Prediction of available heavy metals by six chemical extractants in a sewage sludge‐amended soil

Abstract

In a field experiment conducted during three years in a sandy‐loam, calcareous soil, one aerobically digested sewage sludge (ASL) and another anaerobically digested sewage sludge (ANSL) were applied at rates of 400, 800, and 1,200 kg N/ha/year, and compared with mineral nitrogen fertilizer at rates of 0, 200, 400, and 600 kg N/ha/year in a cropping sequence of potato‐corn, potato‐lettuce, and potato, the first, second, and third year, respectively. Results showed that the highest values of soil extractable metals were obtained with aqua regia, whereas the lowest levels with DTPA. All metal (Zn, Cu, Cd, Ni, Pb, and Cr) gave significant correlations between metal extracted with the different extractants and metal loading applied with the sludges. The metal extractable ion increased over the control for Zn, Cu, Cd, Ni, Pb, and Cr extracted with DTPA, EDTA (pH 8.6) and 0.1 N HC1, for Zn, Cd, Ni, Pb, and Cr extracted with EDTA (pH 4.65) and AB‐DTPA, and for Zn, Cd, Ni, and Cr extracted with aqua regia. The level of metal‐DTPA extractable resulted highly correlated with that obtained by the other methods, except the Ni‐aqua regia extractable. The soil extractable elements which showed significant correlations with metals in plant were: Zn, Cu, Cd, and Ni in potato leaves, Cd, Ni, and Pb in corn grain, and Zn and Cd for lettuce wrapper leaves. In general, all the chelate based extractants (DTPA, EDTA pH 4.6, EDTA pH 8.6, AB‐DTPA) were equally useful as indicator of plant available metals in the soil amended with sludge.     

Heavy metal levels in apple orchards after the application of two composts

Abstract

Two composts were tested in eleven different Malus domestica orchards: one was a sewage sludge and bark compost with a low heavy metal content, the other was a municipal solid waste compost with a higher concentration of metals. For six years the zinc (Zn), copper (Cu), nickel (Ni), lead (Pb), cadmium (Cd), and chromium (Cr) content were monitored in the soil, both in ‘total’ and EDTA extractable form, and in leaves and fruits. The resulting data demonstrate clearly that the sewage sludge and bark compost did not cause any significant increase of heavy metal levels in soil and plants; this compost can thus be used to fertilize the soil with no danger either to the environment or to crops. In contrast, the municipal solid waste compost led to a notable accumulation of all the metals examined in the soil and, above all in the case of Pb and Cd, also in the vegetation and the fruits.     

Verhalten von Schwermetallen in Böden 1. Untersuchungen zur Schwermetallmobilität

Behaviour of heavy metals in soils. 1. Heavy metal mobility 158 soil samples with widely varying composition were analysed for their total, EDTA, DTPA and CaCl₂ extractable contents of Cd, Zn, Mn, Cu and Pb. By means of single and multiple regressions the relations between the different heavy metal fractions and the pH, organic carbon and clay content were considered. The correlations between the total, EDTA and DTPA extractable contents are very close, whereas the CaCl₂ extractable contents are not or only weakly correlated with these fractions. According to these statistical results the former fractions are considered to be the total quantity (total content) and the reactive quantity (EDTA and DTPA extractable contents) of the heavy metals, whereas the CaCl₂ extractable fraction represents the mobile fraction of the heavy metals in soils. The multiple regressions show that the mobile content of heavy metals is closely correlated with each of the quantity fractions and with soil pH. In the same way the proportion of the mobile fraction (in %) of the total, EDTA and DTPA extractable heavy metal content of the soil samples is closely related to the soil pH. Hereby the proportion of the mobile content of the various elements increases in the pH range 6,5 - 3 below element-specific threshold pH values (in brackets) in the order Cd (6,5) > Mn (5,7) > Zn (5,3) > Cu (4,5) > Pb (3,5). In the pH range 6,5 - 7,5 mainly Cu and to a lesser degree also Pb show an increasing mobility due to the influence of soluble organic substances.     

