Effects of heavy metals on the litter consumption by the earthworm Lumbricus rubellus in field soils

Aim of this study was to determine effects of heavy metals on litter consumption by the earthworm Lumbricus rubellus in National Park the “Brabantsche Biesbosch”, the Netherlands. Adult L. rubellus were collected from 12 polluted and from one unpolluted field site. Earthworms collected at the unpolluted site were kept in their native soil and in soil from each of the 12 Biesbosch sites. Earthworms collected in the Biesbosch were kept in their native soils. Non-polluted poplar (Populus sp.) litter was offered as a food source and litter consumption and earthworm biomass were determined after 54 days. Cd, Cu and Zn concentrations were determined in soil, pore water and 0.01 M CaCl₂ extracts of the soil and in earthworms. In spite of low available metal concentrations in the polluted soils, Cd, Cu and Zn concentrations in L. rubellus were increased. The litter consumption rate per biomass was positively related to internal Cd and Zn concentrations of earthworms collected from the Biesbosch and kept in native soil. A possible explanation is an increased demand for energy, needed for the regulation and detoxification of heavy metals. Litter consumption per biomass of earthworms from the reference site and kept in the polluted Biesbosch soils, was not related to any of the determined soil characteristics and metal concentrations.     

The effect of two endogeic earthworm species on zinc distribution and availability in artificial soil columns

The objective of this study was to determine the impact of earthworm bioturbation on the distribution and availability of zinc in the soil profile.Experiments were carried out with Allolobophora chlorotica and Aporrectodea caliginosa in 24 perspex columns (∅ 10 cm), filled with 20-23 cm non-polluted soil (OM 2%, clay 2.9%, pH 0.01 M CaCl₂ 6.4), that was covered by a 3-5 cm layer of aged zinc spiked soil (500 mg Zn/kg dry soil) and another 2 cm non-polluted soil on top. After 80 and 175 days, columns were sacrificed and each cm from the top down to a depth of 15 cm was sampled. Earthworm casts, placed on top of the soil, were collected. Each sample was analyzed for total and CaCl₂-exchangeable zinc concentrations.Effects of earthworm bioturbation were most pronounced after 175 days. For A. chlorotica, total and CaCl₂-exchangeable zinc concentrations in the polluted layers were lower with than without earthworms. Total zinc concentrations in the non-polluted layers were higher in columns with earthworms. Casts of A. chlorotica collected on the soil surface showed slightly higher total zinc concentrations than non-polluted soil. Casts were found throughout the whole column. For A. caliginosa there were no differences in total zinc concentration between columns with and without earthworms. CaCl₂-exchangeable zinc concentrations in the polluted layers were lower for columns with earthworms. Casts were mainly placed on top of the soil and contained total zinc concentrations intermediate between those in non-polluted and polluted soil layers.This study shows that different endogeic earthworm species have different effects on zinc distribution and availability in soils. A. chlorotica transfers soil throughout the whole column, effectively mixing it, while A. caliginosa decreases metal availability and transfers polluted soil to the soil surface.     

Short-term changes of metal availability in soil. II: The influence of earthworm activity

This study aimed to evaluate short-term earthworm-induced changes in the availability of metals applied to soil directly (metal-spiked) or via an organic matrix (sludge-amended). A laboratory experiment was performed using destructive sampling of microcosms filled with agricultural soil. A concentration gradient of industrial sludge contaminated predominantly with Cr, Cu, Ni, and Zn, and a soil freshly spiked with the same metal concentrations were applied on top of the soil columns. Individuals of Dendrobaena veneta (mimicking a realistic density of 500 earthworms per m²) were introduced in half of the replicates of each treatment. Total and 0.01 M CaCl₂ extractable metal concentrations were measured in soil after 0, 3, 6 and 12 weeks and metal concentrations in earthworms and percolates were measured after 3, 6, and 12 weeks. Earthworm activity did not affect metal availability of any treatment over time, but Ni and Cu concentrations in D. veneta were higher at the highest treatment levels. Earthworm Zn concentrations were similar in all treatments while Cr concentrations increased with increasing soil total metal content only for sludge treatments. Existing relationships of earthworm metal concentrations with total metal content in soil, taken from the literature, were not able to predict the metal levels measured in D. veneta. Results demonstrated that although over 12 weeks earthworm activity did not affect metal availability in soil, their burrowing activities did influence the metal concentrations of percolates over time.     

