Evaluation of tests to assess the quality of mine-contaminated soils

An acid metal-contaminated soil from the Aljustrel mining area (a pyrite mine located in SW Portugal in the Iberian Pyrite Belt) was subjected to chemical characterisation and total metal quantification (Cd, Cr, Cu, Ni, Pb and Zn). Water-soluble metals were determined and a sequential extraction procedure was used to investigate metal speciation. Two bioavailable metal fractions were determined: a mobile fraction and a mobilisable fraction. Soil ecotoxicity was studied using a battery of bioassays: plant growth test and seed germination with cress (Lepidium sativum L.), earthworm (Eisenia fetida) mortality, E. fetida avoidance behaviour, luminescent inhibition of Vibrio fischeri and Daphnia magna immobilisation. Although the total content of Cu, Zn and Pb in the soil was large (362, 245 and 1,250 mg/kg dry matter, respectively), these metals were mostly structurally bound (87% for Cu, 81% for Zn and 89% for Pb) and, therefore, scarcely bioavailable. Nonetheless, the D. magna immobilization test using soil leachate showed an EC₅₀ (48 h) of 36.3% (v/v), and the luminescent inhibition of V. fischeri presented an EC₂₀ (15 min) of 45.2% and an EC₂₀ (30 min) of 10.7% (v/v), suggesting a considerable toxic effect. In the direct exposure bioassays, E. fetida avoided the mine soil at the highest concentrations (50%, 75% and 100% v/v). At the same soil concentrations, cress showed negligible growth. The results suggest the need to use a battery of toxicity tests, in conjunction with chemical methods, in order to assess the quality of mine-contaminated soils correctly.     

Relationship between plant biodiversity and heavy metal bioavailability in grasslands overlying an abandoned mine

Abandoned metal mines in the Sierra de Guadarrama, Madrid, Spain, are often located in areas of high ecological value. This is true of an abandoned barium mine situated in the heart of a bird sanctuary. Today the area sustains grasslands, interspersed with oakwood formations of Quercus ilex and heywood scrub (Retama sphaerocarpa L.), used by cattle, sheep and wild animals. Our study was designed to establish a relationship between the plant biodiversity of these grasslands and the bioavailability of heavy metals in the topsoil layer of this abandoned mine. We conducted soil chemical analyses and performed a greenhouse evaluation of the effects of different soil heavy metal concentrations on biodiversity. The greenhouse bioassays were run for 6 months using soil samples obtained from the mine polluted with heavy metals (Cu, Zn, Pb and Cd) and from a control pasture. Soil heavy metal and Na concentrations, along with the pH, had intense negative effects on plant biodiversity, as determined through changes in the Shannon index and species richness. Numbers of grasses, legumes, and composites were reduced, whilst other species (including ruderals) were affected to a lesser extent. Zinc had the greatest effect on biodiversity, followed by Cd and Cu. When we compared the sensitivity of the biodiversity indicators to the different metal content variables, pseudototal metal concentrations determined by X-ray fluorescence (XRF) were the most sensitive, followed by available and soluble metal contents. Worse correlations between biodiversity variables and metal variables were shown by pseudototal contents obtained by plasma emission spectroscopy (ICP-OES). Our results highlight the importance of using as many different indicators as possible to reliably assess the response shown by plants to heavy metal soil pollution.     

雄烯二酮在我国典型土壤中的吸附特性

采用批吸附室内模拟实验研究了雄烯二酮在我国红壤、潮土、黑土3种典型土壤中的吸附特征,以及牛粪溶解态有机质(DOM)对土壤吸附雄烯二酮的影响。结果表明,雄烯二酮在土壤中吸附动力学符合Elovch方程(R20.89),热力学特征可通过Freundlich等温吸附方程(R20.83)描述,土壤对雄烯二酮的吸附呈非线性吸附特征,其中潮土吸附等温线的非线性最强(n=0.37);吸附系数K f介于6.0~20.2,并与有机质含量呈显著正相关(p0.05)。雄烯二酮浓度较低时,共存牛粪DOM抑制其在土壤表面的吸附作用。研究认为,有机质是土壤吸附雄烯二酮的主要组分,共存牛粪DOM可促进雄烯二酮向地表水和地下水的迁移。     