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

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

Extractability and plant uptake of heavy metals in alum shale soils

Abstract

Fifty soil samples (0–20 cm) with corresponding numbers of grain, potatoes, cabbage, and cauliflower crops were collected from soils developed on alum shale materials in Southeastern Norway to investigate the availability of [cadmium (Cd), copper (Cu), zinc (Zn), lead (Pb), nickel (Ni), and manganese (Mn)] in the soil and the uptake of the metals by these crops. Both total (aqua regia soluble) and extractable [ammonium nitrate (NH₄NO₃) and DTPA] concentrations of metals in the soils were studied. The total concentration of all the heavy metals in the soils were higher compared to other soils found in this region. Forty‐four percent of the soil samples had higher Cd concentration than the limit for application of sewage sludge, whereas the corresponding values for Ni, Cu, and Zn were 60%, 38%, and 16%, respectively. About 70% the soil samples had a too high concentration of one or more of the heavy metals in relation to the limit for application of sewage sludge. Cadmium was the most soluble of the heavy metals, implying that it is more bioavailable than the other non‐essential metals, Pb and Ni. The total (aqua regia soluble) concentrations of Cd, Cu, Zn, and Ni and the concentrations of DTPA‐extractable Cd and Ni were significantly higher in the loam soils than in the sandy loam soils. The amount of NH₄NCyextractable metals did not differ between the texture classes. The concentrations of DTPA‐extractable metals were positively and significantly correlated with the total concentrations of the same metals. Ammonium nitrate‐extractable metals, on the other hand, were not related to their total concentrations, but they were negatively and significantly correlated to soil pH. The average concentration of Cd (0.1 mg kg^‐1 d.w.) in the plants was relatively high compared to the concentration previously found in plants grown on the other soils. The concentrations of the other heavy metals Cu, Zn, Mn, Ni, and Pb in the plants were considered to be within the normal range, except for some samples with relatively high concentrations of Ni and Mn (0–11.1 and 3.5 to 167 mg kg‘¹ d.w., respectively). The concentrations of Cd, Cu, Zn, Ni, and Mn in grain were positively correlated to the concentrations of these respective metals in the soil extracted by NH₄NO₃. The plant concentrations were negatively correlated to pH. The DTPA‐extractable levels were not correlated with plant concentration and hence DTPA would not be a good extractant for determining plant availability in these soils.     

Comparison of routine soil tests and EPA method 3050 as extractants for heavy metals in Delaware soils

Abstract

Agricultural use of sewage sludges can be limited by heavy metal accumulations in soils and crops. Information on background levels of total heavy metals in soils and changes in soil metal content due to sludge application are; therefore, critical aspects of long‐term sludge monitoring programs. As soil testing laboratories routinely, and rapidly, determine, in a wide variety of agricultural soils, the levels of some heavy metals and soil properties related to plant availability of these metals (e.g. Cu, Fe, Mn, Zn, pH, organic matter, texture), these labs could participate actively in the development and monitoring of environmentally sound sludge application programs. Consequently, the objective of this study was to compare three soil tests (Mehlich 1, Mehlich 3, and DTP A) and an USEPA approved method for measuring heavy metals in soils (EPA Method 3050), as extractants for Cd, Cu, Ni, Pb and Zn in representative agricultural soils of Delaware and in soils from five sites involved in a state‐monitored sludge application program.

Soil tests extracted less than 30% of total (EPA 3050) metals from most soils, with average percentages of total metal extracted (across all soils and metals) of 15%, 32%, and 11% for the Mehlich 1, Mehlich 3, and DTPA, respectively. Statistically significant correlations between total and soil test extractable metal content were obtained with all extractants for Cu, Pb, and Zn, but not Cd and Ni. The Mehlich 1 soil test was best correlated with total Cu and Zn (r=0.78***, 0.60***, respectively), while the chelate‐based extractants (DTPA and Mehlich 3) were better correlated with total Pb (r=0.85***, 0.63***). Multiple regression equations for the prediction of total Cu, Ni, Pb, and Zn, from soil test extractable metal in combination with easily measured soil properties (pH, organic matter by loss on ignition, soil volume weight) had R² values ranging from 0.41*** to 0.85***, suggesting that it may be possible to monitor, with reasonable success, heavy metal accumulations in soils using the results of a routine soil test.     

