Risk assessment of heavy metal pollution for detritivores in floodplain soils in the Biesbosch, The Netherlands, taking bioavailability into account

Floodplains of the European rivers Rhine and Meuse are heavily polluted. We investigated the risk of heavy metal pollution (Cd, Cu, Pb, Zn) for detritivores living in a floodplain area, the Biesbosch, the Netherlands, affected by these rivers. Total soil, pore water and 0.01 M CaCl(2) extractable concentrations and concentrations in plant leaves, earthworms, isopods and millipedes were measured in two sites and compared with literature data to assess possible risks. Based on total metal concentrations in soil, serious effects on detritivores were expected. However, 0.01 M CaCl(2) extractable, pore water and plant leaf concentrations were similar to metal concentrations found in unpolluted areas. Concentrations of Cu and Cd in earthworms and Cu in millipedes were higher in the Biesbosch than in animals from reference areas. All other measured concentrations of heavy metals in earthworms, isopods and millipedes were similar to the ones found in reference areas. Despite high total soil concentrations, effects of Zn, Cu, Pb and Cd pollution on isopods are therefore not expected, while millipedes may only be affected by Cu. Since Cu and Cd levels in earthworms were increased compared to animals in unpolluted soils, this faunal group seems to be most at risk. Given the engineering role of earthworms in ecosystems, effects on the ecological functioning of floodplain soils therefore cannot be excluded.     

Accumulation of heavy metals from polluted soils by the earthworm, Lumbricus rubellus: can laboratory exposure of 'control' worms reduce biomonitoring problems?

This paper compares the patterns of metal (Pb, Zn, Cd, Cu) accumulation in nine populations of the epigeic earthworm, Lumbricus rubellus, native on metalliferous soils, with the patterns of metal accumulation in batches of L. rubellus sampled from an uncontaminated site and maintained on the nine contaminated soils for 31 days under laboratory conditions. The primary findings were: (1) the Pb, Zn and Cd concentrations in the 'native' worms were significantly higher in most cases than in the 'introduced' worms; (2) multiple regression analyses indicated that the relationships between tissue and soil metal concentrations were similar for 'native' and 'introduced' worms; (3) high soil organic matter content reduced the bioavailability of Pb, but low pH increased Pb bioavailability. It was concluded that, although no phenotypic evidence of metal-tolerant ecotypes was obtained, the exposure of earthworms from uncontaminated soils to contaminated soils under laboratory conditions can provide meaningful integrative data concerning metal bioavailability in soils which, for biomonitoring purposes, often present formidable sampling problems.     

Earthworms as biological monitors of cadmium, copper, lead and zinc in metalliferous soils

Earthworms (Lumbricus rebellus and Dendrodrilus rubidus) were sampled from one uncontaminated and fifteen metal-contaminated sites. Significant positive correlations were found between the earthworm and 'total' (conc. nitric acid-extractable) soil Cd, Cu, Pb and Zn concentrations (data log1) transformed). The relationships were linear, and the accumulation patterns for both species were similar when a single metal was considered, even though there were species difference in mean metal concentrations. Generally, the earthworm Cd concentration exceeded that of the soil; by contrast, the worm Pb concentration was lower than the soil Pb concentration in all but one (acidic, low soil Ca) site. Our observations suggest that Cu and Zn accumulation may be physiologically regulated by both species. Total-soil Cd explained 82-86% of the variability (V2) in earthworm Cd concentration; 52-58% of worm Pb and worm Zn concentrations were explained by the total-soil concentrations of the respective metals. Total-soil Cu explained only 11-32% of the worm Cu concentration. The effect of soil pH, total Ca concentration, cation-exchange capacity (CEC) and organic carbon on metal accumulation by L. rubellus and D. rubidus was investigated by multiple regression analysis. Soil pH (coupled with CEC) and soil Ca had a major influence on Pb accumulation (V2 of worm Pb increased to 77-83%), and there was some evidence that Cd accumulation may be suppressed in extremely organic soils. The edaphic factors investigated had no effect on Cu or Zn accumulation by earthworms. In the context of biomonitoring, it is proposed that earthworms have a potential in a dual role: (1) as 'quantitative' monitors of total-soil metal concentrations (as shown for Cd); and (2) as estimators of 'ecologically significant' soil metal, integrating the effects of edaphic factors (as shown for Pb).     