The effects of soil properties and temperature on the adsorption isotherms of lead on some temperate and semiarid surface soils of Iran

Sorption of metal ions by soil and clay minerals is a complex process involving different mechanisms, and controlled by different variables that can interact. The aim of this work was to study the retention mechanisms of Pb ions on different soil samples. Surface soils were sampled from Guilan and Hamadan provinces in north and northwest of Iran with temperate and semiarid climates. The adsorption isotherms of Pb on the soils have been studied at 15, 27 and 37°C. The adsorption data for different soils were fitted into Langmuir and Freundlich models. Temperate soil samples had higher clay content, cation exchange capacity, dichromate (oxidable) organic carbon, total Kjeldahl-nitrogen, biological activity, amorphous and crystalline Fe and Al, but semiarid soil samples had higher sand content, pH, equivalent calcium carbonate, available P and K. Lead adsorption data obtained from semiarid soils against those obtained from temperate soils were better fitted in both Langmuir and Freundlich models. Langmuir constants Q ₀ for Pb adsorption in semiarid soils were considerably lower than those for Pb adsorption in temperate soils. However, the binding energy (K _L) of Pb and Freundlich constant n were higher for data of semiarid soils. The effect of temperature on the Pb adsorption was positive especially in temperate soils; however, soil properties had higher effects on Pb adsorption.     

Influence of fertilizer and sewage sludge compost on yield and heavy metal accumulation by lettuce grown in urban soils

Previous research has demonstrated that many urban soils are enriched in Pb, Cd and Zn. Culture of vegetable crops in these soils could allow transfer of potentially toxic metals to foods. Tanya lettuce (Lactuca sativa L.) was grown in pots of five urban garden soils and one control agricultural soil to assess the effect of urban-soil metal enrichment, and the effect of soil amendments, on heavy metal uptake by garden vegetables. The amendments included NPK fertilizer, limestone, Ca(H₂PO₄)₂, and two rates of limed sewage sludge compost. Soil Cd ranged from 0.08 to 9.6 mg kg^–1; soil Zn from 38 to 3490 mg kg^–1; and soil Pb from 12 to 5210 mg kg^–1. Lettuce yield on the urban garden soils was as great as or greater than that on the control soil. Lettuce Cd, Zn and Pb concentrations increased from 0.65, 23, and 2.2 mg kg^–1 dry matter in the control soil to as high as 3.53, 422 and 37.0 mg kg^–1 on the metal-rich urban garden soils. Adding limestone or limed sewage sludge compost raised soil pH and significantly reduced lettuce Cd and Zn, while phosphate fertilizer lowered soil pH and had little effect on Zn but increased Cd concentration in lettuce. Urban garden soils caused a significant increase in lettuce leaf Pb concentration, especially on the highest Pb soil. Adding NPK fertilizer, phosphate, or sludge compost to two high Pb soils lowered lettuce Pb concentration, but adding limestone generally did not. On normally fertilized soils, Pb uptake by lettuce was not exceptionally high until soil Pb substantially exceeded 500 mg kg^–1. Comparing garden vegetables and soil as potential sources of Pb risk to children, it is clear that the risk is greater through ingestion of soil or dust than through ingestion of garden vegetables grown on the soil. Urban dwellers should obtain soil metal analyses before selecting garden locations to reduce Pb risk to their children.     

