Distribution, speciation and availability of antimony (Sb) in soils and terrestrial plants from an active Sb mining area

Here, we present one of the first studies investigating the mobility, solubility and the speciation-dependent in-situ bioaccumulation of antimony (Sb) in an active Sb mining area (Xikuangshan, China). Total Sb concentrations in soils are high (527-11,798 mg kg⁻¹), and all soils, including those taken from a paddy field and a vegetable garden, show a high bioavailable Sb fraction (6.3-748 mg kg⁻¹), dominated by Sb(V). Elevated concentrations in native plant species (109-4029 mg kg⁻¹) underpin this. Both chemical equilibrium studies and XANES data suggest the presence of Ca[Sb(OH)₆]₂, controlling Sb solubility. A very close relationship was found between the citric acid extractable Sb in plants and water or sulfate extractable Sb in soil, indicating that citric acid extractable Sb content in plants may be a better predictor for bioavailable Sb in soil than total acid digestible Sb plant content.     

Toxicity and metabolism of copper pyrithione and its degradation product, 2,2'-dipyridyldisulfide in a marine polychaete

We conducted acute toxicity tests and sediment toxicity tests for copper pyrithione (CuPT) and a metal pyrithione degradation product, 2,2′-dipyridyldisulfide [(PS)₂], using a marine polychaete Perinereis nuntia. The acute toxicity tests yielded 14-d LC₅₀ concentrations for CuPT and (PS)₂ of 0.06 mg L⁻¹ and 7.9 mg L⁻¹, respectively. Sediment toxicity tests resulted in 14-d LC₅₀ concentrations for CuPT and (PS)₂ of 1.1 mg kg⁻¹ dry wt. and 14 mg kg⁻¹ dry wt., respectively. In addition to mortality, sediment avoidance behavior and decreases in animal growth rate were observed; growth rate was the most susceptible endpoint in the sediment toxicity tests of both toxicants. Thus, we propose lowest observed effect concentrations of 0.3 mg kg⁻¹ dry wt. and 0.2 mg kg⁻¹ dry wt. for CuPT and (PS)₂, respectively, and no observed effect concentrations of 0.1 mg kg⁻¹ dry wt. for both CuPT and (PS)₂. The difference in the toxicity values between CuPT and (PS)₂ observed in the acute toxicity test was greater than the difference in these values in the sediment toxicity test, and we attribute this to (PS)₂ being more hydrophilic than CuPT. In addition to the toxicity tests, we analyzed conjugation activity of several polychaete enzymes to the toxicants and marked activity of palmitoyl coenzyme-A:biocides acyltransferase and UDP-glucuronosyl transferase was observed.     

Soil pollution assessment and identification of hyperaccumulating plants in chromated copper arsenate (CCA) contaminated sites, Korea

In recent decades, heavy metal contamination in soil adjacent to chromated copper arsenate (CCA) treated wood has received increasing attention. This study was conducted to determine the pollution level (PL) based on the concentrations of Cr, Cu and As in soils and to evaluate the remediative capacity of native plant species grown in the CCA contaminated site, Gangwon Province, Korea. The pollution index (PI), integrated pollution index (IPI), bioaccumulation factors (BAF_shoots and BAF_roots) and translocation factor (TF) were determined to ensure soil contamination and phytoremediation availability. The 19 soil samples from 10 locations possibly contaminated with Cr, Cu and As were collected. The concentrations of Cr, Cu and As in the soil samples ranged from 50.56-94.13 mg kg⁻¹, 27.78-120.83 mg kg⁻¹, and 0.13-9.43 mg kg⁻¹, respectively. Generally, the metal concentrations decreased as the distance between the CCA-treated wood structure and sampling point increased. For investigating phytoremediative capacity, the 19 native plant species were also collected in the same area with soil samples. Our results showed that only one plant species of Iris ensata, which presented the highest accumulations of Cr (1120 mg kg⁻¹) in its shoot, was identified as a hyperaccumulator. Moreover, the relatively higher values of BAF_shoot (3.23-22.10) were observed for Typha orientalis, Iris ensata and Scirpus radicans Schk, suggesting that these plant species might be applicable for selective metal extraction from the soils. For phytostabilization, the 15 plant species with BAF_root values > 1 and TF values < 1 were suitable; however, Typha orientalis was the best for Cr.     