Lethal critical body residues as measures of Cd,Pb, and Zn bioavailability and toxicity in the earthworm<Emphasis Type="Italic">Eisenia fetida</Emphasis>

Background. Earthworm heavy metal concentrations (critical body residues, CBRs) may be the most relevant measures of heavy metal bioavailability in soils and may be linkable to toxic effects in order to better assess soil ecotoxicity. However, as earthworms possess physiological mechanisms to secrete and/or sequester absorbed metals as toxicologically inactive forms, total earthworm metal concentrations may not relate well with toxicity. Objective  The objectives of this research were to: i) develop LD₅₀s (total earthworm metal concentration associated with 50% mortality) for Cd, Pb, and Zn; ii) evaluate the LD₅₀ for Zn in a lethal Zn-smelter soil; iii) evaluate the lethal mixture toxicity of Cd, Pb, and Zn using earthworm metal concentrations and the toxic unit (TU) approach; and iv) evaluate total and fractionated earthworm concentrations as indicators of sublethal exposure. Methods  Earthworms (Eisenia fetida (Savigny)) were exposed to artificial soils spiked with Cd, Pb, Zn, and a Cd-Pb-Zn equitoxic mixture to estimate lethal CBRs and mixture toxicity. To evaluate the CBR developed for Zn, earthworms were also exposed to Zn-contaminated field soils receiving three different remediation treatments. Earthworm metal concentrations were measured using a procedure devised to isolate toxicologically active metal burdens via separation into cytosolic and pellet fractions. Results and Discussion  Lethal CBRs inducing 50% mortality (LD₅₀, 95% CI) were calculated to be 5.72 (3.54-7.31), 3.33 (2.97-3.69), and 8.19 (4.78-11.6) mmol/kg for Cd, Pb, and Zn, respectively. Zn concentrations of dead earthworms exposed to a lethal remediated Zn-smelter soil were 3-fold above the LD₅₀ for Zn and comparable to earthworm concentrations in lethal Zn-spiked artificial soils, despite a 14-fold difference in total soil Zn concentration between lethal field and artificial soils. An evaluation of the acute mixture toxicity of Cd, Pb, and Zn in artificial soils using the Toxic Unit (TU) approach revealed an LD₅₀ (95% CI) of 0.99 (0.57-1.41) TU, indicating additive toxicity. Conclusions  Total Cd, Pb, and Zn concentrations in earthworms were good indicators of lethal metal exposure, and enabled the calculation at LD₅₀s for lethality. The Zn-LD₅₀ developed in artificial soil was applicable to earthworms exposed to remediated Zn-smelter soil, despite a 14-fold difference in total soil Zn concentrations. Mixture toxicity evaluated using LD₅₀s from each single metal test indicated additive mixture toxicity among Cd, Pb, and Zn. Fractionation of earth worm tissues into cytosolic and pellet digests yielded mixed results for detecting differences in exposure at the sublethal level Recommendation and Outlook  CBRs are useful in describing acute Cd, Pb, and Zn toxicity in earthworms, but linking sublethal exposure to total and/or fractionated residues may be more difficult. More research on detoxification, regulation, and tissue and subcellular partitioning of heavy metals in earthworms and other invertebrates is needed to establish the link between body residue and sublethal exposure and toxicity. Keywords: Bioavailability; Cd; critical body residues; earthworms; metals; Pb; soil; Zn An erratum to this article is available at .     

The effect of EDTA on the extractability of Zinc (Zn), Cadmium (Cd) and Nickel (Ni) in Vertisol and Alluvial soils

Ethylendiamintetraacetic acid (EDTA) is persistent in the environment. The presence of EDTA in soil may alter the mobility and transport of Zn, Cd and Ni in soils because of the formation of water soluble chelates, thus increasing the potential for metal pollution of natural waters. Mobility of metals is related to their extractability. To investigate metal extractability affected by EDTA, Zn, Cd and Ni were added to Vertisol and Alluvial soil at rates of 50, 2 and 5 mg kg^-1, respectively. Both natural and metal amended soils were treated with Na₂EDTA at rates of 0; 0.2 and 0.5 mg kg^-1. After five months of incubation soil samples were extracted with 0.1 N HCl, 0.005 M DTPA + 0.01 M CaCl₂ + 0.1 M TEA (0.005 M Diethylenetriaminepentaacetic acid + 0.01 M Calcium cloride + 0.1 M Triethanolamine) and 1 M Mg(NO₃)₂, the latter of which extracts the exchangeable from of metald (Zn, Cd and Ni).