长期化肥配施不同有机肥对土壤和玉米中重金属累积的影响

  【目的】  明确长期化肥配施有机肥对重金属元素在土壤和农作物籽粒、秸秆中积累的影响及其环境效应,为安全高效施肥提供科学依据。  【方法】  在北京市农林科学院新型肥料长期定位试验站进行了为期10年的田间试验,其种植模式为冬小麦–夏玉米轮作,试验处理为不施肥 (CK)、单施化肥 (NPK)、氮磷钾 + 鸡粪堆肥的有机肥料 (NPKJF)、氮磷钾 + 污泥堆肥的有机肥料 (NPKWN)、氮磷钾 + 垃圾堆肥的有机肥料 (NPKLJ) 和氮磷钾 + 秸秆粉碎还田 (NPKJG) 共6个处理,施肥处理依据等氮量施肥原则,每季作物施 N 180 kg/hm2、P₂O₅ 90.0 kg/hm2、K₂O 90.0 kg/hm2。在玉米收获后测定了玉米秸秆、籽粒和0—20 cm耕层土壤中重金属全量。  【结果】  添加污泥处理显著提高了土壤中Cd、Hg、As、Cu、Zn的含量,单因子污染指数分别比对照提高了45.10%、150.00%、104.00%、44.60%、65.80%。不同施肥处理对土壤中全量Cd、Cr、Hg、Cu、Zn存在一定的富集效果。各处理重金属单项污染指数在0.02～0.46,远小于1,综合污染指数为0.23～0.36,均小于0.7,试验区土壤重金属均为无污染等级。施用有机废弃物堆肥的处理玉米籽粒Cd、Cu、Zn含量比对照显著增加,各处理间Hg、As、Cr、Pb、Ni含量差异不显著,连续10年定位施肥后试验站土壤以及玉米籽粒中重金属含量均未超标。同一作物不同部位对重金属的富集能力不同,玉米秸秆对重金属的富集能力大于籽粒。玉米籽粒中Pb、Cu、Zn含量与土壤Pb、Cu、Zn含量存在正相关性,玉米秸秆中Cd、Hg、Cr、Ni含量与土壤中Cd、Hg、Cr、Ni含量呈正相关或者显著负相关。  【结论】  在施氮总量不变的前提下,连续施用供试有机堆肥10年后,土壤重金属含量均未超标,土壤重金属单项污染指数在0.02～0.46,综合污染指数为0.23～0.36,无污染风险。只有污泥堆肥需要加强土壤Cd的监测。玉米秸秆对重金属的富集能力大于籽粒。玉米籽粒中Pb、Cu、Zn含量与土壤相应重金属含量存在正相关性,秸秆中Cd、Pb、Hg、Zn与Cr、Ni含量与土壤中相应重金属含量呈正相关,而秸秆中Cr、Ni含量与土壤中相应重金属含量呈负相关。     

Total soil heavy‐metal concentrations and mobile fractions after 10 years of biowaste‐compost fertilization

The accumulation of heavy metals (HMs) in soils is the most often cited potential risk of compost application. As the ecological effects of metals are related to mobile fractions rather than to total concentrations in the soil, we measured the total (aqua regia–extractable) HM concentrations, the readily available water‐soluble and the potentially bioavailable LiCl‐extractable fraction of soil HMs in a field experiment after 10 y with total applications of 95, 175, and 255 t ha^–1 biowaste compost (fresh matter). Total soil concentrations of Cd, Cr, Cu, Ni, and Pb in the compost treatments were not significantly higher than in the unfertilized control. Total Zn concentrations increased in the treatment with the highest application rate, as expected from the calculation of the Zn load in the composts. In the mobile fractions, as measured in soil saturation extract and LiCl extract, Cd and Pb were not detectable. Concentrations of Cr, Ni, and Zn were in the range published for unpolluted soils in other studies and did not show any differences according to treatment. Easily exchangeable Cu (in LiCl extract) was increased with compost fertilization, most probably due to complexation with low‐molecular organic complexants. Except for Cd and Zn, the results of the mobile HM fractions in the soil were in good agreement with plant HM concentrations. In conclusion, fertilization with high‐quality biowaste compost at such rates and after 10 y of application gives no cause for concern with regard to both total HM concentrations and available HM fractions.     

