Effect of sewage sludge on some chemical properties of calcareous sandy soils

Abstract

City sewage sludge was applied to the surface layer (0–10 cm) of two sandy soils, slightly calcareous with 8.9% CaCO₃ and moderately calcareous with 26.7% CaCO₃, at the rates of 0, 25, 50, 75, and 100 Mg ha^‐1. The effects of sewage sludge and its rates on total soluble salts, pH of soils and concentration and movement of some heavy metals within soils were investigated. Soil samples were packed at bulk density of 1.5 g cm^‐3 in PVC columns and incubated for 19 weeks. The results indicated that total soluble salts (EC) of the treated layer increased with increasing sewage sludge rates. Soluble salts also increased with an increase in soil depth for both soils. The pH values of treated layers in two soils decreased with increasing sewage sludge rates. With increasing sewage sludge rates, concentrations of heavy metals [cobalt (Co), nickel (Ni), cadmium (Cd), and leaf (Pb)] increased in the treated layers compared to the untreated layers and their mobility was restricted mostly to the upper 30‐cm depth. Movement of Co and Pb in both the soils was predominately limited up to a depth of 40 cm for Co and 5 cm for Pb below the treated soil layer. Nickel and Cd movement was mostly limited to a depth of 10 cm in slightly calcareous soil and 5 cm in moderately calcareous soil. Metal movement in the respective soils is ranked as Co>Ni=Cd>Pb and Co>Ni=Cd>Pb. The low concentrations of heavy metals and the restricted mobility with soil depth, suggest that this material may be used for agricultural crop production without any toxic effect on plants.     

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

Purpose

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

Material and methods

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

Results and discussion

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

Conclusions

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

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

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

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。     

The Nature and Distribution of Metals in Soils of the Sydney Estuary Catchment, Australia

Total topsoil 50th percentile Cu, Pb and Zn concentrations (n?=?491) in the Sydney estuary catchment were 23 ??g?g^?1, 60 ??g?g^?1 and 108 ??g?g^?1, respectively. Nine percent, 6% and 25% of samples were above soil quality guidelines, respectively and mean enrichment was 14, 35 and 29 times above background, respectively. Soils in the south-eastern region of the catchment exhibited highest metal concentrations. The close relationship between soil metal and road network distributions and outcomes of vehicular emissions modelling, strongly suggested vehicular traffic was the primary source of metals to catchment soils. Catchment soil and road dust probably make an important contribution to contamination of the adjacent estuary. The concentration of soil metals followed the land use trend: industrial?>?urban?>?undeveloped areas. A high proportion (mean 45%, 62% and 42%, for Cu, Pb and Zn, respectively) of metals in the soils may be bioavailable.     

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.     

Heavy metal uptake by wheat seedlings grown in fly ash-amended soils

A bioassay technique was used to investigate heavy metals uptake by wheat seedlings grown in fly ash-amended soils. No negative effect of fly ash on the growth of wheat seedlings was found. The addition of the fly ash generally decreased the heavy metal concentration in the wheat seedlings. The total accumulation largely depended on the soil characteristics. The variation in the soil pH induced by the fly ash treatment could be considered the most important parameter that influenced heavy metals uptake. In the soil with a higher increase of pH (2 units) total accumulation of heavy metals decreased with increasing fly ash addition. In the other soils where the pH variation was lower (0.4 units), total accumulation of some heavy metals increased. These obtained data provide useful information which is required before the agronomic use of fly ash can be recommended in Italian soils.     

Effects of time and temperature on the bioavailability of Cd and Pb from sludge-amended soils

A pot experiment was conducted to compare the behaviour and bioavailability of Cd and Pb from two soils mixed with sewage sludge at three rates (0, 50 and 150 t ha^?1) and maintained at two contrasting ambient temperatures (15°C and 25°C) over a period of one year following the treatments. Ryegrass (Lolium perenne) accumulated Cd and Pb in the sewage sludge treated soils, although accumulation was significantly lower in the soils treated at the high rate (150 t ha^?1) compared to the low rate (50 t ha^?1). Ryegrass grown in the warm environment (25°C) accumulated significantly higher levels of Cd and Pb than that grown in cooler conditions (15°C). Samples of the soils spiked with nitrate salts of Cd and Pb at equivalent rates of metal loading resulted in the ryegrass accumulating much higher levels of both the metals than on the sludge treated soils. Metal uptake by the ryegrass from the sludge treatments increased over successive harvests while that from metal salt treatments decreased. The observed trend of increasing plant metal uptake over time coincided with a trend of decreasing pH in the sludge treatments. However, the concentrations of Cd and Pb extracted by DTPA failed to predict the changes in plant metal uptake. The importance of sewage sludge as both a source and a sink of pollutant metals and the trend of increasing bioavailability over time shown by this experiment are discussed.     