Distribution and mobility of metals in agricultural soils near a copper smelter in South China

The distribution and mobility of heavy metals in the paddy soils surrounding a copper smelting plant in south China was investigated. We assessed the degree of metal contamination using an index of geoaccumulation. The metals were divided into two groups: (1) Cu, Zn, Pb and Cd, whose concentrations were heavily affected by anthropogenic inputs, and (2) Ni, Co and Cr, which were mainly of geochemical origin. Concentrations of Cu, Cd, Zn, and Pb in the polluted soils were higher than the Chinese soil quality criteria. The chemical partitioning patterns of Pb, Zn and Cu indicated that Pb was largely associated with the residual and NH₂OH HCl extractable fractions. In contrast, Cd was predominantly associated with the MgCl₂ extractable fraction. A large proportion of Cu was bound to the acidic H₂O₂ extractable fractions, while Zn was predominantly found in the residual phase. The fraction of mobile species, which potentially is the most harmful to the environment, was found to be elevated compared to unpolluted soils in which heavy metals are more strongly bound to the matrix. The mobility of the metals was studied by water extraction using a modification of Tessier’s procedure, and the order of mobility was Zn > Cd > Cu  > Pb.     

重金属积累对土壤酶活性的影响

研究了华北平原某铅冶炼厂附近农田33个土壤样品中重金属积累对土壤酶活性的影响。结果表明,样品中Pb和Cd全量的平均值分别为144和5.59mg·kg-1,DTPA态Pb和Cd含量平均值分别为54.1和0.964mg·kg-1,均超过了未污染农田潮土的正常范围,而Cu、Ni和Zn的有效性和全量与未污染土壤接近;土壤过氧化氢酶活性与DTPA态Pb和Cd含量、全Pb含量均呈显著的负线性关系(P<0.01);与磷酸酶和脲酶相比,土壤脱氢酶活性更易受到土壤中Pb和Cd积累的影响;随DTPA-Ni含量增加,土壤蛋白酶和碱性磷酸酶活性增加(P<0.1);土壤脲酶活性与重金属全量或有效态重金属含量无显著相关性(P>0.1)。以上结果说明,利用土壤过氧化氢酶和脱氢酶活性能够表征基本性质较为一致的土壤中重金属污染程度;与重金属全量相比,有效态重金属对土壤酶活性影响更大。     

Chelator-induced bioextraction of heavy metals from artificially contaminated soil by mushroom (Coprinus comatus)

This study investigated the potential use of chelator-induced bioextraction of heavy metals from soil by Coprinus comatus in a pot experiment. Two production waves of the mushroom were obtained to determine biomass and metal concentration. The application of ethylenediaminetetraacetic acid (EDTA) or nitrilotriacetate (NTA) slightly inhibited the growth of C. comatus, but significantly enhanced the accumulation of heavy metals in fruiting bodies compared with the control. The highest concentrations of Pb, Cu and Cd reached 900.60, 783.61 and 23.64 mg·kg^?1 in a single pot, respectively. However, application of citric acid (CA) had no effect on metal uptake. Moreover, chelators applied to soil after fructification increased the dry biomass and metal concentration in fruiting bodies compared with those applied before sowing mycelia. EDTA was more efficient for inducing metal uptake by C. comatus than NTA or CA, and split applications of EDTA after fructification resulted in the highest total metal uptake by mushroom, i.e. 19.08±2.84, 17.57±0.69 and 0.55±0.06 mg for Pb, Cu and Cd, respectively, which were 130, 12 and 5 times values obtained with the control. Interestingly, many mushrooms turned blue after soil had been treated with chelator, indicating that these mushrooms are rich in Cu.     

Phytoavailability and potential transfer of Pb from a salt-affected soil to Atriplex verucifera,Salicornia europaea and Chenopodium album

The phytoavailability and potential transfer of Pb to Atriplex verucifera, Salicornia europaea and Chenopodium album in two calcareous soils with different salinity/sodicity were compared. The soils were spiked with 0, 250, 500 and 1000 mg Pb kg^?1 soil. Plant shoots were harvested and analysed for total Pb after they had been grown in the contaminated soils. Visual MINTEQ 3.0 was used to calculate the speciation of soluble Pb in the experimental soils. Results showed that although the concentrations of 1 M NH₄NO₃-extractable Pb were relatively similar, speciation of Pb in the soils were not the same. Salicornia europea was found to be the most salinity/sodicity-tolerant plant. When the plants were grown in non-saline soil, the Pb tolerance of the three plants was as follows: A. verucifera > C. album >S. europea, whereas in saline (sodic) soil, Pb tolerance was in the order S. europea > C. album > A. verucifera. Lead phytotoxicity to A. verucifera and C. album was higher in the saline soil, whereas for S. europea, Pb toxicity was higher in the non-saline soil. It could be concluded that the phytoavailability of Pb and its interactions with plants are widely dependent on soil salinity level and type of plant.     