Mechanisms of enhanced mobilisation of trace metals by anionic surfactants in soil

Long-term applications of small concentrations of surfactants in soil via wastewater irrigation or pesticide application may enhance trace metal solubility. Mechanisms by which anionic surfactants (Aerosol 22, SDS and Biopower) affect trace metal solubility were assessed using batch, incubation and column experiments. In batch experiments on seven soils, the concentrations of Cu, Cd, Ni and Zn in the dissolved fraction of soils increased up to 100-fold at the high application rates, but increased less than 1.5-fold below the critical micelle concentration. Dissolved metal concentrations were less than 20% affected by surfactants in long-term incubations (70 days) up to the largest dose of 200 mg C kg⁻¹ soil. Leaching soil columns with A22 (100-1000 mg C L⁻¹) under unsaturated conditions increased trace metal concentrations in the leachates 2-4 fold over the control. Correlation analysis and speciation modelling showed that the increased solubility of metals upon surfactant application was more related to the solubilisation of soil organic matter from soil than to complexation of the metals with the surfactant. Organic matter from soil was solubilised in response to a decrease of solution Ca²⁺ as a result of Ca-surfactant precipitation. At environmentally relevant concentrations, surfactant application is unlikely to have a significant effect on trace metal mobility.     

Cadmium accumulation in and tolerance of rice (Oryza sativa L.) varieties with different rates of radial oxygen loss

Cadmium (Cd) uptake and tolerance were investigated among 20 rice cultivars based on a field experiment (1.2 mg Cd kg⁻¹ in soil) and a soil pot trial (control, 100 mg Cd kg⁻¹), and rates of radial oxygen loss (ROL) were measured under a deoxygenated solution. Significant differences were found among the cultivars in: (1) brown rice Cd concentrations (0.11-0.29 mg kg⁻¹) in a field soil, (2) grain Cd tolerance (34-113%) and concentrations (2.1-6.5 mg kg⁻¹) in a pot trial, and (3) rates of ROL (15-31 mmol O₂ kg⁻¹ root d.w. h⁻¹). Target hazard quotients were calculated for the field experiment to assess potential Cd risk. Significant negative relationships were found between rates of ROL and concentrations of Cd in brown rice or straw under field and greenhouse conditions, indicating that rice cultivars with higher rates of ROL had higher capacities for limiting the transfer of Cd to rice and straw.     

Accumulation of mercury and methylmercury by mushrooms and earthworms from forest soils

Accumulation of total and methyl-Hg by mushrooms and earthworms was studied in thirty-four natural forest soils strongly varying in soil physico-chemical characteristics. Tissue Hg concentrations of both receptors did hardly correlate with Hg concentrations in soil. Both total and methyl-Hg concentrations in tissues were species-specific and dependent on the ecological groups of receptor. Methyl-Hg was low accounting for less than 5 and 8% of total Hg in tissues of mushrooms and earthworms, respectively, but with four times higher concentrations in earthworms than mushrooms. Total Hg concentrations in mushrooms averaged 0.96 mg Hg kg⁻¹ dw whereas litter decomposing mushrooms showed highest total Hg and methyl-Hg concentrations. Earthworms contained similar Hg concentrations (1.04 mg Hg kg⁻¹ dw) whereas endogeic earthworms accumulated highest amounts of Hg and methyl-Hg.     

Arsenic contamination and potential health risk implications at an abandoned tungsten mine, southern China

In an extensive environmental study, field samples, including soil, water, rice, vegetable, fish, human hair and urine, were collected at an abandoned tungsten mine in Shantou City, southern China. Results showed that arsenic (As) concentration in agricultural soils ranged from 3.5 to 935 mg kg⁻¹ with the mean value of 129 mg kg⁻¹. In addition, As concentration reached up to 325 μg L⁻¹ in the groundwater, and the maximum As concentration in local food were 1.09, 2.38 and 0.60 mg kg⁻¹ for brown rice, vegetable and fish samples, respectively, suggesting the local water resource and food have been severely contaminated with As. Health impact monitoring data revealed that As concentrations in hair and urine samples were up to 2.92 mg kg⁻¹ and 164 μg L⁻¹, respectively, indicating a potential health risk among the local residents. Effective measurements should be implemented to protect the local community from the As contamination in the environment.     