According to experiment results, Zn, Cd and Ni in all extraction increased with increasing rates of EDTA in the natural and metal amended soils.     

Mobilization of Cu and Zn in contaminated soil by nitrilotriacetic acid

Batch and upflow column leaching experiments were used to evaluate the nature and extent of Cu and Zn solubilization from contaminated soil by nitrilotriacetic acid (NTA) in 0.025 M NaClO₄. In batch soil suspensions, NTA levels of 10^?5 to 10^?3 M substantially promoted Cu and Zn release from the metal-enriched soil. The ability of NTA to enhance Cu and Zn solubility decreased with increasing solution acidity probably due to competitive binding of NTA by protons and Fe released by hydrous oxide dissolution. However, in the pH range typically encountered in northeastern U.S. soils, soluble metal levels were nearly constant for a given NTA concentration. Leaching soil columns with NTA solutions enhanced Cu release more than Zn, as the enrichment ratio (cumulative metal leached by NTA compared to the 0.025 M NaClO₄ control leachate) after 85 pore volumes displacements was 23.6 and 4.3 for Cu and Zn, respectively. While Cu release by 0.01 M CaCl₂ differed little from the control, 0.01 M CaCl₂ was substantially more effective than 10^?5 M NTA in displacing bound Zn. The data reflect different retention mechanisms for Cu and Zn in this soil.     

Soil solution concentration of Cd and Zn canbe predicted with a CaCl2 soil extract

Risk assessment of heavy metals in soil requires an estimate of the concentrations in the soil solution. In spite of the numerous studies on the distribution of Cd and Zn in soil, few measurements of the distribution coefficient in situ, K_d, have been reported. We determined the K_d of soils contaminated with Cd and Zn by measuring metal concentrations in the soil and in the soil solution and attempted to predict them from other soil variables by regression. Soil pH explained most of the variation in logK_d (R² = 0.55 for Cd and 0.70 for Zn). Introducing organic carbon content or cation exchange capacity (CEC) as second explanatory variable improved the prediction (R² = 0.67 for Cd and 0.72 for Zn), but these regression models, however, left more than a factor of 10 of uncertainty in the predicted K_d. This large degree of uncertainty may partly be due to the variable degree of metal fixation in contaminated soils. The labile metal content was measured by isotopic dilution (E value). The E value ranged from 18 to 92% of the total metal content for Cd and from 5 to 68% for Zn. The prediction of K_d improved when metals in solution were assumed to be in equilibrium with the labile metal pool instead of the total metal pool. It seems necessary therefore to discriminate between ‘labile’ and ‘fixed’ pools to predict K_d for Cd and Zn in field contaminated soils accurately. Dilute salt extracts (e.g. 0.01 m CaCl₂) can mimic soil solution and are unlikely to extract metals from the fixed pool. Concentrations of Cd and Zn in the soil solution were predicted from the concentrations of Cd and Zn in a 0.01 m CaCl₂ extract. These predictions were better correlated with the observations for field contaminated soils than the predictions based on the regression equations relating logK_d to soil properties (pH, CEC and organic C).     

Oral sealing using glue: a new method to distinguish between intestinal and dermal uptake of metals in earthworms

Earthworms may take up chemicals from soil and pore water, both through their skin (dermal) and by ingestion (oral). It remains unclear, however, what the relative importance of these pathways is. To assess bioavailability of pollutants in soil to earthworms, it is necessary that the contribution of each pathway is known. Lumbricus rubellus were sealed by means of medical histoacryl glue, to block ingestion of soil particles and pore water. For 6 d, these earthworms showed good survival and vitality and no soil ingestion was found. Equal metal uptake was found by sealed and unsealed earthworms exposed to an inert sand matrix continuously flushed with contaminated water. Therefore, pore water uptake via ingestion contributes little to metal accumulation. Uptake rates of Cd, Cu and Pb in sealed and unsealed earthworms exposed to two contaminated field soils were similar. Uptake and elimination kinetics of Zn were significantly lower in sealed earthworms exposed to one of the two field soils. Body concentrations of Cu and Pb could be completely attributed to the dermal route. For internal Cd and Zn concentrations, however, 0-17 and 21-30%, respectively, were derived from ingestion. It is concluded that for metals the dermal route is the uptake route of importance. The sealing method described here may be useful in a variety of earthworm nutrition and contamination-effect studies.     