Heavy metals in soils and crops in Southeast Asia

In a reconnaissance soil geochemical and plant survey undertaken to study the heavy metal uptake by major food crops in Malaysia, 241 soils were analysed for cation exchange capacity (CEC), organic carbon (C), pH, electrical conductivity (EC) and available phosphorus (P) using appropriate procedures. These soils were also analysed for arsenic (As), cadmium (Cd), cobalt (Co), chromium (Cr), copper (Cu), mercury (Hg), nickel (Ni), lead (Pb) and zinc (Zn) using aqua regia digestion, together with 180 plant samples using nitric acid digestion. Regression analysis between the edible plant part and aqua regia soluble soil As, Cd, Cr, Cu, Hg, Ni, Pb and Zn concentrations sampled throughout Peninsular Malaysia, indicated a positive relationship for Pb in all the plants sampled in the survey (R ² = 0.195, p < 0.001), for Ni in corn (R ² = 0.649, p < 0.005), for Cu in chilli (R ² = 0.344, p < 0.010) and for Zn in chilli (R ² = 0.501, p < 0.001). Principal component analysis of the soil data suggested that concentrations of Co, Ni, Pb and Zn were strongly correlated with concentrations of Al and Fe, which is suggestive of evidence of background variations due to changes in soil mineralogy. Thus the evidence for widespread contamination of soils by these elements through agricultural activities is not strong. Chromium was correlated with soil pH and EC, Na, S, and Ca while Hg was not correlated with any of these components, suggesting diffuse pollution by aerial deposition. However As, Cd, Cu were strongly associated with organic matter and available and aqua regia soluble soil P, which we attribute to inputs in agricultural fertilisers and soil organic amendments (e.g. manures, composts).     

4种草对铅锌尾矿污染土壤重金属的抗性与吸收特性

盆栽试验的结果表明,高羊毛、早熟禾、黑麦草、紫花苜蓿在纯尾矿污染土壤或经处理的尾矿污染土壤上都能生长,但在处理的土壤上生长的植物长势明显优于对照,其中紫花苜蓿的生物量所受影响比其他几种草坪草更大,说明其重金属抗性低于其他几种植物。单位面积上 4 种植物体内重金属质量分数高低均为 w(Zn)>w(Pb)>w(Cu)>w(Cd),但每种植物对 Cd、Pb、Zn 和 Cu 的吸收质量分数和分布均不相同,一般为根系质量分数大于茎叶。加入改良剂(CaCO3)和有机肥(菜枯)使生长在铅锌尾矿污染土壤上的 4 种草坪草生物量显著增加,植物体中的 Cd、Pb、Zn 质量分数下降,但 Cu 质量分数反而上升,结果单位面积上草坪草吸收各重金属元素的量均有所增加,可见利用改良措施与草坪草相结合的方法来修复重金属污染土壤具有可行性。     

Soil pollution by trace metals derived from animal feed and manure in the Bursa region of Turkey

The Bursa region of Turkey has important agricultural production areas. Animal producers use agricultural fields in this region for disposal of manure. Therefore, in this study the concentrations of the seven trace metals Zn, Mn, Cu, Ni, Cr, Pb, and Cd in 324 animal feed and manure samples from three dairy cattle, three laying hens farms, and three broiler farms have been determined. The average concentrations in dairy cattle manure were 130 (Zn), 150 (Mn), 4.2 (Cu), 6.8 (Ni), 44 (Cr), 0.8 (Pb), and 0.09 (Cd) mg kg^?1 dry weight; for laying hens manure 240 (Zn), 190 (Mn), 0.63 (Cu), 3.8 (Ni), 30 (Cr), 0.55 (Pb), and 0.12 (Cd) mg kg^?1 dry weight; and for broiler manure 240 (Zn), 280 (Mn), 1.4 (Cu), 3.8 (Ni), 35 (Cr), 3.4 (Pb), and 0.16 (Cd) mg kg^?1 dry weight. The calculated trace metal loading rate indicated that manure application might pose a potential risk to agricultural fields according to the current soil protection regulations of Turkey.     

