe, and Mn contents in the samples collected in October 2008 were higher than those observed in April 2009. Conversely, the values for other available nutrients were lower than those in the samples collected in April 2009. The available nutrients and organic matter (O.M.) content in different pH ranges varied. The soil pH was significantly or very significantly correlated with N (NH₄⁺ and NO₃^-), available K, Cu, Fe, and exchangeable Ca for the October 2008 samples, while a significant or very significant correlation existed between N (NH₄⁺), available P, Zn, exchangeable Ca, and exchangeable Mg for the April 2009 samples. The correlations between soil pH and the amounts of available nutrients and organic matter (O.M.) along the rows of trees in September 2009 were nearly consistent with those between the rows.     

Effect of annual variation in soil pH on available soil nutrients in pear orchards

Soil pH is an important factor affecting the availability of soil nutrients that impact plant growth. Given the susceptibility of soil pH to excessive fertilization and the widespread use of manures, it is essential to examine the influence of soil pH on the distribution and availability of soil nutrients. We sampled and analyzed brown soils from pear orchards in thirteen towns in Wendeng county. Samples were obtained from areas along or between rows of trees at specified distances and depths. The results showed that the soil pH fluctuated from 4.06 to 6.59 in October 2008 and from 4.24 to 7.57 in April 2009. The quantity of soil samples with pH below 5.50 increased by 34.6%. Analysis of the soil pH for samples obtained along the rows of trees showed that the pH decreased as the depth increased (except for the range 5.5 to 6.0); soil pH in the samples obtained between the rows of trees demonstrated different trends. The average organic matter (O.M.) content as well as the N (NH₄⁺) and available P, K, Cu, Zn, Fe, and Mn contents in the samples collected in October 2008 were higher than those observed in April 2009. Conversely, the values for other available nutrients were lower than those in the samples collected in April 2009. The available nutrients and organic matter (O.M.) content in different pH ranges varied. The soil pH was significantly or very significantly correlated with N (NH₄⁺ and NO₃^-), available K, Cu, Fe, and exchangeable Ca for the October 2008 samples, while a significant or very significant correlation existed between N (NH₄⁺), available P, Zn, exchangeable Ca, and exchangeable Mg for the April 2009 samples. The correlations between soil pH and the amounts of available nutrients and organic matter (O.M.) along the rows of trees in September 2009 were nearly consistent with those between the rows.     

The distribution and bioavailability of Cd and Zn in cultivated soil of Henan Province

Abstract

Concentrations of surface soil Zn and Cd from agricultural areas of the Henan Province were measured. About 234 soil samples were collected. Total metal analyses, sequential chemical fractionation which were divided into seven fractions according to the method of the Geological Survey Technical Standard (DD2005-03) set by the China Geological Survey were carried out on the samples. Total Cd and Zn concentrations of the topsoil were 0.1909 (0.1–0.549) and 63.07 (33.3–344.3) mg kg^?1 respectively. Compared with the values permitted in China’s control standards for soil (GB 15618–1995) and background value in Henan Province, the soil samples showed high levels of Cd. The soil organic carbon has a significantly positive correlation with Cd and Zn concentration in the soil. Significant positive correlation between pH and Cd, Zn concentration was observed. On average, the order of Cd in each fraction was exchangeable, (27.3%)>weakly bound to organic matter; (22.7%)>strongly bound to organic matter; (16.4%)>residual; (15.1%)>carbonate; (12.1%)>Fe/Mn oxide bound; (4.5%)>water soluble; (2.0%), Zn was residual; (66.3%)>Fe/Mn oxide bound; (10.9%)> weakly bound to organic matter; (9.4%)> exchangeable; (6.0%)> strongly bound to organic matter; (3.9%)> carbonate (2.9%)> water soluble (0.6%). The accuracy of the sequential extraction was judged by the relative error (RE). RE for Cd ranged from 0 to 45% with a mean of 16.3%. RE for Zn ranged from 0.1 to 11.4% with a mean of 3.4%. On average, bioavailability index (BI) for Cd and Zn was 39.1% and 9.0% respectively. The mobility of the elements in the order Cd> Zn corresponds with the plant-availability of individual elements. Comparisons between activities of Cd²⁺ and Zn²⁺ calculated by Sauve semi-mechanistic equations and that of the water soluble fractions were demonstrated. The activities of Cd²⁺ and Zn²⁺ calculated by the semi-empirical equation are lower than its water soluble fraction.     