长江三角洲地区土壤盐酸可提取态重金属含量的空间变异特征

以江苏昆山市为典型区，对长三角地区土壤盐酸可提取态重金属含量的结构特征进行分析，得出该区盐酸可提取态重金属的空间分布格局并揭示了引起这种分布格局的成因和污染来源，结果表明：昆山市盐酸可提取态Cd、Cr、Cu、Pb、Zn、Hg属强变异，Ni和Co为中等变异。半方差函数模型拟合表明所有盐酸可提取态重金属元素均符合球状模型，8种重金属元素在一定范围内均存在空间相关性。采用Kriging最优内插法得到了盐酸可提取态重金属含量的空间分布格局，表明土壤盐酸可提取态重金属含量与工业活动、污水灌溉和大气降尘密切相关。通过主成分分析与地统计学相结合的方法，得出该区盐酸可提取态重金属由4个主成分构成，第一主成分为Cd、Cu、Pb、Cr和Zn，决定这一成分的主要因素为工业污水灌溉、大气降尘和元素地球化学特征；第二主成分为Ni，决定这一成分的主要因素为土壤内部因子；第三主成分为Hg，该成分主要受工业点源污染的影响；第四主成分为Co，该成分可能主要受地形影响。     

Reference concentrations for heavy metals in mineral soils, oat, and orchard grass (Dáctylis glomeráta) from three agricultural regions in Norway

Background values for heavy metals are necessary for the assessment of metal pollution of soils and plants. Samples of cultivated and uncultivated soils, oat grain, and seed heads of orchard grass (Dáctylis glomeráta) were collected from central, southeastern, and southwestern Norway. Total and easily extractable concentrations of As, Cd, Cr, Cu, Hg, Ni, Pb, and Zn were determined in soil samples and total concentrations in plant samples. Element distributions have been correlated with petrology of soil parent material, type of mineral deposit, soil depth, geographic area, and land use. Concentrations of heavy metals are generally within the lower part of the normal global range. The petrology of the soil parent material has the greatest influence on aqua regia extracted metal concentrations among the factors studied. DTPA extracted metals show less dependence on rock types. Presence of alum shale results in particularly high values for Cd in both soil extracts and in oat grain. Soil cultivation seems to influence the relative concentration of metals in the topsoil. The ratios of easily extractable to total concentrations of metals are primarily related to the organic matter content. Metal concentrations in oat grain can best be predicted by concentrations in DTPA extracts and soil pH among the factors studied. Seed heads of orchard grass are less affected by concentrations in the soil and appear therefore to be a poor indicator of heavy metals in soils.     

Organic Acids for the In Situ Remediation of Soils Polluted by Heavy Metals: Soil Flushing in Columns

To compare the soil remediation effectiveness of saltsof weak organic acids with strongchelating agents, three soils of different textures,all polluted by heavy metals, were washed in a column,at optimum pH, with salts of weak organic acids,namely, citrate, tartarate or oxalate + citrate orchelating agents (EDTA or DTPA). For the clay loam,Cr, Mn, Hg and Pb were removed by citrate andtartarate at levels of 43 to 45, 37 to 41, 91 to 92and 75%, respectively. EDTA and DTPA effectivelyleached only Pb after 20 pore volumes. For the loam,citrate leached 98 and 89% of Cd and Pb after 20 porevolumes, respectively, while tartarate leached out 91and 87% of Cd and Pb. EDTA and DTPA removed 93 to97% of these metals after 20 pore volumes. For thesandy clay loam, 84 to 91, 73 to 84, 56 to 70 and 72to 81% of Cd, Cu, Pb and Zn were removedrespectively, by citrate and tartarate. EDTA and DTPAremoved 93 to 97% of these metals after 20 porevolumes. An in situ soil remediation simulation wasalso tested using the sandy clay loam in a tub. After12 hr of retention, the citrate solution washed 81, 82,73 and 90%, of Cd, Cu, Pb and Zn, respectively, aftersix pore volumes. EDTA and DTPA effectively removedall heavy metals, except for Hg, but also extractedlarge quantities of soil nutrients and pollute thesoil by being adsorbed on the soil particles. Thesalts of citrate and tartarate effectively removed theheavy metals from the three polluted soils whileleaching little macro-nutrients and improving soilstructure. Each soil reached C and B levels ofsoil-clean-up criteria after 10 to 20 pore volumes andwithin 10 to 15 hr of flushing.     