Effects of carbon nanotube and biochar on bioavailability of Pb,Cu and Sb in multi-metal contaminated soil

This study examined the effects of carbon nanotube and biochar on the bioavailability of Pb, Cu and Sb in the shooting range soils for developing low-cost remediation technology. Commercially available multi-walled carbon nanotube (MWCNT) and biochar pyrolyzed from soybean stover at 300 °C (BC) at 0.5, 1 and 2.5% (w w^?1) were used to remediate the contaminated soil in an incubation experiment. Both DTPA (bioavailable) and TCLP (leaching) extraction procedures were used to compare the metal/loid availability and leaching by the amendments in soil. The addition of BC was more effective in immobilizing mobile Pb and Cu in the soil than that in MWCNT. The BC reduced the concentrations of Pb and Cu in the soil by 17.6 and 16.2%, respectively. However, both MWCNTs and BC increased Sb bioavailability by 1.4-fold and 1.6-fold, respectively, in DTPA extraction, compared to the control. The toxicity characteristic leaching procedure (TCLP) test showed that the leachability of Pb in the soil amended with 2.5% MWCNT was 1.3-fold higher than that the unamended soil, whereas the BC at 2.5% decreased the TCLP-extractable Pb by 19.2%. Precipitation and adsorption via electrostatic and π–π electron donor–acceptor interactions were postulated to be involved in the interactions of Pb and Cu with surfaces of the BC in the amended soils, whereas ion exchange mechanisms might be involved in the immobilization of Cu in the MWCNT-amended soils. The application of BC derived from soybean stover can be a low-cost technology for simultaneously immobilizing bioavailable Pb and Cu in the shooting range soils; however, neither of amendments was effective in Sb immobilization.     

Determination of the levels of selected metals in seeds,flowers and fruits of medicinal plants used for tapeworm treatment in Ethiopia

The level of accumulation of selected essential and non-essential metals, namely; Ca, Cu, Fe, Zn, Mn, Cd, Pb, and Cr have been investigated in the seeds, fruits, and flowers of some medicinal plants utilized for tapeworm treatment in Ethiopia and their respective soil samples. These include seed of Cucurbita maxima (Duba), fruit of Embelia abyssinica (Ankoko), flowers of Hagenia abyssinica (Kosso), and fruits of Rosa abyssinica (Kega) and their respective soil samples. A wet digestion procedure with a mixture of conc. HNO₃ and HClO₄ for the plant samples and a mixture of conc. HNO₃, HCl, and H₂O₂ for soil samples were used to solubilize the metals. Ca (1280–12,670?mg?kg^?1) was the predominant metal followed by Fe (104–420?mg?kg^?1), and Zn (18–185?mg?kg^?1) in all the plant materials except for Hagenia abyssinica flower from Hirna in which Mn (16–42?mg?kg^?1) followed by Fe. Among the non-essential toxic metals, Pb was not detected in Cucurbita maxima of Boji, Gedo and Hirna origins and in Rosa abyssinica of Hirna site. Similarly, Cr was not detected in Rosa abyssinica fruits of Boji and Gedo sites. The sampled soils were found to be between strongly acidic to weakly basic (pH: 4.7–7.1). In the soil samples, Ca (8528–18,900?mg?kg^?1) was the most abundant metal followed by Fe (417–912?mg?kg^?1), Zn (155–588?mg?kg^?1), Mn (54–220?mg?kg^?1), Cr (21–105. mg?kg^?1), Cu (11–58?mg?kg^?1), Pb (13–32?mg?kg^?1) and Cd (2.8–4.8?mg?kg^?1). The levels of most of the metals determined in the medicinal plants and the respective soil samples are in good agreement with those reported in the literature and the standards set for the soil by various legislative authorities.     