Dynamics of trace metals in the system water – soil – plant – wild rats – tapeworms (Hymenolepis diminuta) in Maglizh area,Bulgaria

BackgroundThe impact of chemical elements on the biosphere is a function of their concentration and chemical form. Elucidation and prognosing of the latters in water basins and soil extracts is of particular significance for the assessment of their bioaccumulation in plants and animals.ObjectivesTrace metals dynamics in the system water – soil–plant–wild rats – Hymenolepis diminuta in two agro-industrial zones (East and West) around Maglizh city, Bulgaria were investigated through experimental studies and thermodynamic modelling of the chemical species.MethodsSamples from surface waters of rivers, their nearby uncultivated soils, meadow uncultivated vegetation (Ranunculus acris and Gramineae) and field rats were collected. In situ measurements and laboratory analyses were performed for the determination of the physico-chemical characteristics and total concentrations of Al, Fe, Mn, Ni, Cu, Zn and Pb. The distribution of their dissolved chemical species in water samples and in the aqueous soil extracts was calculated using a thermodynamic approach. The relationship chemical species - bioaccumulation was discussed.ResultsWaters and soils in the East zone of Maglizh area were found to be more polluted compared to those in the West one, regarding Ni, Mn, Zn, Pb and Cu, while Mn and Cu displayed the highest mobility in West zone soils. Trace metals contents in Ranunculus acris exceed that in Gramineae, since the highest accumulation factors were calculated for Cu and Zn. The highest accumulation in rats was found for Zn followed by Cu, being higher in the West zone. Thermodynamic modelling shows that Mn²⁺ free ions are dominant in both waters and aqueous soil extracts. Ni²⁺ and Zn²⁺ ions followed by metal-organic complexes are dominant in waters of East zone while metal-organic complexes followed by free ions are dominant in waters of West zone and both soil extracts. Metal-organic complexes are dominant for Fe, Cu and Pb in all samples studied, while mainly hydroxy forms (Al(OH)₄⁻) followed by metal-organic complexes are typically for Al depending on pH.ConclusionsExperimentally established bioaccumulation of trace metals in the studied vegetation and rats is a consequence of the total concentration of trace metals in waters and soils, their mobility and chemical species. The dominance of organic complexes of trace metals is a prerequisite for their bioaccumulation in plants. Rats are in direct contact with the soil solution and therefore, of importance is the content of free ions of Mn²⁺, Ni²⁺, Zn²⁺, which are easily absorbed through the skin. The host-helminth system wild rat/H. diminuta could be used as a bioindicator for trace metals pollution.     

The Concentration and Partitioning of Heavy Metals in Surface Sediments of the Maharlu Lake,SW Iran

In this study, an assessment is made of the environmental impacts of heavy metal concentration and fractionation in bed sediments of the saline Maharlu Lake, SW Iran. Total elemental analysis indicated that sediments were highly enriched in Pb and Cd. Sequential extraction analysis revealed that salt of the lake is probably highly contaminated with Cd, Pb, and Co. Due to the oxidizing conditions of the lake, the organic matter fraction of the elements was not significant. In all sediments, Cd, Pb, Co, Mn, and Zn were strongly associated with exchangeable plus carbonate fractions, with mean percentage of 76.4%, 65.3%, 56%, 40.9%, and 34.3%, respectively. On average, the percentage of Ni associated with the sum of the exchangeable and carbonate fractions was 19.8%. Cr, Fe, and Cu fractionation indicated that these metals are environmentally inert and immobile. Statistical relationships among metal fractions and sediment properties showed that Cd, Pb, Zn, Ni, Co, and Mn were mainly from recent anthropogenic sources, while such sources were less important for Cr, Cu, and Fe. The latter metals represented natural geochemical levels.     

Metal contents and fractionation in contaminated soil after column leaching using [S,S]-EDDS

Abstract

Column leaching using [S, S]-ethylene diamine disuccinate ([S, S]-EDDS) on copper tailing soils was carried out to investigate metal content and fractionation after leaching. The soil column was divided into four layers after leaching. Fractionation of Cu, Pb, Zn, and Mn in soil was analyzed using a modified BCR sequential extraction method. Metal contents (Cu, Pb, Ca, Mn) in soil layers increased with the depth of the soil column after leaching in the [S, S]-EDDS treatment. The cumulative extraction efficiency was approximately 43.1% for Cu, 26.8% for Zn, 19.5% for Pb, 10.5% for Ca, 2.07% for Mg, 58.5% for Mn, and 7.92% for Fe. The removal of the reducible fractions of Cu and Mn and the exchangeable fraction of Zn was the most significant in the treatment with [S, S]-EDDS. The exchangeable fraction of Pb was the main fraction that was affected by leaching using [S, S]-EDDS. Distribution of Cu and Mn were severely modified by leaching with [S, S]-EDDS. Percentages of residual fractions of the tested heavy metals in the treatment with [S, S]-EDDS after leaching were much higher than that in the control. Although column leaching using [S, S]-EDDS could remove target metals effectively and impaired their availability, it also dissolved large amounts of major elements and modified the distribution of Mn appreciably.     