Evaluation of Different Extraction Methods for the Assessment of Heavy Metal Bioavailability in Various Soils

The main objective of this study was to compare the effectiveness of different methods (heavy metals in pore water (PW), diffusive gradients in thin films (DGT), diethylene triamine pentaacetic acid (DTPA) extraction, and total heavy metals (THM) in soil) for the assessment of heavy metal bioavailability from soils having various properties and heavy metal contents. The effect of soil heavy metal pollution on shoot yield and sulfatase enzyme activity was also studied. Wheat (Triticum aestivum) was grown in different soils from Spain (n?=?10) and New Zealand (n?=?20) in a constant environment room for 25 days. The bioavailabilities of Cd, Cr, Cu, Ni, Pb, and Zn were assessed by comparing the metal contents extracted by the different methods with those found in the roots. The most widely applicable method was DGT, as satisfactory Cu, Ni, Pb, and Zn root concentrations were obtained, and it was able to distinguish between low and high Cr values. The analysis of the metal concentrations in PW was effective for the determination of Cr, Ni, and Zn content in root. Copper and Pb root concentrations were satisfactorily assessed by DTPA extraction, but the method was less successful with determining the Ni and Cr contents and suitable just to distinguish between high and low concentrations of Zn. The THM in soil method satisfactorily predicted Cu and Pb root concentrations but could only be used to distinguish between low and high Cr and Zn values. The Cd root concentration was not successfully predicted for any of the used methods. Neither shoot yield nor sulfatase enzyme activity was affected by the metal concentrations.     

Regulating the mobility of Cd, Cu and Pb in an acid soil with amendments of phosphogypsum, sugar foam, and phosphoric rock

When acid soil has been contaminated by metals as a result of industrial discharges, accidental spills, or acid mine drainage it may be desirable to retain the metals in the soil rather than allow them to leach away. We have investigated the potential of phosphogypsum (PG), sugar foam (SF), and phosphoric rock (PR) to regulate the availability and mobility of Pb, Cd and Cu. We have also identified changes in attenuation during incubation for 1 year and the effect of aging on metal speciation in amended soils. We studied miscible displacement in columns of undisturbed soil previously treated with solutions of the amendments and soluble metals and, subsequently, single and sequential chemical metal extractions. All amendments increased the soil's metal retention capacity. This, in turn, increased the amount of metal extractable by diethylenetriaminepentaacetic acid (DTPA). However, over time the amounts of DTPA‐extractable metal decreased, particularly for Cu and Pb. Both Cu and Cd were held preferentially within the acetic acid‐extractable fraction (operationally defined exchangeable fraction – EX fraction), whereas Pb was associated mainly with the hydroxylammonium‐extractable fraction (operationally defined bound to Fe and Al hydroxides – OX fraction). Both Pb and Cu in the oxide and organic fractions increased in the PG‐ and SF‐treated soils. In general, the distribution of metal did not change in the PR‐treated columns after the incubation. Finally, scanning electron microscopy in back‐scattered electron mode (SEM–BSE) showed the formation of Al‐hydroxy polymers which provides the soils with additional cation sorption capacity. In the PG‐ and PR‐treated columns, P and S were associated with these formations. The three metals were associated with the Al polymers, probably through direct coordination or the formation of ternary complexes with the inorganic ligands phosphate and sulphate.     

Effect of Application of Chromium Feedstock Compost on the Growth and Bioavailability of Some Trace Elements in Lettuce

A pot experiment was conducted to investigate the effect of chromium compost (0, 10, 30, and 50%) on the growth and the concentrations of some trace elements in lettuce (Lactuca sativa L.) and in the amended soils. Compost addition to the soil (up to 30%) increased dry matter yield (DMY); more than 30% decreased DMY slightly. The application of compost increased soil pH; nitric acid (HNO₃)–extractable copper (Cu), chromium (Cr), lead (Pb), and zinc (Zn); and diethylenetriaminepentaacetic acid (DTPA)–, Mehlich 3 (M3)–, and ammonium acetate (AAc)–extractable soil Cr and Zn. The addition of Cr compost to the soil increased tissue Cr and Zn but did not alter tissue cadmium (Cd), Cu, iron (Fe), manganese (Mn), nickel (Ni), and Pb. The Cr content in the lettuce tissue reached 5.6 mg kg^?1 in the 50% compost (326 mg kg^?1) treatment, which is less than the toxic level in plants. Our results imply that compost with high Cr could be used safely as a soil conditioner to agricultural crops.     