Correlation of foliar MT2b expression with Cd and Zn concentrations in hybrid aspen (Populus tremula × tremuloides) grown in contaminated soil

Metal uptake and its effect on foliar metallothionein 2b (MT2b) mRNA levels were studied in hybrid aspen (Populus tremula × tremuloides) in field conditions. The trees were planted on a site contaminated with several metals, including cadmium (mean 5.1 mg kg⁻¹), chromium (80 mg kg⁻¹), copper (180 mg kg⁻¹), nickel (81 mg kg⁻¹), vanadium (240 mg kg⁻¹) and zinc (520 mg kg⁻¹). Of the ten trace elements analyzed, only Cd and Zn accumulated in the leaves with maximal foliar concentrations of 35 and 2400 mg kg⁻¹ (dry weight), respectively. There was a strong correlation between Cd and Zn concentrations and bioaccumulation factors (concentration in plant/soil) in the leaves, branches and roots, suggesting similar transport mechanisms for these two metals. The levels of MT2b correlated with Cd and Zn concentrations in the leaves, demonstrating that increased MT2b expression is one of the responses of hybrid aspen to chronic metal exposure.     

Influence of humified organic matter on copper behavior in acid polluted soils

The main purpose of this work was to identify the role of soil humic acids (HAs) in controlling the behavior of Cu(II) in vineyard soils by exploring the relationship between the chemical and binding properties of HA fractions and those of soil as a whole. The study was conducted on soils with a sandy loam texture, pH 4.3-5.0, a carbon content of 12.4-41.0 g kg⁻¹ and Cu concentrations from 11 to 666 mg kg⁻¹. The metal complexing capacity of HA extracts obtained from the soils ranged from 0.69 to 1.02 mol kg⁻¹, and the stability constants for the metal ion-HA complexes formed, log K, from 5.07 to 5.36. Organic matter-quality related characteristics had little influence on Cu adsorption in acid soils, especially if compared with pH, the degree of Cu saturation and the amount of soil organic matter.     

Prediction of Cadmium uptake by brown rice and derivation of soil–plant transfer models to improve soil protection guidelines

Cadmium (Cd) levels in paddy fields across Taiwan have increased due to emission from industry. To ensure the production of rice that meets food quality standards, predictive models or suitable soil tests are needed to evaluate the quality of soils to be used for rice cropping. Levels of Cd in soil and rice grains were measured in 19 paddy fields across the western plains in Taiwan. Cadmium levels in soil range from less than 0.1 mg kg^?1 to 30 mg kg^?1. Measured Cd levels in brown rice were predicted very well (R² > 0.8) based on Cd and Zinc in a 0.01 M CaCl₂ extract or a soil–plant transfer model using the reactive soil Cd content, pH, and cation exchange capacity. In contrast to current soil quality standards used in Taiwan, such models are effective in identifying soils where Cd in rice will exceed food quality standards.     

Influence of activated charcoal amendment to contaminated soil on dieldrin and nutrient uptake by cucumbers

Activated charcoal (AC) amendments have been suggested as a promising, cost-effective method to immobilize organic contaminants in soil. We performed pot experiments over two years with cucumber (Cucumis sativus L.) grown in agricultural soil with 0.07 mg kg^?1 of weathered dieldrin and 0, 200, 400, and 800 mg AC per kg soil. Dieldrin fresh weight concentrations in cucumber fruits were significantly reduced from 0.012 to an average of 0.004 mg kg^?1, and total uptake from 2 to 1 μg in the 800 mg kg^?1 AC treatment compared to the untreated soil. The treatment effects differed considerably between the two years, due to different meteorological conditions. AC soil treatments did neither affect the availability of nutrients to the cucumber plants nor their yield (total fruit wet weight per pot). Thus, some important prerequisites for the successful application of AC amendments to immobilize organic pollutants in agricultural soils can be considered fulfilled.     

Strategies for enhancing the phytoremediation of cadmium-contaminated agricultural soils by Solanum nigrum L

Field trials contribute practical information towards the development of phytoremediation strategies that cannot be provided by laboratory tests. We conducted field experiments utilizing the Cd hyperaccumulator plant Solanum nigrum L., on farmland contaminated with 1.91 mg kg⁻¹ Cd in the soil. Our study showed that S. nigrum has a relatively high biomass. Planting density had a significant effect on the plant biomass and thus on overall Cd accumulation. For double harvesting, an optimal cutting position influenced the amount of Cd extracted from soils. Double cropping was found to significantly increase the amount of Cd extracted by S. nigrum. Fertilizing had no significant effect on plant biomass or on the Cd remediation of the soil over the short-term period. Our study indicates that S. nigrum can accumulate Cd from soils where the concentrations are relatively low, and thus has application for use in decontamination of slightly to moderately Cd-contaminated soil.     