Introducing a new metal accumulator plant and the evaluation of its ability in removing heavy metals

A field study was conducted in a dried waste pool of a lead (Pb) mine in Arak (Iran) to find the accumulator plant(s) and to evaluate the amount of metal bioaccumulation in the root and shoot portion of the naturally growing vegetation. Concentrations of heavy metals were determined both in the soil and the plants that were grown in the dried waste pool. The concentrations of total Cu, Zn, Pb, and Ni in the waste pool were found to be higher than the natural soil and the toxic levels. The results showed that six dominant vegetations, namely, Centaurea virgata, Eleagnum angustifolia, Euphorbia macroclada, Gundelia tournefortii, Reseda lutea, and Scariola orientalis accumulated heavy metals. Based on the results, it was concluded that E. macroclada belonging to Euphorbiaceae is the best Pb accumulator and also a good accumulator for Zn, Cu, and Ni. The bioaccumulation ability of E. macroclada was evaluated in experimental pots. The study showed that the amount of heavy metals in polluted soils decreased several times during two years of phytoremediation. The accumulation of metal in the root, leaves, and shoot portions of E. macroclada varied significantly, but all the concentrations were within the toxic limits. Based on the obtained data, E. macroclada is an effective accumulator plant for soil detoxification and phytoremediation in critical conditions.     

Biosolids application affects the competitive sorption and lability of cadmium,copper, nickel,lead, and zinc in fluvial and calcareous soils

The objective of this research was to investigate the effects of biosolids on the competitive sorption and lability of the sorbed Cd, Cu, Ni, Pb, and Zn in fluvial and calcareous soils. Competitive sorption isotherms were developed, and the lability of these metals was estimated by DTPA extraction following their sorption. Sorption of all metals was higher in the fluvial than in the calcareous soil. Sorption of Cu and Pb was stronger than that of Cd, Ni, and Zn in all soils. Biosolids application (2.5%) reduced the sorption of all metals especially Cu and Pb (28–43%) in both soils (especially the calcareous soil) at the lower added metal concentrations (50 and 100 mg L^?1). However, it increased the sorption of all metals especially Pb and Cu in both soils (especially the calcareous soil; 15.5-fold for Cu) at the higher added concentrations (250 and 300 mg L^?1). Nickel showed the highest lability followed by Cd, Zn, and Pb in both soils. Biosolids increased the lability of the sorbed Ni in the fluvial soils at all added concentrations and the lability of Cd, Pb, and Zn at 50 mg L^?1, but decreased the lability of Cd, Pb, and Zn at 250 and 300 mg L^?1 in both soils. We conclude that at low loading rate (e.g., 50 mg L^?1) biosolids treatment might increase the lability and environmental risk of Cd, Cu, Pb, and Zn. However, at high loading rate (e.g., 300 mg L^?1) biosolids may be used as an immobilizing agent for Cd, Cu, Pb, Zn and mobilizing agent for Ni.     

Remediation rates and translocation of heavy metals from contaminated soil through Parthenium hysterophorus

The potential translocation of heavy metals by Parthenium hysterophorus over 30 and 90 days and its effect on biomass, chlorophyll content and photosynthetic activity were studied on 0, 10, 25, 50 and 100% fly-ash-amended soil (FAS). The results showed a decrease in chlorophyll content and photosynthetic area on exposure to 50–100% FAS. Heavy metal reduction was in the order Pb>Cd>Zn>Fe>according to accumulation trends. The plant exhibited good biomass growth on exposure to 25–50% FAS, but this decreased at>100% FAS. Heavy metal concentrations in P. hysterophorus after 90 days of the experiment were in the order Fe>Zn>Cu>Pb>Cd>Ni. Parthenium hysterophorus was suitable for translocating Fe, Zn and Cu based on translocation factors (TF=1.5, 1.3 and 1.05), but was more efficient for Pb, Ni and Cd (TF=8.5, 4.3 and 3.3). Plant uptake of Pb, Ni and Cd was high, whereas translocation of Fe, Zn and Cu was poor. These results indicated that P. hysterophorus can efficiently reduce heavy metal pollution in soil.     