Heavy-Metal Bioavailability and Chelate Mobilization Efficiency in an Assisted Phytoextraction Process by Sesbania sesban (L.) Merr

Chelate-induced phytoextraction is an innovative technique for cleaning metal- contaminated soil. The present study evaluates the degree of metal mobilization in soil and enhancement of phytoextraction of cadmium (Cd), lead (Pb), and zinc (Zn) by Sesbania sesban (L.) Merr. from artificially contaminated soil by application of ethylenediaminetetraacetic acid (EDTA). After 30 days of plant growth, the pots were divided into three sets (0.0, 2.5, and 5.0 mmol EDTA per kg soil). Experimental results indicated that levels of diethylenetriaminepentaacetic acid (DTPA)–extractable metals and metals in the leachate decreased as the EDTA dose increased. Plant growth parameters and total chlorophyll contents in the plants with EDTA applied were less than those of control. However, EDTA application significantly reduced metal accumulation in root and increased metal accumulation in the shoot of plants; similar results were obtained for the bioconcentration factor and translocation factor. The application of 5 mmol EDTA kg^?1 to metal-spiked soil may be an efficient alternative for the chemically enhanced phytoextraction by S. sesban.     

肥料重金属含量状况及施肥对土壤和作物重金属富集的影响

本文对肥料中重金属的含量状况以及施肥对土壤和农作物重金属累积影响的研究进展进行了系统分析和总结。过磷酸钙中锌（Zn）、 铜（Cu）、 镉（Cd）、 铅（Pb）含量高于氮肥、 钾肥和三元复合肥,有机-无机复混肥料中的Pb含量高于其他化肥。有机肥如畜禽粪便、 污泥及其堆肥中的重金属含量高于化肥,猪粪中的Cu、 Zn、 砷（As）、 Cd含量明显高于其他有机废弃物,鸡粪中铬（Cr）含量高;污泥和垃圾堆肥中Pb或汞（Hg）含量高。商品有机肥Zn、 Pb和镍（Ni）含量高于堆肥,Hg含量高于畜禽粪便。多数研究表明,氮磷钾配施与不施肥相比土壤Cd和Pb含量增加,施用有机肥比不施肥提高土壤Cu、 Zn、 Pb、 Cd含量。施用化肥对农作物重金属富集的影响不明确,而施用有机肥可提高作物可食部位Cu、 Zn、 Cd、 Pb 的含量,影响大小与有机肥种类、 用量、 土壤类型和pH以及作物种类等有很大关系。在今后的研究中应着重以下几个方面, 1）典型种植体系下土壤重金属的投入/产出平衡; 2）不同种植体系下长期不同施肥措施对土壤重金属含量、 有效性影响的动态趋势; 3）典型种植体系和施肥措施下土壤对重金属的最高承载年限; 4）现有施肥措施下肥料中重金属的最高限量标准。     

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

Abstract

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

酸雨地区蔬菜对重金属的吸收及重金属健康风险基准的估算

通过盆栽实验,以小白菜(上海青)、大白菜和萝卜为指示作物,研究了酸雨作用下Cu,Zn,Pb,Cd,Cr和Ni复合污染物在土壤-作物系统中的吸收与富集情况。结果表明,酸雨-重金属复合污染处理使Cu,Pb,Cr和Ni在蔬菜中积累量明显高于对照处理;Zn和Cd一般只有在复合污染处理中外源Zn或Cd含量较高时才明显高于对照处理。与对照相比,酸雨-重金属复合污染处理使Pb和Ni的富集系数增大,Cu的富集系数多数情况下增大,Cd的富集系数多数情况下减小,Zn和Cr富集系数的变化在不同蔬菜之间存在较明显的差异;重金属在不同蔬菜中的富集系数一般表现为萝卜>上海青>大白菜,蔬菜中不同重金属富集系数一般表现为Zn>Cd>Ni>Cu>Pb>Cr。酸雨-重金属复合污染条件下蔬菜中重金属积累量与其在土壤中总量之间的相关性均达到显著或极显著水平。以大宗蔬菜上海青、大白菜和萝卜为指示作物对酸雨地区蔬菜地中重金属的健康风险基准进行了估算,这对开展酸雨地区土壤重金属环境容量评价、重金属污染修复目标及地方性土壤环境质量标准的制订提供了参考依据。     

Heavy‐Metal Concentration of Sewage‐Contaminated Water and Its Impact on Underground Water,Soil, and Crop Plants in Alluvial Soils of Northwestern India