The effect of Lumbricus rubellus and Lumbricus terrestris on zinc distribution and availability in artificial soil columns

This study investigated the impact of epigeic and (epi)anecic earthworms on the distribution and availability of zinc in the soil profile. Experiments were carried out with Lumbricus rubellus and Lumbricus terrestris in perspex columns (Ø 10 cm), filled with 20 to 23 cm non-polluted soil [organic matter 2%, clay 2.9%, pH 6.4 (0.01 M CaCl₂)], that was covered by a 3- to 5-cm layer of aged zinc-spiked soil (500 mg Zn/kg dry soil) and another 2 cm non-polluted soil on top. After 80 days, columns were sacrificed and sampled in a depth profile. Earthworm casts, deposited on top of the soil, were collected. Each sample was analyzed for total and 0.01 M CaCl₂-exchangeable zinc concentrations. L. rubellus did not go deeper than 3 cm into the soil and therefore no effect on zinc distribution in the soil could be detected. For L. terrestris, total zinc concentrations in the non-polluted layers were slightly but significantly higher in columns with earthworms, and so were the CaCl₂-exchangeable zinc concentrations in the polluted layers of these columns. Casts of L. terrestris collected from the soil surface showed higher total zinc concentrations than those from non-polluted soil. Casts were mainly placed on top of the soil. This study showed that these epigeic and (epi)anecic species have only a slight effect on zinc availability, and that deep burrowing species, like L. terrestris, are able to transport polluted soil from deeper layers to the soil surface.     

Regenwürmer als Bioindikatoren für Schwermetallbelastungen von Böden unter Freilandbedingungen

The use of earthworms in monitoring soil pollution by heavy metals Total heavy metal contents (HNO₃-soluble) and exchangeable fractions (Ca(NO₃)₂-soluble) of Pb, Zn and Cd were measured in soils, litter layers and earthworms (dry masses) from forest, arable and pasture sites in a transect of the main wind direction and varying distances (1.5, 5.4, 11.4, 15.6 km) to a lead smelter near Bad Ems, Germany. Additionally, cast materials of Lumbricus terrestris-individuals were collected from the surface of the pasture sites. In the observed area total soil contents of Pb and Cd exceeded the C-level and total contents of Zn the B-level of the “Netherland-list”. Heavy metal contents in soils and earthworms decreased with increasing distance to the smelter. Pb showed the best correlation. Correlation between total contents of Pb and Cd in soils and earthworms were significant (rs = 0.66; p < 0.05 and rs = 0.67; p < 0.01, respectively). The uptake of heavy metals by Lumbricus rubellus, L. terrestris and Aporrectodea caliginosa was metal specific rather than species specific with factors of accumulation being <1 (Pb), 2.7–7.6 (Zn) and 19.5–85.5 (Cd). The heavy metal contents of the observed cast materials signified the different transfer of elements from soil material via earthworm individuals to the faeces. In the cast materials the amounts of Pb were high and the amounts of Zn and Cd were low. This indicates a high accumulation rate for Zn and especially for Cd in the tissues of the observed earthworm individuals. The present data support the necessity of ecotoxicological threshold levels.     

Applicability of 0.01 M CaCl2 as a single extraction solution for the assessment of the nutrient status of soils and other diagnostic purposes

Abstract

The applicability of 0.01 M CaCl₂ solution as a single extraction agent for soils as a basis for fertilizer recommendation was tested on a variety of soils both from the Netherlands and from some tropical countries. Air‐dry soil samples were subjected to extraction with 0.01 M CaCl₂ and to several conventional extraction procedures, and the results were compared. In the soil suspensions pH was measured, whereas in the extracts Na, K, Mg, P, different extractable N‐forms and Zn were measured. The values found in CaCl₂ extracts are discussed in relation to results of other extraction procedures and as to their potential value in soil quality assessment. It is concluded that a single extraction procedure with 0.01 M CaCl₂ can be applied for fertilizer recommendation purposes. The possibility of determining different extractable N‐forms (NH₄, NO₃, soluble organic N) significantly enhances the value of the method in predicting the N‐fertilizer needs. Furthermore it was found that the concentration of Zn in 0.01 M CaCl₂ extracts was a good indicator of phytotoxicity in a polluted area. Additional advantages of this extraction are low costs, simplicity and repro‐ducibility.     