Competitivity,selectivity, and heavy metals-induced alkaline cation displacement in soils

Abstract

The simultaneous incorporation of heavy metals into the soil is still a matter of great concern. Interaction (competitive sorption) between these metals and the soil solid phase may result in a deterioration of soil quality which relies basically on amounts of alkaline cations saturating soils sorptive complex. Results of this study indicate that Pb, Cu, C d, and Zn have induced solution pH decreases which were more intensive at highest metal loading rates. Partition parameters (Kd)-based sequences showed that Pb and Cu were more competitive than Cd and Zn and the overall selectivity sequence followed: Pb > Cu > Cd > Zn. Metal loadings and their competitive sorption have led to a strengthened displacement of alkaline cations (i.e. Ca²⁺, Mg²⁺, K⁺, Na⁺), especially of Ca²⁺ as a factor “stabilizing” soil sorptive complex. Such metals impact jointly with soils acidification are of great environmental concern since tremendous amounts of alkaline cations (especially Ca²⁺) may be potentially leached out, irrespective of the degree of soil contamination, as evidenced in the current study. High and positive ΔG values implied that the studied soils were characterized by generally low concentrations of exchangeable potassium which required high energy to get displaced (desorbed). Further studies on heavy metal uncontaminated or contaminated areas should be undertaken to provide with data which should be used for predictions on changes related to soil buffering capacity as impacted by heavy metal inputs.     

Heavy Metal Fractionation and Extractability in Dredged Sediment Derived Surface Soils

The objective of this study was to characterise pollution with heavy metals in surface soils sampled at various dredged sediment disposal sites in the Flemish region (Belgium). The sites selected varied in the period since sediment disposal ceased and in current vegetation and land use. Total metal contents (Cd, Co, Cu, Fe, Mn, Ni, Pb, and Zn) in the surface soils varied widely. For some disposal sites Cd and Zn concentrations greatly exceeded reference values for clean soil. The distribution of the metals as determined by sequential extraction differed between elements, but was simular for all the soils. This suggested that metals in these sediment derived surface soils were accumulated and transformed in a similar way. Residual fractions were low compared to total contents (2 – 4% for Cd, 25% – 35% for Co, 7 – 18% for Mn, 4 – 22% for Zn, 12 – 41% for Ni, 11 – 42% for Pb, 20 – 45% for Cu, < 10% for Zn). High metal concentrations in the acid-extractable and reducible fractions may indicate pollution from anthropogenic sources. DTPA-extractable metals, which may be considered indicative of plant-available contents, were relatively high compared to the total contents. The relative extractability, expressed as the ratio of DTPA-extractable to total contents, decreased in the order Cd (38%) > Cu (28%) = Zn (26%) > Pb (13%) > Ni (10%) > Co (3%). Most of the sites studied would be of concern if they were used for agricultural activities. No trends in metal availability in the period following disposal were apparent from the data.     

Bioaccumulation of Lead and the Effects of Lead on Catalase Activity,Glutathione Levels,and Chlorophyll Content in the Leaves of Wheat