Fractionation of metals in the Sa1/2 sediment core from Lake Sarbsko (northern Poland) and its palaeolimnological implications

Abstract

This article documents and interprets stratigraphical changes in fractionation of Fe, Mn, Mg, K, Pb, Cu and Zn in the Sa1/2 sediment core from a coastal freshwater lake, Lake Sarbsko (northern Poland). The elements were sequentially extracted from the samples to distinguish five geochemical fractions: exchangeable, acid-extractable, reducible, oxidisable and residual. The analyses revealed substantial variations in geochemical partitioning of the elements and showed no correlation between the fractionation patterns and lithology of the sediments. In the sediments of Lake Sarbsko, iron is mainly bound to sulfides. Potassium occurs in its residual form. Magnesium and zinc are associated with carbonates and aluminosilicates, while copper occurs in compounds with organic matter and sulfides. Lead is found in connection with aluminosilicates and, to a lesser extent, with sulfides and organic matter. Manganese is partitioned between the oxidisable, acid-extractable, and exchangeable fractions. Heavy metals and potassium display the overall tendency to reduce the contents of their residual forms towards the top of the depositional sequence. Fe, Mn, Mg and Zn were found to be the most susceptible to post-sedimentary mobilisation.     

Chemical partitioning of Cu,Pb and Zn in the soil profile of a semi arid dry woodland

Abstract

The chemical partitioning of Cu, Pb and Zn was examined in the soil profile of the woodland system in Keoladeo National Park, India using a five-step sequential extraction procedure (SEP). Metal partitioning was assessed in the soil up to a depth of 100cm with 25-cm intervals. The amount of metals obtained from the SEP exceeded pseudototal metal levels obtained from aqua regia digestion. The SEP results showed high preferential attachment of metals with Fe—Mn hydroxides. All the three metals showed least preferences to the exchangeable pool. The attachment of metals to the OM-S phase was also less, may be because of the low organic matter in the soil. In the case of Cu, the order of the fractions in terms of metal concentrations was Fe—Mn>RES>OM-S>CA>EXC and in the case of Pb the order was Fe—Mn>OM-S>RES>CA>EXC. Zn was different from Cu and Pb in showing higher affinity towards RES phase and the order of its concentration was RES>Fe—Mn>OM-S>EXC>CA. This suggests hydrous oxides of Fe—Mn as an important binding site for Cu and Pb, whereas silicate mineral matrix (RES phase) for Zn.     

Quantitative speciation of heavy metals in soil and crops of agricultural fields of Islamabad,Pakistan

Abstract

Two root crops: carrot (Daucus carota) and spring onion (Allium fistulosum) and soil samples were selected from the agricultural fields located near Islamabad, Pakistan to determine their elemental content. Field soil speciation of the two crops was also carried out to analyse the correlation of the elements in field crop and soil. Concentrations of selected elements were evaluated in the leaf, stem, root and flowering part of the crops using flame atomic absorption spectrophotometry. The results showed that elements are mostly concentrated in soil rather than crop parts following the sequence Zn>Cu>Pb>Ni>Cr>Cd. Furthermore, soil speciation showed that Ni and Cr are more prevalent in the Fe–Mn oxide fraction, Zn and Cd as the carbonate bound fraction and Cu is found in the organic bound form. However, concentrations of Pb are similar across the carbonate, Fe–Mn oxide and organic bound fractions. The highest average concentration of Zn is found as the carbonate bound fraction (2.09 ± 0.005 mg kg^?1) and Cu as the organic bound (1.51 ± 0.029 mg kg^?1) in soil samples taken from the agricultural field of Daucus carota.     