The distribution and intracellular compartmentation of metals in the endogeic earthworm Aporrectodea caliginosa sampled from an unpolluted and a metal-contaminated site

The tissue distribution of Cd, Cu, Pb, Zn and Ca in the endogeic earthworm Aporrectodea caliginosa living in a non-polluted and a heavy metal polluted soil was investigated. The tissues of animals from the contaminated soil contained greater concentrations of Cd, Pb and Zn than the corresponding tissues of animals from the unpolluted soil. The greatest concentrations of Cd, Pb, Zn, and Ca were primarily accumulated within the posterior alimentary canal (PAC), a tissue fraction which contained the greatest proportion of the whole-worm burdens of the respective metals. Cu was distributed fairly evenly in the tissue fractions investigated. The pattern of accumulation for the 'heavy' metals is broadly similar to that for epigeic earthworms; in contrast, a different pattern of tissue accumulation was found for Ca. In animals from the uncontaminated site, the major elemental constituents of the chloragosomes were P, Ca, Zn and S. A significant positive correlation exists between P and Ca within the chloragosomal matrix. These intracellular vesicles are major foci for Pb and Zn accumulation within the PAC, with 'excess' metals associated with P ligands within the chloragosome matrix. The incorporation of Pb and Zn appears to involve the cationic displacement of Ca. Such compartmentation appears to prevent dissemination of large concentrations of these metals into other earthworm tissues, and may thus represent a detoxification strategy based on accumulative immobilization. No intracellular localization of Cd was identified in the study, although the Cd concentration in the metalliferous soils examined was not exceptionally high. The observations are discussed in the context of a contribution to enhanced understanding of metal ecotoxicology in earthworms by providing baseline data on a little investigated ecophysiological group of earthworms. Comparisons of metal distribution and mechanisms of metal sequestration are made with other ecophysiological groups of earthworms, and the significance of the findings to biomonitoring and toxicity-testing programmes is considered.     

Survival, Pb-uptake and behaviour of three species of earthworm in Pb treated soils determined using an OECD-style toxicity test and a soil avoidance test

Mature (clitellate) Eisenia andrei Bouché (ultra epigeic), Lumbricus rubellus Hoffmeister (epigeic), and Aporrectodea caliginosa (Savigny) (endogeic) earthworms were placed in soils treated with Pb(NO(3))(2) to have concentrations in the range 1,000 to 10,000 mg Pb kg(-1). After 28 days LC50(-95%confidence limit)(+95%confidence limit) values were E. andrei 5824(-361)(+898) mg Pb kg(-1), L. rubellus 2867(-193)(+145) mg Pb kg(-1) and A. caliginosa2747(-304)(+239) mg Pb kg(-1) and EC50s for weight change were E. andrei2841(-68)(+150) mg Pb kg(-1), L. rubellus1303(-201)(+240) mg Pb kg(-1) and A. caliginosa1208(-206)(+212) mg Pb kg(-1). At any given soil Pb concentration, Pb tissue concentrations after 28 days were the same for all three earthworm species. In a soil avoidance test there was no difference between the behaviour of the different species. The lower sensitivity to Pb exhibited by E. andrei is most likely due to physiological adaptations associated with the modes of life of the earthworms, and could have serious implications for the use of this earthworm as the species of choice in standard toxicological testing.     

Heavy metal concentrations in soil and earthworms in a floodplain grassland

We determined accumulated heavy metal concentrations (Cd, Pb, Cu, Zn) of earthworms in moderately contaminated floodplain soils. Both soil and mature earthworms were sampled before and after flooding and earthworm species were identified to understand species specific differences in bioconcentration. Accumulated metal concentrations in floodplain earthworms differed before and after flooding. Differences in uptake and elimination mechanisms, in food choice and living habitat of the different earthworm species and changes in speciation of the heavy metals are possible causes for this observation. Regression equations taken from literature, that relate metal accumulation by earthworms in floodplains as a function of metal concentration in soil, performed well when all species specific data were combined in an average accumulation, but did not address differences in accumulation between earthworm species.     