Soil contamination with heavy metals can lead to losses in agricultural yield and affect human health as the metals enter the food chain, which has become a worldwide problem. Compared with other heavy metals, lead (Pb) contamination is high because of its long persistence in soil and highly toxic effects on crop production and human health. Wheat is the world's most widely grown cereal and can be cultivated in a wide range of soils. Recently, wheat has been grown widely in northern China. The aims of the present studies are to investigate the effect of Pb on antioxidative metabolisms and chlorophyll synthesis of wheat ‘Jinan No. 17.’ Moreover, calcium ion (Ca²⁺) levels and bioaccumulation of Pb in the leaves of wheat were investigated. The soil was artificially contaminated with different concentrations of Pb [0, 100, 500, and 2000 Pb mg kg^?1 dry weight (DW) soil as lead nitrate, Pb(NO₃)₂]. The catalase (CAT) activity and glutathion (GSH), chlorophyll a, chlorophyll b, and total chlorophyll contents in the leaves of wheat were analyzed with a spectrophotometer at different stages of wheat growth. Calcium levels and bioaccumulation of Pb in the leaves of wheat were studied with inductively coupled plasma sector field mass spectrometry (ICP-SF-MS). The results indicated that Pb stress can increase the content of GSH in leaves of wheat, thereby affecting the activity of CAT. Both low and high concentrations of Pb stimulated chlorophyll synthesis at early stages of wheat growth and inhibited chlorophyll synthesis at later stages of wheat growth. Furthermore, Ca and Pb in leaves of wheat increased with increasing concentrations of Pb on day 34 as determined with ICP-SF-MS.     

Assessment of Heavy Metals in Spinach (Spinacia oleracea L.) Grown in Sewage Sludge–Amended Soil

The assessment of heavy metals in spinach (Spinacia oleracea) grown in sewage sludge–amended soil was investigated. The results revealed that sewage sludge significantly (P < 0.01) increased the nutrients and heavy metals such as cadmium (Cd), chromium (Cr), copper (Cu), manganese (Mn), and zinc (Zn) in the soil. The contents of metals were found to be below the maximum levels permitted for soils in India. The most agronomic performance and biochemical components of S. oleracea were found at 50% concentrations of sewage sludge in both seasons. The contents of Cd, Cr, Cu, Mn, and Zn in S. oleracea were increased from 5% to 100% concentrations of sewage sludge in both seasons. The order of contamination factor (Cf) of different heavy metals was Mn > Cd > Cr > Zn > Cu for soil and Cr > Cd > Mn > Zn > Cu for S. oleracea plants after application of sewage sludge. Therefore, use of sewage sludge increased concentrations of heavy metals in soil and S. oleracea.     

Stabilization of tannery sludge amended soil using Ricinus communis,Brassica juncea and Nerium oleander

Purpose

Characterization of tannery sludge (TS) for its plausible use in amelioration and phytoremediation of heavy metal rich TS treated soil by growing economically important plants (Ricinus communis, Brassica juncea and Nerium oleander).

Materials and methods

Treatments were prepared by amalgamation of TS (0, 5, 10, 20, 30, 50, 75, 100 %) with garden soil (GS). All treatments were analysed for chemical properties, total and DTPA (Diethylene triamine pentaacetic acid) extractable heavy metals (Cr, Pb, Cu, and Mn). Seed germination experiment was conducted; unvarying saplings were selected and planted in concerned pots and allowed to grow for 90 days in green house. At harvest, plant samples were washed with distilled water and used for determination of growth parameters (biomass of root, shoot and total biomass on dry weight basis) and metal accumulation in different parts of the plant. Translocation factor (TF) and bioconcentration factor (BCF) have been calculated to check the phytostabilization capability of studied plants.

Results and discussion

Application of TS in fixed quantity as an amendment resulted in significant improvements of GS characteristics (alkaline pH with high electrical conductivity, organic carbon, available NPK and heavy metals) and in treatments. DTPA extractable heavy metal concentrations were found very low and total heavy metal concentrations were also found under allowable range in control and treated soil (T-I to T-VI). The maximum seed germination percentage, plant growth, biomass production for all plant species were observed in T-III treatment (20 % TS + 80 % GS) with majority of the metal accumulation in underground part (BCF >1) and meagre translocation in aerial part (TF <1). From T-IV to T-VII treatment, accumulation of heavy metals in plant parts has generally increased; however, biomass has been tremendously decreased.

Conclusions

TS was found rich in NPK content with significant concentration of heavy metals. Pot growth experiment suggested amelioration of GS with specific quantity of 20 % TS can tremendously enhance the plant growth, help in the utilization of TS and can act as a substitute of synthetic fertilizer. Majority of the metals was accumulated in root part (BCF >1) and meagre translocation (TF <1) in aerial part, concludes R. communis and B. juncea could be suitable plant species to be grown in heavy metal rich TS treated soil, vis-à-vis for phytostabilization of heavy metals. In addition, these oil yielding and medicinal plants can also be used for phytoremediation of moderately contaminated tannery soils.