Mercury in United Kingdom topsoils; concentrations, pools, and Critical Limit exceedances

The median total mercury concentration in 898 UK rural topsoils, sampled between 1998 and 2008, was 0.095 μg g⁻¹. Approximate adjustment for unreactive metal produced an estimate of 0.052 μg g⁻¹ for reactive Hg. The highest concentrations were in the north and west, where organic-rich soils with low bulk densities dominate, but the spatial pattern was quite different if soil Hg pools (mg m⁻²) were considered, the highest values being near to the industrial north of England and London. Possible toxic effects of Hg were best evaluated by comparison with soil Critical Limits expressed as ratios of Hg to soil organic matter, or soil solution Hg²⁺ concentrations, estimated by chemical speciation modelling. Only a few percent of the rural UK soils showed exceedance, and this also applied to rural soils from the whole of Europe. UK urban and industrial soils had higher Hg concentrations and more cases of exceedance.     

Amendment of arsenic and chromium polluted soil from wood preservation by iron residues from water treatment

An iron-rich water treatment residue (WTR) consisting mainly of ferrihydrite was used for immobilization of arsenic and chromium in a soil contaminated by wood preservatives. A leaching batch experiment was conducted using two soils, a highly contaminated soil (1033 mg kg⁻¹ As and 371 mg kg⁻¹ Cr) and slightly contaminated soil (225 mg kg⁻¹ As and 27 mg kg⁻¹ Cr). Compared to an untreated reference soil, amendment with 5% WTR reduced leaching in the highly contaminated soil by 91% for Cr and 98% for As. No aging effect was observed after 103 d. In a small field experiment, soil was mixed with 2.5% WTR in situ. Pore water was extracted during 3 years from the amended soil and a control site. Pore water arsenic concentrations in the amended soil were more than two orders of magnitude lower than in the control for the upper samplers. An increased release of arsenic was observed during winter in both fields, mostly in the deepest samplers. This is likely due to the formation of a pseudo-gley because of precipitation surplus. Stabilization of arsenic and chromium contaminated soil using WTR is a promising method but the transformation of ferrihydrite in soil proves a concern in case of waterlogged soils. Still the amendment minimized the leaching of arsenic, even in cases of seasonal releases.     

Triclosan affects the microbial community in simulated sewage-drain-field soil and slows down xenobiotic degradation

Effects of the common antibacterial agent triclosan on microbial communities and degradation of domestic xenobiotics were studied in simulated sewage-drain-field soil. Cultivable microbial populations decreased 22-fold in the presence of 4 mg kg⁻¹ of triclosan, and triclosan-resistant Pseudomonas strains were strongly enriched. Exposure to triclosan also changed the general metabolic profile (Ecoplate substrate profiling) and the general profile (T-RFLP) of the microbial community. Triclosan degradation was slow at all concentrations tested (0.33-81 mg kg⁻¹) during 50-days of incubation. Mineralization experiments (¹⁴C-tracers) and chemical analyses (LC-MS/MS) showed that the persistence of a linear alkylbenzene sulfonate (LAS) and a common analgesic (ibuprofen) increased with increasing triclosan concentrations (0.16-100 mg kg⁻¹). The largest effect was seen for LAS mineralization which was severely reduced by 0.16 mg kg⁻¹ of triclosan. Our findings indicate that environmentally realistic concentrations of triclosan may affect the efficiency of biodegradation in percolation systems.     

Organ-wise accumulation of fluoride in Prosopis juliflora and its potential for phytoremediation of fluoride contaminated soil

Fluoride (F) contamination is a global environmental problem, as there is no cure of fluorosis available yet. Prosopis juliflora is a leguminous perennial, phreatophyte tree, widely distributed in arid and semi-arid regions of world. It extensively grows in F endemic areas of Rajasthan (India) and has been known as a “green” solution to decontaminate cadmium, chromium and copper contaminated soils. This study aims to check the tolerance potential of P. juliflora to accumulate fluoride. For this work, P. juliflora seedlings were grown for 75 d on soilrite under five different concentrations of F viz., control, 25, 50, 75 and 100 mg NaF kg⁻¹. Organ-wise accumulation of F, bioaccumulation factor (BF), translocation factor (TF), growth ratio (GR) and F tolerance index (TI) were examined. Plant accumulated high amounts of F in roots. The organ-wise distribution showed an accumulation 4.41 mg kg⁻¹dw, 12.97 mg kg⁻¹dw and 16.75 mg kg⁻¹dw F, in stem, leaves and roots respectively. The results indicated significant translocation of F from root into aerial parts. The bioaccumulation and translocation factor values (>1.0) showed high accumulation efficiency and tolerance of P. juliflora to F. It is concluded that P. juliflora is a suitable candidate for phytoremediation purpose and can be explored further for the decontamination of F polluted soils.     