Uptake pathways and toxicity of Cd and Zn in the earthworm Eisenia fetida

The uptake of Cd and Zn by the earthworm Eisenia fetida was determined at varying Ca concentrations and with pre-exposure to different metabolic inhibitors in simulated soil solutions over a 48-h period. The presence of Ca in the solution had complex actions on Cd uptake. At a low Cd concentration of 0.1 μM, Ca (0.1-1 mM) slightly but significantly stimulated Cd uptake, whereas it inhibited Cd uptake at a higher Cd level (10 μM). Pre-exposure to a Ca-channel blocker (Lanthanum) inhibited Cd uptake over a relatively wide range of Cd concentrations, but not Zn uptake, suggesting that the uptake of Zn was not exerted at a Ca channel. N-ethylmaleimide, which specifically binds to sulfhydryl groups, inhibited Zn uptake at both 0.1 and 10 μM, implying that the transport of Zn is carrier-mediated by proteins or other SH-containing compounds. The present study provides evidence that the mechanisms of Cd and Zn uptake in earthworms are pharmacologically different, although both metals have similar geochemical and environmental properties. After 24 h pre-exposure to a sublethal concentration (1.0 μM) of Cd, Zn toxicity for E. fetida was significantly reduced with 48-h LC₅₀ values (with 95% confidence interval) increasing from 145 (105-201) to 316 (212-470) μM Zn. Pre-exposure to Zn (1.0 μM) did not, however, affect Cd toxicity. Pre-exposure to Cd significantly changed the subcellular Zn distribution, with a decreasing fraction of Zn associated with Fraction B (associated with granules and cell membranes), which is believed to be most indicative of toxic pressure and an increased fraction associated with Fraction G (associated with cytosol). This most likely explains the observed Zn tolerance of E. fetida after low level Cd pre-exposure. These results help to understand the uptake mechanism and interactions of Zn and Cd in earthworms.     

Characterization of soil heavy metal pools in paddy fields in Taiwan: chemical extraction and solid-solution partitioning