     

Pollution and Ecological Risk Assessment of Heavy Metals in Farmland Soils in Yanqi County,Xinjiang, Northwest China

A total of 50 farmland soil samples were collected from the Yanqi County, Xinjiang, China, and the concentrations of eight heavy metal elements (As, Cd, Cr, Cu, Mn, Ni, Pb and Zn) were determined by standard methods. The spatial distribution, pollution level and ecological risk status of heavy metals were analyzed based on GIS technology, the Geo-accumulation Index (Igeo), the Pollution Load Index (PLI) and the Potential Ecological Risk Index (RI). Results indicated that: (1) The average contents of Cd, Cr, Ni, Pb, and Zn of farmland soils exceeded the background values of irrigation soils in Xinjiang by 1.5, 1.40, 1.33, 2.63, and 4.92 times, respectively. Cd showed a no-pollution level, Zn showed a partially moderate pollution level, Pb showed a slight pollution level, and Cr, Cu, As, Mn, and Ni showed no-pollution level, compared to the classification standard. The PLI values of heavy metal elements of farmland soils varied from 0.83 to 1.89, with an average value of 1.29, at the moderate pollution level. (2) The Individual Potential Ecological Risk Index for heavy metals in the study area was ranked in the order of: As > Ni > Cu > Cd > Pb > Cr> Zn. The RI values of heavy metals of farmland soils varied from 3.45 to 11.34, with an average value of 6.13, at the low ecological risk level. (3) Cu and Mn of farmland soils were mainly originated from the soil parent material and topography of the study area. As, Cd, Ni and Pb were mainly originated from human activities, and Cr and Zn may originated from both natural and anthropogenic factors in the study area.     

Heavy Metal Accumulation in Soil Amended with Roadside Pond Sediment and Uptake by Rice (Oryza sativa L.)

The effect of addition of roadside pond sediments on heavy metal contents of flooded rice paddies was studied to investigate the yield of rice and uptake of heavy metal by rice straw and grain. Sequential extraction of heavy metals on sediments shows that the percentage contribution of metals in the labile fraction follows the order lead (Pb, 48%) > copper (Cu, 42%) > zinc (Zn, 31%) > cadmium (Cd, 16%) > chromium (Cr, 9%) > nickel (Ni, 6%). The risk assessment code (RAC) for pond sediment revealed that Cr and Ni were found in the low-risk zone, Zn and Cd in the medium-risk zone, and Cu and Pb in the high-risk zone. However, though the heavy metal concentration in rice grain does not exceed the range acceptable for human consumption, it still represents a significant additional source of heavy metals in the diet. The addition of pond sediment significantly increased the rice yield over control. Therefore, pond sediment would be a valuable resource for agriculture if it is properly used.     

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.     

Fractionation and Prediction of Copper,Lead, and Zinc Uptake by Two Leaf Vegetables from Their Geochemical Fractions in Urban Garden Fields in Northern Nigeria

The bioavailability and mobility of heavy metals in soil are strongly influenced by the chemical or geochemical species of the metals in soils. We determined the geochemical fractions of copper (Cu), lead (Pb), and zinc (Zn) in garden soils, using the seven-step Zeien and Bruemmer fractionation scheme in relation to metal uptake by two leaf vegetables (lettuce, Latuca sativa, and amaranthus, Amaranthus caudatus). Our objective was to develop predictive models for assessing the lability of these metals from the soil metal fractions. The sums of fractions of Cu, Pb, and Zn did not differ by more than 10% from the “pseudo” total concentrations of the metals determined independently by aqua regia digestion. The general distribution of Cu and Pb among the soil fractions was in the order organic-matter-bound > Fe_o and Fe_c > Mn_ox > exchangeable > residual > mobile, except for Cu, where residual and the exchangeable were reversed. Zinc was fairly evenly distributed among organic matter (20%), Fe_o (22%), Fe_c (20%), and residual (21%). Averaged across sites, Cu, Pb, and Zn concentrations in the lettuce were almost twice as great as the concentrations in amaranthus even though they were raised in the same fields. The variance in Cu, Pb, and Zn uptake by amaranthus was predicted up to 51–99% from soluble, exchangeable, organic matter, and Fe_o-bound fractions; the variance in metal uptake by lettuce was best predicted from Fe_c- and Fe_o-bound fractions up to 76–90%. Our results indicated differential accessibility to metal fractions by lettuce and amaranthus grown in the same field.     