Impact of the earthworm Lumbricus terrestris (L.) on As, Cu, Pb and Zn mobility and speciation in contaminated soils

To assess the risks that contaminated soils pose to the environment properly a greater understanding of how soil biota influence the mobility of metal(loid)s in soils is required. Lumbricus terrestris L. were incubated in three soils contaminated with As, Cu, Pb and Zn. The concentration and speciation of metal(loid)s in pore waters and the mobility and partitioning in casts were compared with earthworm-free soil. Generally the concentrations of water extractable metal(loid)s in earthworm casts were greater than in earthworm-free soil. The impact of the earthworms on concentration and speciation in pore waters was soil and metal specific and could be explained either by earthworm induced changes in soil pH or soluble organic carbon. The mobilisation of metal(loid)s in the environment by earthworm activity may allow for leaching or uptake into biota.     

Linking biosensor responses to Cd, Cu and Zn partitioning in soils

Soils bind heavy metals according to fundamental physico-chemical parameters. Bioassays, using bacterial biosensors, were performed in pore waters extracted from 19 contrasting soils individually amended with Cd, Cu and Zn concentrations related to the EU Sewage Sludge Directive. The biosensors were responsive to pore waters extracted from Zn amended soils but less so to those of Cu and showed no toxicity to pore water Cd at these environmentally relevant amended concentrations. Across the range of soils, the solid-solution heavy metal partitioning coefficient (K(d)) decreased (p<0.01) with increasing amendments of Cu and Zn; Cu exhibited the highest K(d) values. Gompertz functions of Cu and Zn, K(d) values against luminescence explained the relationship between heavy metals and biosensors. Consequently, biosensors provide a link between biologically defined hazard assessments of metals and standard soil-metal physico-chemical parameters for determining critical metal loadings in soils.     

Influence of hydrological regime on pore water metal concentrations in a contaminated sediment-derived soil

Options for wetland creation or restoration might be limited because of the presence of contaminants in the soil. The influence of hydrological management on the pore water concentrations of Cd, Cr, Cu, Fe, Mn, Ni and Zn in the upper soil layer of a contaminated overbank sedimentation zone was investigated in a greenhouse experiment. Flooding conditions led to increased Fe, Mn, Ni and Cr concentrations and decreased Cd, Cu and Zn concentrations in the pore water of the upper soil layer. Keeping the soil at field capacity resulted in a low pore water concentration of Fe, Mn and Ni while the Cd, Cu, Cr and Zn concentrations increased. Alternating hydrological conditions caused metal concentrations in the pore water to fluctuate. Formation and re-oxidation of small amounts of sulphides appeared dominant in determining the mobility of Cd, Cu, and to a lesser extent Zn, while Ni behaviour was consistent with Fe/Mn oxidation and reduction. These effects were strongly dependent on the duration of the flooded periods. The shorter the flooded periods, the better the metal concentrations could be linked to the mobility of Ca in the pore water, which is attributed to a fluctuating CO(2) pressure.     

PB uptake by ecologically dissimilar earthworm (Lumbricidae) species near a lead smelter in south Finland