Abstract

Heavy‐metal concentration in underground and surface water, soil, and crop plants growing in farmers' fields near the industrial city of Ludhiana, Punjab, India, that receive irrigation with water contaminated with sewer and untreated industrial effluents was studied. The concentrations of lead (Pb), chromium (Cr), cadmium (Cd), and nickel (Ni) in sewage‐contaminated water were 18, 80, 88, and 210 times higher than in shallow handpump water, and 21, 133, 700, and 2200 times higher than in deep tube‐well water, respectively. The concentrations of Cd and Ni in shallow handpump underground water were significantly higher than in deep tube‐well underground water. The concentrations of Pb, Cr, Cd, and Ni in deep tube‐well water were 0.017, 0.003, 0.0002, and 0.0002 mg L^?1, respectively. Soils irrigated with sewage‐contaminated water had higher electrical conductivity, cation exchange capacity, organic carbon (C), and clay content but had lower pH and calcium carbonate content compared to soils irrigated with deep underground water. The concentrations of diethylenetriamine pentaacetic acid (DTPA)–extractable Pb, Cr, Cd, and Ni in soils irrigated with sewage‐contaminated water were 1.8, 35.5, 3.6, and 14.3 times higher, and total concentrations of these heavy metals were 1.5, 3.0, 3.7, and 2.2 times higher than that in soils irrigated with deep underground water. The mean concentrations of Pb, Cr, Cd, and Ni in crop plants growing on soils irrigated with sewage‐contaminated water were 4.88, 4.20, 0.29, and 3.99 mg kg^?1, which were 1.2, 2.1, 8.7, and 1.9 times higher than in plants irrigated with deep tube‐well water, respectively. The amounts of potentially toxic metals were significantly and positively correlated with cation exchange capacity and organic C content and negatively correlated with soil pH. In conclusion, long‐term accumulation of toxic metals in soils and their uptake by crop plants has a high potential for phytotoxicity as well as for entering into the food chain. The findings also suggest contamination of underground shallow drinking water through leaching of some highly mobile metals.     

Residual heavy metal concentrations in sludge‐amended coastal plain soils ‐ I. Comparison of extractants

Abstract

The purposes for this research were: to examine the long‐term residual effects of farmland applications of municipal sludges from four treatment technologies on the total and extractable Zn, Cu, Mn, Fe, Pb, Ni and Cd concentrations in Coastal Plain soils; to investigate the effects of sludge sources and rates on the effectiveness of soil extractants to remove the various metals; and to determine correlation coefficients for soil extractable versus plant accumulation in tobacco. The extractants evaluated were Mehlich 1 and 3, and DTPA‐pH 7.3. Composite Ap horizon soil samples and tobacco leaf samples were obtained in 1984 from research plots at two sites in Maryland that were established in 1972 and 1976, respectively, using sludge materials from three wastewater treatment facilities in the Washington, D.C. metropolitan region. Similar application rates were used at both sites.

A wide range in soil pH values was found among treatments at each site. Significant (p ≤ 0.05) increases were observed in total Zn, Cu, Fe, Pb, Ni, and Cd for all sludge sources with increased rates; however, values for total soil Mn exhibited high variability in all cases. The rankings among the extractants varied for some elements depending on the sludge sources. For Zn, the rankings were Mehlich 1 > Mechlich 3 > DTPA‐pH 7.3 across all sources and rates. For Cu, Mehlich 3 > Mehlich 1 > DTPA‐pH 7.3 was found for soils amended with Blue Plains digested (BPD) and Piscataway limeddigested (PLD) sludges but Mehlich 1 ≥ DTPA pH 7.3 > Mehlich 3 for Blue Plains limed compost (BPLC) and Annapolis Fe and heat treated (AFH) sludges. Concerning extractable Mn, Mehlich Mehlich 1 > Mechlich 3 > DTPH pH 7.3 was the order for BPLC and AFH sludges but Mehlich 3 > Mehlich 1 > DTPA‐pH 7.3 was observed for BPD and PLD sludges. The rankings among extractants for Fe (Mehlich 3 > Mehlich 1 > DTPA‐pH7.3), Ni (Mehlich 3 ≥ Mehlich 1 > DTPA‐pH 7.3), Pb (Mehlich 3 > DTPA‐pH 7.3 > Mehlich 1) and Cd (Mehlich 1 > Mehlich 3 > DPTA‐pH7.3) were somewhat similar across all sludge sources. Significant correlation coefficients were obtained for all three extractants for soil extractable vs. plant Zn, Cu, Ni, and Cd at both sites; however, Mehlich 3 was not significant for Mn. Also, neither of the extractants produced significant coefficients for Fe and Pb.