Mikrosondenuntersuchungen an unterschiedlich stark mit Schwermetallen belasteten Böden. 2. Gehalte an Schwermetallen und anderen Elementen in Huminstoffaggregationen,Streustoffen und Holzkohlepartikeln

Electron microprobe studies on soil samples with varying heavy metal contamination. 2. Contents of heavy metals and other elements in aggregations of humic substances, litter residues and charcoal particles EMA point analysis show that the organic matter constituents of heavy metal contaminated soils are highly enriched with heavy metals. The maximal trace element accumulation were for Cu up to 13,000 mg/kg, for Zn up to 48,000 mg/kg, for Cd up to 2,100 mg/kg and for Pb up to 193,000 mg/kg. The affinity for the accumulation of the different heavy metals in aggregations of humic substances can be described by the sequence Cu > Pb ? Cd > Zn ? Ni > Co. In very strongly acidified humic top soil horizons the Pb and Cd accumulation in the organic matter constituents is in competition with the accumulation in Fe and Mn oxides. The heavy metal contents (especially of Cu) of the organic matter are often correlated with the content of organically bound calcium. The EMA results also show that high heavy metal amounts occur in combination with Ca-accumulations in the epidermis and the outer bark parenchym of decayed roots. EMA point analysis of the interior of fungus sclerotias show that sclerotias can contain high amounts of heavy metals, in particular lead (up to 49,700 mg Pb/kg). From statistical results of EMA point analysis follows that lead and other heavy metals attached to humic substances are not only bound as metal organic complexes but also as organic metal phosphate complexes. Also charcoal particles of polluted soils contain high amounts of heay metals. The accumulation affinity is quite similar to that of humic substances.     

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

Purpose

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

Materials and methods

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

Results and discussion

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

Conclusions

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

     

The influence of compost addition on heavy metal distribution between operationally defined geochemical fractions and on metal accumulation in plant

Purpose

Metal distribution patterns among geochemical fractions are informative for metal phytoavailability. Compost added to polluted soils may adsorb metals on the less phytoavailable fractions. A bioassay experiment was conducted to establish possible correlations between metal concentrations in different soil fractions and metal contents in edible plant parts and to investigate the influence of different compost loads on heavy metal availability to plants.

Materials and methods

Chinese cabbage plants were grown in pots with sandy and clayey soils and soils mixed with different doses of biosolid compost spiked with soluble heavy metal salts (Cd, Cu, and Pb). The metals’ distribution pattern in the soil and mixed samples was determined by sequential extraction procedure (modified BCR protocol). The studied fractions, from most to least bioavailable, were water-extractable (WE), exchangeable-adsorbed (EXC), associated with carbonates and acetic acid-soluble forms (CARB), occluded by reducible (hydro)oxides of Fe and Mn (RO), and associated with organic matter (OM) and a residual fraction (RES). Metal concentrations in soil extracts and in the digested plant tissue were measured by ICP-AES.

Results and discussion

The highest compost doses (72 and 115 Mg ha^?1) enhanced cabbage yield significantly. No excessive phytoaccumulation of metals was observed in plants grown in the clayey soil or its mixtures with compost. The compost dose of 72 Mg ha^?1 was optimal in decreasing Cu accumulation by plants grown in sandy soil, and 28.8 Mg ha^?1 was found to be effective in reducing Cd and Pb uptake. Metals were accumulated in plants primarily from the WE, EXC, and CARB fractions, whereas other fractions decreased phytoaccumulation. Compost addition suppressed heavy metal mobility, but different fractions were active in pollutant sorption, depending on soil type and metal.

Conclusions

Compost addition increased metal proportions in the RO and OM fractions, reducing metal phytoavailability. This is especially important for sandy soils with low adsorption ability and higher vulnerability to metal pollution than clayey soils. A compost dose of 20% v/v (or 28.8 Mg ha^?1) effectively reduced plant accumulation of Cd and Pb. We propose using the first three steps of the modified BCR protocol as a three-step sequential-extraction procedure for the most phytoavailable fractions of heavy metal: WE, EXC, and CARB.