The number of species and individuals, and the total biomass of earthworms decreased with decreasing distance from a lead smelter in southern Finland, as the Pb load of the soil increased. In soils highly polluted with Pb significant interspecific differences were found in the Pb concentration and the Pb concentration factor of lumbricids, whereas in slightly Pb polluted 'control' soils there were no significant interspecific differences. Near the smelter, the Pb concentration of the endogeic Aporrectodea caliginosa was higher than in the epigeic Lumbricus rubellus and L. casteneus. Pb concentration factors of these three species were lower in the highly polluted soil than in the 'control' soil, indicating that they were able to regulate their Pb accumulation. Contradicting these field observations, of the worms from the 'control' soil but reared in highly Pb polluted soil for up to 70 days, the epigeic L. castaneus, L. rubellus and Dendrodrilus rubidus took up more Pb than did the endogeic A. caliginosa and A. rosea. They also accumulated more Pb during the rearing periods than their counterparts permanently living in the highly Pb polluted soil, indicating that besides interspecific differences in Pb accumulation there seem to be intraspecific differences as well. Acclimatization and/or genotype differences can underlie earthworms' adaptation to Pb polluted soil, where they may have dissimilar physiological pathways to cope with high soil Pb concentrations. The amount of Pb rendered available to a local food chain by a population of earthworms will depend on the ability of the worms to accumulate Pb in their tissues, which in turn, is a function of the population's history of Pb exposure. Species such as A. caligonosa, which accumulate and continuously withstand high Pb concentrations in their tissues, are most appropriate for biomonitoring.     

Metal accumulation in earthworms inhabiting floodplain soils

The main factors contributing to variation in metal concentrations in earthworms inhabiting floodplain soils were investigated in three floodplains differing in inundation frequency and vegetation type. Metal concentrations in epigeic earthworms showed larger seasonal variations than endogeic earthworms. Variation in internal levels between sampling intervals were largest in earthworms from floodplain sites frequently inundated. High and low frequency flooding did not result in consistent changes in internal metal concentrations. Vegetation types of the floodplains did not affect metal levels in Lumbricus rubellus, except for internal Cd levels, which were positively related to the presence of organic litter. Internal levels of most essential metals were higher in spring. In general, no clear patterns in metal uptake were found and repetition of the sampling campaign will probably yield different results.     

Relation between heavy metal concentrations in salt marsh plants and soil

The aim of the research reported here was to investigate the relation between heavy metal concentrations in salt marsh plants, extractability of the metals from soil and some soil characteristics. In April 1987, Spartina anglica and Aster tripolium plants and soil were collected from four salt marshes along the Dutch coast. The redox potential of the soil between the roots of the plants and at bare sites was measured. Soil samples were oven-dried and analyzed for chloride concentration, pH, fraction of soil particles smaller than 63 microm (f < 63 microm), loss on ignition (LOI) and ammonium acetate and hydrochloric acid extractable Cd, Cu and Zn concentrations. The roots and shoots of the plants were analyzed for Cd, Cu and Zn. Because drying of the soil prior to chemical analysis might have changed the chemical speciation of the metals, and therefore the outcome of the ammonium acetate extraction, a second survey was performed in October 1990. In this survey A. tripolium plants and soil were collected from two salt marshes. Fresh and matched oven-dried soil samples were analyzed for water, ammonium acetate and diethylene triaminepentaacetic acid (DTPA) extractable Cd, Cu and Zn concentrations. The soil samples were also analyzed for f < 63 microm, LOI and total (HNO(3)/HCl digestion) metal concentrations. Soil metal concentrations were correlated with LOI. Drying prior to analysis of the soil had a significant effect on the extractability of the metals with water, ammonium acetate or DTPA. Plant metal concentrations significantly correlated only with some extractable metal concentrations determined in dried soil samples. However, these correlations were not consistently better than with total metal concentrations in the soil. It was concluded that extractions of metals from soil with water, ammonium acetate or DTPA are not better predictors for metal concentrations in salt marsh plants than total metal concentrations, and that a major part of the variation in metal concentrations in the plants cannot be explained by variation in soil composition.     

Earthworm communities along a gradient of urbanization

Earthworms were studied at six sites along a gradient of urbanization and their relations with several soil abiotic factors were determined. Concentrations of heavy metals, calcium and magnesium in earthworms and in soils were measured by atomic absorption spectroscopy. Strong negative correlations were detected between earthworm density and soil concentrations of cadmium and magnesium. Earthworm biomass was negatively correlated with lead, copper and zinc, and positively correlated with the distance from the centre of the city. High concentrations of Cd and Zn (concentration factors 49 and 32) were accumulated by earthworms in contrast to those of Cu and Pb (2 and 1). Relations between worm and soil concentrations of heavy metals, Ca and Mg are discussed.     