Background, aim, and scope  Ongoing industrialization has resulted in an accumulation of metals like Cd, Cu, Cr, Ni, Zn, and Pb in paddy fields across Southeast Asia. Risks of metals in soils depend on soil properties and the availability of metals in soil. At present, however, limited information is available on how to measure or predict the directly available fraction of metals in paddy soils. Here, the distribution of Cd, Cu, Cr, Ni, Zn, and Pb in 19 paddy fields among the total, reactive, and directly available pools was measured using recently developed concepts for aerated soils. Solid-solution partitioning models have been derived to predict the directly available metal pool. Such models are proven to be useful for risk assessment and to derive soil quality standards for aerated soils. Material and methods  Soil samples (0–25 cm) were taken from 19 paddy fields from five different communities in Taiwan in 2005 and 2006. Each field was subdivided into 60 to 108 plots resulting in a database of approximately 3,200 individual soil samples. Total (Aqua Regia (AR)), reactive (0.43 M HNO₃, 0.1 M HCl, and 0.05 M EDTA), and directly available metal pools (0.01 M CaCl₂) were determined. Solid-solution partitioning models were derived by multiple linear regressions using an extended Freundlich equation using the reactive metal pool, pH, and the cation exchange capacity (CEC). The influence of Zn on metal partitioning and differences between both sampling events (May/November) were evaluated. Results  Total metals contents range from background levels to levels in excess of current soil quality standards for arable land. Between 3% (Cr) and 30% (Cd) of all samples exceed present soil quality standards based on extraction with AR. Total metal levels decreased with an increasing distance from the irrigation water inlet. The reactive metal pool relative to the total metal content is increased in the order Cr << Ni = Zn < Pb < Cu < Cd and ranged from less than 10% for Cr to more than 70% for Cd. Despite frequent redox cycles, Cd, Pb, and Cu appear to remain rather reactive. The methods to determine the reactive metal pool in soils yield comparable results, although the 0.43 M HNO₃ extraction is slightly stronger than HCl and EDTA. The close correlation between these methods suggests that they release similar fractions from soils, probably those reversibly sorbed to soil organic matter (SOM) and clay. The average directly available pool ranged from less than 1% for Cu, Pb, and Cr to 10% for Ni, Zn, and Cd when compared to the reactive metal pool. For Cd, Ni, Zn, and to a lesser extent for Cu and Pb, solid-solution partitioning models were able to explain up to 93% (Cd) of the observed variation in the directly available metal pool. CaCl₂ extractable Zn increased the directly available pool for Ni, Cd, and Cu but not that of Pb and Cr. In the polluted soils, the directly available pool was higher in November compared to that in May. Differences in temperature, rainfall, and changes in soil properties such as pH are likely to contribute to the differences observed within the year. The solid-solution partitioning model failed to explain the variation in the directly available Cr pool, probably because Cr is present in precipitates rather than being adsorbed onto SOM and clay. Despite obvious differences in parent material, source of pollution, climate, and land use, solid-solution partitioning of Cd in paddy fields studied here was similar to that in soils from Belgium and the Netherlands. Discussion  To assess risks of metals in soils, both analytical procedures as well as models are needed. The three methods tested here to determine the reactive metal pool are highly correlated and either of these can be used. The directly available pool was predicted most accurately by the 0.43 M HNO₃ method. The similarity of metal partitioning in paddy soils compared to well-drained soils suggests that changing redox conditions in paddy fields have a limited effect on the geochemical behavior of metals like Cd, Ni, and Zn. Small but significant differences in the directly available metal pool during the year suggest that redox cycles as well as differences in rainfall and temperature affect the size of the directly available metal pool. The large observed spatial heterogeneity of contaminant levels requires ample attention in the setup of soil monitoring programs. Conclusions  The directly available pool (0.01 M CaCl₂) of Cd, Zn, and Ni in paddy fields can be described well by an extended Freundlich model. For Cu and Pb, more information on dissolved organic carbon is needed to obtain a more accurate estimate of the directly available pool. Recommendations and perspectives  Soil testing protocols and models used in risk assessment consider the availability of pollutants rather than the total metal content. Results from extensive testing indicate that approaches developed for nontropical regions can be applied in paddy fields as well for metals like Cd, Ni, and Zn. This study shows that the chemical behavior under drained conditions in paddy fields is comparable to that observed in soils across the European Union, which allows regions with large scale soil pollution including Taiwan to apply such concepts to derive meaningful experimental protocols and models to assess risks of metals in soils.     

Effects of earthworms on decomposition and metal availability in contaminated soil: Microcosm studies of populations with different exposure histories

Population-specific differences in the responses of earthworms to simultaneous exposure to Cu and Zn were studied in microcosm experiments. Two populations of Aporrectodea caliginosa tuberculata (Eisen) with different metal exposure histories were chosen for the studies. Microcosms were prepared containing either uncontaminated soil or soils with low or high combined Cu/Zn -concentrations (79/139 or 178/311 mg kg⁻¹ dry mass of soil, respectively). Earthworms from each population were introduced to the microcosm treatments with some microcosms serving as controls without earthworms. One series of microcosms was destructively sampled after 16 weeks incubation in a climate chamber. Survival, growth, reproduction and decomposition by earthworms in each treatment were measured. An additional microcosm series was sampled for soil and earthworm measurements at four weeks intervals to determine temporal changes in the availability of metals in the soils and their accumulation into earthworms. Cu and Zn were sequentially extracted from the soil samples of both microcosm series to estimate mobility and availability of the metals in the soil. Earthworms with long-term exposure history to metal-contaminated soil seemed to tolerate higher soil metal concentrations than earthworms without earlier exposure. Both earthworms and metals affected soil respiration (CO₂ production) and nitrogen mineralization. In addition, earthworms seemed to decrease the mobility and bioavailability of metals in the soil through their burrowing activity.     