Susceptibility of epigeic earthworm Eisenia fetida to agricultural application of six insecticides

Ecotoxicological risks of agricultural application of six insecticides to soil organisms were evaluated by acute toxicity tests under laboratory condition following OECD guidelines using the epigeic earthworm Eisenia fetida as the test organism. The organochlorine insecticide endosulfan (LC₅₀ - 0.002 mg kg⁻¹) and the carbamate insecticides aldicarb (LC₅₀ - 9.42 mg kg⁻¹) and carbaryl (LC₅₀ - 14.81 mg kg⁻¹) were found ecologically most dangerous because LC₅₀ values of these insecticides were lower than the respective recommended agricultural dose (RAD). Although E. fetida was found highly susceptible to the pyrethroid insecticide cypermethrin (LC₅₀ - 0.054 mg kg⁻¹), the value was higher than its RAD. The organophosphate insecticides chlorpyrifos (LC₅₀ - 28.58 mg kg⁻¹), and monocrotophos (LC₅₀ - 39.75 mg kg⁻¹) were found less toxic and ecologically safe because the LC₅₀ values were much higher than their respective RAD.     

Impact of earthworms on trace element solubility in contaminated mine soils amended with green waste compost

The common practice of remediating metal contaminated mine soils with compost can reduce metal mobility and promote revegetation, but the effect of introduced or colonising earthworms on metal solubility is largely unknown. We amended soils from an As/Cu (1150 mgAs kg⁻¹ and 362 mgCu kg⁻¹) and Pb/Zn mine (4550 mgPb kg⁻¹ and 908 mgZn kg⁻¹) with 0, 5, 10, 15 and 20% compost and then introduced Lumbricus terrestris. Porewater was sampled and soil extracted with water to determine trace element solubility, pH and soluble organic carbon. Compost reduced Cu, Pb and Zn, but increased As solubility. Earthworms decreased water soluble Cu and As but increased Pb and Zn in porewater. The effect of the earthworms decreased with increasing compost amendment. The impact of the compost and the earthworms on metal solubility is explained by their effect on pH and soluble organic carbon and the environmental chemistry of each element.     

Influence of tidal regime on the distribution of trace metals in a contaminated tidal freshwater marsh soil colonized with common reed (Phragmites australis)

A historical input of trace metals into tidal marshes fringing the river Scheldt may be a cause for concern. Nevertheless, the specific physicochemical form, rather than the total concentration, determines the ecotoxicological risk of metals in the soil. In this study the effect of tidal regime on the distribution of trace metals in different compartments of the soil was investigated. As, Cd, Cu and Zn concentrations in sediment, pore water and in roots were determined along a depth profile. Total sediment metal concentrations were similar at different sites, reflecting pollution history. Pore water metal concentrations were generally higher under less flooded conditions (mean is (2.32 ± 0.08) × 10⁻³ mg Cd L⁻¹ and (1.53 ± 0.03) × 10⁻³ mg Cd L⁻¹). Metal concentrations associated with roots (mean is 202.47 ± 2.83 mg Cd kg⁻¹ and 69.39 ± 0.99 mg Cd kg⁻¹) were up to 10 times higher than sediment (mean is 20.48 ± 0.19 mg Cd kg⁻¹ and 20.42 ± 0.21 mg Cd kg⁻¹) metal concentrations and higher under dryer conditions. Despite high metal concentrations associated with roots, the major part of the metals in the marsh soil is still associated with the sediment as the overall biomass of roots is small compared to the sediment.     

Effects of petroleum contamination on soil microbial numbers, metabolic activity and urease activity

The influence of petroleum contamination on soil microbial activities was investigated in 13 soil samples from sites around an injection water well (Iw-1, 2, 3, 4) (total petroleum hydrocarbons (TPH): 7.5-78 mg kg⁻¹), an oil production well (Op-1, 2, 3, 4, 5) (TPH: 149-1110 mg kg⁻¹), and an oil spill accident well (Os-1, 2, 3, 4) (TPH: 4500-34 600 mg kg⁻¹). The growth rate constant (μ) of glucose stimulated organisms, determined by microcalorimetry, was higher in Iw soil samples than in Op and Os samples. Total cultivable bacteria and fungi and urease activity also decreased with increasing concentration of TPH. Total heat produced demonstrated that TPH at concentrations less than about 1 g kg⁻¹ soil stimulated anaerobic respiration. A positive correlation between TPH and soil organic matter (OM) and stimulation of fungi-bacteria-urease at low TPH doses suggested that TPH is bound to soil OM and slowly metabolized in Iw soils during OM consumption. These methods can be used to evaluate the potential of polluted soils to carry out self-bioremediation by metabolizing TPH.