Strategies of heavy metal uptake by three plant species growing near a metal smelter

Some higher plant species have developed heavy metal tolerance strategies which enable them to survive and reproduce in highly metal-contaminated soils. We have investigated such heavy metal uptake and accumulation strategies of two absolute metallophyte species (Armeria maritima ssp. halleri and Cardaminopsis halleri) and one pseudometallophyte (Agrostis tenuis) growing near a former metal smelter. Samples of plant parts and soil were analysed for Zn, Cd, Pb, and Cu. In soil, there were two dominant types of metal concentration gradients with depth. Under the absolute metallophytes, extremely high metal contents were measured in the surficial Ah horizon, followed by a strong decrease in the underlying soil horizons (L(11) and L(12)). Under the pseudometallophyte, metal concentrations in the Ah horizon were much lower and fewer differences were observed in metal concentrations among the Ah, L(11), and L(12) horizons. The concentrations of Zn, Cd, Pb, and Cu in Agrostis tenuis roots were greater than concentrations in leaves, indicating significant metal immobilisation by the roots. For C. halleri, Zn and Cd concentrations in leaves were >20,000 and >100 mg kg(-1), respectively, indicating hyperaccumulation of these elements. Armeria maritima ssp. halleri exhibited root concentrations of Pb and Cu that were 20 and 88 times greater, respectively, than those in green leaves, suggesting an exclusion strategy by metal immobilisation in roots. However, Zn, Cd, Pb, and Cu concentrations in brown leaves of Armeria maritima ssp. halleri were 3-8 times greater than in green leaves, suggesting a second strategy, i.e. detoxification mechanism by leaf fall.     

Speciation of Cd and Zn in contaminated soils assessed by DGT-DIFS, and WHAM/Model VI in relation to uptake by spinach and ryegrass

A pot experiment was carried out to investigate the impact of Cd and Zn extractability in soil and speciation in pore water of industrial contaminated soils, on metal concentration in a metal sensitive species like spinach (Spinacia oleracea) and a more metal tolerant species like Italian ryegrass (Lolium multiflorum). For chemical speciation of Cd and Zn in pore water, WHAM/Model VI version 6.0 was used. The DGT technique was used to determine the effective concentration, C(E), of Cd and Zn in soils. The free ion activity in pore water correlated well with the contents in plants, and there was a linear relationship between the C(E) values and the concentration of Cd and Zn in both spinach and ryegrass in the non-toxic range. However, the C(E) values usually overestimated the plant contents when plants, particularly the spinach plants, were subjected to toxic concentration in the pore water. Metal uptake decreased in plants affected by toxicity, whereas metal binding to the Chelex resin did not. Thus, we found no linear relationship between the C(E) and metal contents in spinach, whereas a linear relationship was found between C(E)-Zn and the Zn concentration in ryegrass (r2=0.96, p<0.001). For Cd in ryegrass this relationship was weak (r2=0.53, p=0.18). This study indicates that the transport of metals from labile metal pools to the DGT-resin is linearly related to plant uptake only when plants are growing well, and that the applicability of DGT as an indicator for plant uptake seems species dependent.     

人工湿地宽叶香蒲对重金属的累积与机理

宽叶香蒲(Typha latifolia L.)对环境胁迫具有较强的耐性。为了解宽叶香蒲对重金属的富集能力与耐性机理,通过野外调研,采集韶关凡口铅锌矿废水处理人工湿地中的宽叶香蒲与相应土壤样品,测定了土壤、植物的重金属总量与叶片亚细胞中重金属含量,分析了植物重金属含量与土壤重金属含量的相关性,并估算了宽叶香蒲地上部对重金属的提取量。土壤pH值在6.83~7.70之间,宽叶香蒲能有效降低土壤中的Cd、Pb、Zn、Cu和Mn的含量,对重金属的吸收主要受土壤重金属含量的影响,Pb和Cd的富集系数平均在0.5以上;除Fe外,叶片重金属主要分布在细胞壁和胞基质中。结果表明,宽叶香蒲是多种重金属的耐性植物,根系对重金属的富集与选择性向上运输、叶片细胞壁和胞基质对过量重金属的阻隔与结合作用是宽叶香蒲耐受重金属的重要机理。     