Oxidation and Removal of 1,2,4-Trichlorobenzene using Sodium Persulfate in a Sorption-Desorption Experiment

Peat soils with a gradient of naturally high Cd and Zn (up to 190 and 70,000,mg/kg, respectively) were sampled at several depths from a wetland overlying Zn-rich dolomitic bedrock. Total concentrations of Zn, Cd and S were generally much higher in the seasonally water-saturated subsoils than at the surface. Leaching studies with intact soil columns showed the subsoils generally have a greater tendency to release Zn, Cd and S than the topsoils. Zn and Cd leaching were correlated to sulfate dissolution, with 6 successive leaching events removing up to 4% and 13% of the total Zn and S, respectively, from the most metal-rich subsoils. Relative leaching losses were less from the surface soils, not exceeding 1% and 3% of total Zn and S. Because Zn was relatively more soluble and extractable by 0.01,M CaCl₂ than Cd, Zn/Cd ratios in column leachates and field-sampled groundwater were higher than the soil Zn/Cd ratios. Consequently, the potential for loss of Zn from the soil by leaching was higher than that of Cd, particularly from the subsoil. Nevertheless, some soil layers of the profile were enriched in total Zn relative to Cd, indicated by Zn/Cd ratios well above that of the Cd-rich sphalerite in the parent dolomitic rock. This enrichment may be explained by historical migration and re-immobilization of Zn as sulfides. The low solubility of Cd in the peats despite high total Cd suggests preferential immobilization of this metal by organic sulfur or sulfide.     

Availability of Cd,Ni and Zn to Ryegrass in Sewage Sludge-Treated Soils at Different Temperatures

A pot experiment to compare the availability of Cd, Ni and Znto ryegrass (Lolium perenne L.) was conducted at 15 and 25 °C. For this purpose, three ratesof sewage sludge (0, 10 and 50 t ha^-1) were applied in aloamy sand (LS) and a clay loam (CL). Heavy metal availabilityassessed by soil extractions with 0.05 M CaCl₂ and the organic matter content were monitored during a period of twoyears, while uptake by ryegrass was monitored over one year after addition of the sludge. The concentrations of Cd and Ni in both the ryegrass and the soil extracts increased significantly, during the first year, especially at 50 t ha^-1. However, in the second year metal availability reached a plateau. During the first year, in the ryegrass Znconcentrations did not show an increase, but in the soil CaCl₂-extracted Zn increased. During the same period,the organic matter content decreased rapidly, especially at25 °C, in the first year and much more slowly in thesecond, giving a total decrease of 16%. Temperature had a marked effect on metal availability; both soil extracts andplant samples from the 25 °C treatment had greater concentrations of Cd, Ni and Zn than those at 15 °C. This may be attributed to the organic matter, which decomposedmore rapidly at 25 °C. Moreover, soil-plant transfercoefficients (Tc) of the metals were significantly higher at 25 °C than at 15 °C, with Cd showing the greatest difference, followed in decreasing order by Zn and Ni.     

Earthworm-mycorrhiza interaction on Cd uptake and growth of ryegrass

The effects of inoculation of earthworms and arbuscular mycorrhiza separately, and in combination, on Cd uptake and growth of ryegrass were studied in soils contaminated with 0, 5, 10, 20 mg of Cd kg⁻¹ soil. Both earthworms and mycorrhiza were able to survive in all the treatments with added Cd. Earthworm activity significantly increased mycorrhizal infection rate of root and ryegrass shoot biomass. Earthworm activity decreased soil pH by about 0.2 units, and enhanced root Cd concentration and ryegrass Cd uptake. Mycorrhiza inoculation increased shoot and root Cd concentration substantially, and at the highest dosage of 20 mg Cd kg⁻¹ decreased biomass of ryegrass. Inoculation of both earthworms and mycorrhiza increased ryegrass shoot Cd uptake at low Cd concentrations (5 and 10 mg Cd kg⁻¹ soil), when compared with inoculation of earthworms or mycorrhiza alone. In conclusion, earthworm, mycorrhiza and their interaction may have a potential role in elevating phytoextraction efficiency in low to medium level metal contaminated soil.     