Characteristics of Copper Sorption by Various Agricultural Soils in China and the Effect of Exogenic Dissolved Organic Matter on the Sorption

To explore the effect of exogenic dissolved organic matter (DOM) on Cu(II) sorption in agricultural soils, 26 agricultural soils were collected across China. Exogenic dissolved organic matter, extracting from wheat straw (DOM_W) and swine manure (DOM_S), respectively, were added to the soils to conduct a series of batch sorption and characterization experiments. The solid-liquid partition coefficient (K_d) ranged from 0.02 to 76.46 L g^?1, suggesting different Cu(II) sorption on various soils. PCA analysis indicated that pH, free Fe/Al oxides, carbon, and total Cu content had a significant positive relationship with the Cu(II) sorption, respectively. And the contribution rate of pH was the highest (38.15%). Moreover, DOM markedly inhibited the Cu(II) sorption in alkaline soils while promoted the Cu(II) sorption in acidic soils, which were interacted by the soil properties and DOM characteristics. The effect of DOM_S on Cu(II) sorption were more obvious than DOM_W, which were further confirmed by Fourier transform infrared (FTIR) spectroscopy. FTIR also showed Cu(II) was primarily adsorbed on the specific functional groups, such as CO, OH, and CO, providing direct evidences for the binding of Cu(II) with DOM. This study can guide the rational use of organic fertilizers, and also provide baseline knowledge for the prevention and control of soil pollution.     

Chemical speciation of Zn in acidic soils: suitable soil extractant for assessing Zn availability to maize (Zea mays L.)

Abstract

Chemical fractions of soil Zn namely: water soluble (WS), exchangeable (EX), Pb displaceable (Pb-disp.), acid soluble (AS), Mn oxide occluded (MnOX), organically bound (OB), amorphous Fe oxide occluded (AFeOX), crystalline Fe oxide occluded (CFeOX), residual (RES) were determined in 20 surface (0–15 cm) samples of acidic soils from the provinces of Uttarakhand and Uttar Pradesh, India. The chemical fractions of soil Zn in acidic soils were found to be in the following descending order of Zn concentration: RES > CFeOX > Pb-Disp. > AFeOX > MnOX > AS > OB > EX > WS. These soil samples were also extracted by: DTPA (pH 7.3), DTPA (pH 5.3), AB-DTPA (pH 7.6), Mehlich 3 (pH 2.0), Modified Olsen, 0.01 N CaCl₂, 1 M MgCl ₂ and ion exchange resins. Chemical fractions and the soil extractable content of Zn estimated by different soil extractants were significantly correlated with some general soil properties. Maize (cv. Pragati) plants were grown in these soils for 35 days after emergence and Zn uptake by plants was compared with the amount of Zn extracted by different soil extractants and chemical fractions of Zn. Among chemical fractions of soil Zn, Pb-displaceable and acid soluble chemical fractions of soil Zn showed a significant and positive correlation with Zn uptake by maize. Path coefficient analysis also revealed that the acid soluble Zn fraction showed the highest positive and direct effect on Zn uptake (P=0.960). Among different multinutrient soil extractants evaluated for their suitability to assess Zn availability in acidic soils, DTPA (pH=5.3) was most suitable soil extractant, as the quantity of soil Zn extracted by this extractant showed a significant and positive correlation with the dry matter yield, Zn concentration and uptake by maize plants.     

Enrichment and Chemical Fraction of Copper and Zinc in the Sediments of the Daliao River System,China

Copper and zinc contents and their chemical forms in the surface sediments of the Daliao River system (DRS) were investigated to quantitatively assess their contamination, mobility, and potential bioavailability. Twenty-seven surface sediment samples were collected and analyzed for total contents of Cu, Zn, Al, Fe and Mn and for chemical forms of Cu and Zn. These results reveal that the total contents of Cu and Zn in the sediment of DRS mainly ranged from 4.5 to 86.1 and 17.7 to 1340.9 mg kg^?1, respectively. The enrichment factors (EFs) were generally lower than 1.0 at most sampling sites, while at T3, B5 and B7 sites of the Taizi River near Benxi, Liaoyang and Anshan cities, respectively, they were more than 2.0. The primary sources of Zn and Cu contamination at these three sites are considered to be iron mining and smelting and some chemical industries. Hence, the total contents of Cu and Zn in the sediments of the Daliao River system mainly ranged around background levels. In general, less than 2% and more than 60% of total Cu and Zn contents in the sediment at most sampling sites were associated to the exchangeable fraction and residual fraction, respectively, showing their low mobility and bioavailability. The major sink for anthropogenic Cu might be organic matter and Fe oxides, while for anthropogenic Zn it was carbonate and the easily reducible phase dominated by Mn and amorphous Fe oxides. Therefore, anthropogenic Cu and Zn have relatively high potential mobility and bioavailability. In comparison with the sediments of other rivers in China and in the world, the sediment of the DRS contained relatively low contents of Cu and Zn.