Use of sequential extraction to assess metal partitioning in soils

The state of heavy metal pollution and the mobility of Cd, Cu, Ni, Cr, Pb and Zn were studied in three texturally different agricultural soil profiles near a Cu-Ni smelter in Harjavalta, Finland. The pseudo-total concentrations were determined by an aqua regia procedure. Metals were also determined after division into four fractions by sequential extraction with (1) acetic acid (exchangeable and specifically adsorbed metals), (2) a reducing agent (bound to Fe/Mn hydroxides), (3) an oxidizing agent (bound to soil organic matter) and (4) aqua regia (bound to mineral structures). Fallout from the smelter has increased the concentrations of Cd, Cu and Ni in the topsoil, where 75-90% of Cd, 49-72% of Cu and 22-52% of Ni occurred in the first two fractions. Slight Pb and Zn pollution was evident as well. High proportions of mobile Cd, Cu and Ni also deeper in the sandy soil, closest to the smelter, indicated some downward movement of metals. The hydroxide-bound fraction of Pb dominated in almost all soils and horizons, while Ni, Cr and Zn mostly occurred in mineral structures. Aqua regia extraction is usefully supplemented with sequential extraction, particularly in less polluted soils and in soils that exhibit substantial textural differences within the profiles.     

Habitat type-based bioaccumulation and risk assessment of metal and As contamination in earthworms, beetles and woodlice

The present study investigated the contribution of environmental factors to the accumulation of As, Cd, Cu, Pb and Zn in earthworms, beetles and woodlice, and framed within an exposure assessment of the European hedgehog. Soil and invertebrate samples were collected in three distinct habitat types. Results showed habitat-specific differences in soil and invertebrate metal concentrations and bioaccumulation factors when normalized to soil metal concentration. Further multiple regression analysis showed residual variability (habitat differences) in bioaccumulation that could not be fully explained by differences in soil metal contamination, pH or organic carbon (OC). Therefore, the study demonstrated that in bioaccumulation studies involving terrestrial invertebrates or in risk assessment of metals, it is not sufficient to differentiate habitat types on general soil characteristics such as pH and/or OC alone. Furthermore, simple generic soil risk assessments for Cd and Cu showed that risk characterization was more accurate when performed in a habitat-specific way.     

Heavy metals in urban soils of East St. Louis, IL, Part I: Total concentration of heavy metals in soils

The city of East St. Louis, IL, has a history of abundant industrial activities including smelters of ferrous and non-ferrous metals, a coal-fired power plant, companies that produce organic and inorganic chemicals, and petroleum refineries. A protocol for soil analysis was developed to produce sufficient information on the extent of heavy metal contamination in East St. Louis soils. Soil cores representing every borough of East St. Louis were analyzed for heavy metals--As, Cd, Cu, Cr, Hg, Ni, Pb, Sb, Sn, and Zn. The topsoil contained heavy metal concentrations as high as 12.5 ppm Cd, 14,400 ppm Cu, ppm quantities of Hg, 1860 ppm Pb, 40 ppm Sb, 1130 ppm Sn, and 10,360 ppm Zn. Concentrations of Sb, Cu, and Cd were well correlated with Zn concentrations, suggesting a similar primary industrial source. In a sandy loam soil from a vacated rail depot near the bank of the Mississippi River, the metals were evenly distributed down to a 38-cm depth. The clay soils within a half-mile downwind of the Zn smelter and Cu products company contained elevated Cd (81 ppm), Cu (340 ppm), Pb (700 ppm), and Zn (6000 ppm) and displayed a systematic drop in concentration of these metals with depth. This study demonstrates the often high concentration of heavy metals heterogeneously distributed in the soil and provides baseline data for continuing studies of heavy metal soil leachability.