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 (3.54–7.91), 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 of 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 earthworm tissues into cytosolic and pellet digesis 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.

     

Bioavailability of trace metals in brownfield soils in an urban area in the UK

Thirty-two brownfield sites from the city of Wolverhampton were selected from those with a former industrial use, wasteland or areas adjacent to industrial processes. Samples (<2 mm powdered soil fraction) were analysed, using inductively coupled plasma–atomic emission spectrometry (ICP–AES) for 20 elements. Loss on ignition and pH were also determined. A five-step chemical sequential extraction technique was carried out. Single leach extraction with 0.12 M hydrochloric acid of Pb, Cu and Zn in soil was determined as a first approximation of the bioavailability in the human stomach. Some of the sites were found to have high concentrations of the potentially toxic elements Pb, Zn, Cu and Ni. The partitioning of metals showed a high variability, however a number of trends were determined. The majority of Zn was partitioned into the least chemically stable phases (steps 1, 2 and 3). The majority of Cu was associated with the organic phase (step 4) and the majority of Ni was fractionated into the residue phase (step 5). The majority of Pb was associated with the residue fraction (step 5) followed by Fe–Mn oxide fraction (step 3). The variability reflects the heterogeneous and complex nature of metal speciation in urban soils with varied historic histories. There was a strong inverse linear relationship between the metals Ni, Zn and Pb in the readily exchangeable phase (step 1) and soil pH, significant at P < 0.01 level. There was a significant increase (P < 0.05) in the partitioning of Cu, Ni and Zn into step 4 (the organic phase) in soils with a higher organic carbon content (estimated by loss on ignition). Copper was highly partitioned into step 4 as it has a strong association with organics in soil but this phase was not important for the partitioning of Ni or Zn. The fractionation of Ni, Cu and Zn increased significantly in step 3 when the total metal concentration increases (P < 0.01). The Fe–Mn oxide fraction becomes more important in soils elevated in these metals, possibly due to the scavenging of metals by oxides. Cu and Pb extracted by HCl was statistically similar to the sum of the metals in steps 1 to 4 (P < 0.01) and HCl available Zn was statistically similar to the sum of Zn in steps 1 to 3 (P < 0.01). Step 4 (the organic phase) was not an important phase for Zn, so it was concluded that any Cu, Zn and Pb present in soil in a nonresidue phase would be potentially available for uptake into the human system once soil has been ingested.     

Trace metals accumulation in soil irrigated with polluted water and assessment of human health risk from vegetable consumption in Bangladesh

Trace metals accumulation in soil irrigated with polluted water and human health risk from vegetable consumption was assessed based on the data available in the literature on metals pollution of water, soil, sediment and vegetables from the cites of Bangladesh. The quantitative data on metal concentrations, their contamination levels and their pollution sources have not been systematically gathered and studied so far. The data on metal concentrations, sources, contamination levels, sample collection and analytical tools used were collected, compared and discussed. The USEPA-recommended method for health risk assessment was used to estimate human risk from vegetable consumption. Concentrations of metals in water were highly variable, and the mean concentrations of Cd, Cr, Cu and As in water were found to be higher than the FAO irrigation water quality standard. In most cases, mean concentrations of metals in soil were higher than the Bangladesh background value. Based on geoaccumulation index (I _geo) values, soils of Dhaka city are considered as highly contaminated. The I _geo shows Cd, As, Cu, Ni, Pb and Cr contamination of agricultural soils and sediments of the cities all over the Bangladesh. Polluted water irrigation and agrochemicals are identified as dominant sources of metals in agricultural soils. Vegetable contamination by metals poses both non-carcinogenic and carcinogenic risks to the public. Based on the results of the pollution and health risk assessments, Cd, As, Cr, Cu, Pb and Ni are identified as the priority control metals and the Dhaka city is recommended as the priority control city. This study provides quantitative evidence demonstrating the critical need for strengthened wastewater discharge regulations in order to protect residents from heavy metal discharges into the environment.