Soil Zinc Fractions Determine Inhibition of Nitrification

The thresholds for heavy metal loading of soils that do not impair microbially mediated processes need to be determined. This study assessed the limits for Zn in relation to the inhibition of nitrification. Different Zn concentrations in soil were achieved by spiking with ZnCl₂ or from the long-term application of biosolids. Potentially available Zn was evaluated by fractionation using sequential extractions with water, 0.05 M CaCl₂, and 0.11 M CH₃COOH solutions at a soil:liquid ratio 1:40. pH (0.01 M CaCl₂) and electrical conductivity were measured in all treatments. It was not possible to obtain very clear cutoffs of Zn concentrations based on nitrification inhibition, which could apply to different soils. However, water-extractable Zn fraction was best related to nitrification inhibition limits when soils were considered together. Three approximate ranges of nitrification inhibition were identified: 0 to 0.125 mg Zn L^-1 (no inhibition); 0.125to 0.5 mg Zn L^-1 (partial inhibition); and over 0.5 mg Zn L^-1 (complete inhibition). For the same Zn loading, the water-soluble fraction was much lower in biosolid-amended soils than in the spiked ones. Consequently, biosolid-amended soils were more resilient toward Zn contamination. Weakly bounded Zn was a more reliable index than stronger bound fractions to determine common thresholds with respect to nitrification inhibition in the soils studied. Therefore, we suggest maximum Zn loadings based on the amounts in the soil solution rather than on total inputs or total content.     

Modelling trace metal extractability and solubility in French forest soils by using soil properties

Soil/solution partitioning of trace metals (TM: Cd, Co, Cr, Cu, Ni, Sb, Pb and Zn) has been investigated in six French forest sites that have been subjected to TM atmospheric inputs. Soil profiles have been sampled and analysed for major soil properties, and CaCl₂‐extractable and total metal content. Metal concentrations (expressed on a molar basis) in soil (total), in CaCl₂ extracts and soil solution collected monthly from fresh soil by centrifugation, were in the order: Cr > Zn > Ni > Cu > Pb > Co > Sb > Cd , Zn > Cu > Pb = Ni > Co > Cd > Cr and Zn > Ni > Cu > Pb > Co > Cr > Cd > Sb , respectively. Metal extractability and solubility were predicted by using soil properties. Soil pH was the most significant property in predicting metal partitioning, but TM behaviour differed between acid and non‐acid soils. TM extractability was predicted significantly by soil pH for pH < 6, and by soil pH and Fe content for all soil conditions. Total metal concentration in soil solution was predicted well by soil pH and organic carbon content for Cd, Co, Cr, Ni and Zn, by Fe content for Cu, Cr, Ni, Pb and Sb and total soil metal content for Cu, Cr, Ni, Pb and Sb, with a better prediction for acidic conditions (pH < 6). At more alkaline pH conditions, solute concentrations of Cu, Cr, Sb and Pb were larger than predicted by the pH relationship, as a consequence of association with Fe colloids and complexing with dissolved organic carbon. Metal speciation in soil solutions determined by WHAM‐VI indicated that free metal ion (FMI) concentration was significantly related to soil pH for all pH conditions. The FMI concentrations of Cu and Zn were well predicted by pH alone, Pb by pH and Fe content and Cd, Co and Ni by soil pH and organic carbon content. Differences between soluble total metal and FMI concentrations were particularly large for pH < 6. This should be taken into account for risk and critical load assessment in the case of terrestrial ecosystems.     

植物吸取修复及钝化处理对后茬水稻镉吸收的影响

采集湖南湘潭县某地镉(Cd)污染酸性农田土壤及其经伴矿景天分别吸取修复两季和三季后的土壤,采用盆栽试验研究了经伴矿景天修复及钝化改良与否对土壤pH、有效态Cd、Zn以及水稻生长和稻米Cd、Zn浓度的影响。结果表明:未改良的处理,随着修复次数的增加,土壤pH显著降低,降低幅度为0.26~0.38个单位;且修复两季、三季土壤CaCl_2提取态Cd浓度较未修复土壤分别降低19.4%、24.0%;修复后土壤种植水稻品种W184,其糙米中Cd浓度显著降低,但依然超标;修复三季土壤种植低积累水稻品种IRA7190,其糙米中Cd由0.47 mg/kg降为0.03 mg/kg。施加钝化剂海泡石和石灰(10 g/kg+1 g/kg)后,修复两季、三季土壤的pH显著升高,较未施钝化剂处理土壤pH分别提高0.95、0.72;土壤CaCl_2提取态Cd浓度分别降低79.8%、79.5%;修复两季、三季土壤上水稻W184糙米的Cd浓度与未施加钝化剂相比,分别降低27.3%、44.4%,均降至国家食品安全限值0.2 mg/kg以下;无论是否添加钝化剂,伴矿景天吸取修复三季的土壤上水稻IRA7190糙米中Cd浓度均仅0.03 mg/kg。