Comparison of a rhizosphere-based method with other one-step extraction methods for assessing the bioavailability of soil metals to wheat

There is no method recognized as a universal approach for evaluation of bioavailability of heavy metals in soil. Based on the simulation of the rhizosphere soil conditions and integration of the combined effects of root-soil interactions as a whole, a rhizosphere-based method has been proposed. Wet fresh rhizosphere soil was extracted by low-molecular-weight organic acids (LMWOAs) to fractionate metal fractions of soil pools, which were then correlated with the metal contents of wheat roots and shoots. The rhizosphere-based method was compared with other one-step extraction methods using DTPA, EDTA, CaCl2, and NaNO3 as extractants and the first step of the Community Bureau of Reference (BCR) method. Simple correlation and stepwise multiple regression analysis were used for the comparison. Simple correlation indicated that the extractable Cu, Zn, Cr, and Cd of soils by the rhizosphere-based method were significantly correlated with the metal contents of wheat roots. For DTPA, BCR1 and EDTA methods there was a relatively poor correlation between the extractable Cu, Zn and Cd of soil and metal contents of wheat roots. Stepwise multiple regression analysis revealed that the equation of the rhizosphere-based method was the simplest one, and no soil properties variables needed to be added. In contrast, the equations of other one-step extraction methods were more complicated, and soil properties variables needed to be entered. The most distinct feature of the rhizosphere-based method was that the recommended method was suitable for acidic, neutral and near alkaline soils. However, the DTPA and EDTA extraction methods were suitable for calcareous soils only-or-only for acidic soils. The CaCl2, and NaNO3 extraction methods were only suitable for exchangeable metals. In short, the rhizosphere-based method was the most robust approach for evaluation of bioavailability of heavy metals in soils to wheat.     

Toxicity and bioaccumulation of thallium in Hyalella azteca, with comparison to other metals and prediction of environmental impact

Thallium (Tl) is an extremely toxic but little studied metal. For Hyalella azteca exposed in Lake Ontario water, a 25% reduction in survival (the LC25) occurred at about 48 nmol litre(-1) after 4 weeks. Body concentrations of Tl, which were proportional to water concentrations, averaged 290 nmol g(-1) dry mass at the LC25. Growth was reduced at slightly lower concentrations. Concentrations affecting reproduction were variable at < 50% of the LC25. On a water-concentration basis Tl was more toxic than Ni, Cu or Zn, but less toxic than Cd or Hg to Hyalella; toxicity to Pb was similar. On a body-concentration basis, the toxicities of Tl, Cd, Hg and Pb were all similar. Unlike Cd, Tl toxicity and uptake was affected by K concentrations in the water, and not by Ca, Mg, Na or other ions. Toxicity was proportional to uptake, and body concentrations were better predictors of toxicity than water concentrations in media with varying K concentrations. Preliminary measurements of Tl and Cd uptake by Hyalella from Hamilton Harbour and Lake Ontario sediments suggested that total bioavailable metal concentrations were greater in deep-water sediments from Lake Ontario than in sediments from the harbour. The ratio of bioavailable metal to the toxic threshold was slightly higher for Cd than for Tl, but well below 1 for both metals.     

The effect of earthworms on the fractionation, mobility and bioavailability of Pb, Zn and Cd before and after soil leaching with EDTA

The effect of two ecologically contrasting earthworm species Eisenia fetida (epigeic) and Octolasion tyrtaeum (endogeic) on the fractionation (accessed using sequential extractions), mobility (toxicity characteristic leaching procedure, TCLP) and oral bioavailability (Ruby's physiologically based extraction test, PBET) of Pb, Zn and Cd was studied before and after soil remediation with soil leaching. Twenty-step leaching, with 2.5 mmol kg(-1) EDTA used in each step, removed 58.4%, 25.0% and 68.0% of initial soil Pb, Zn and Cd, respectively, shifted the fractionation of residual heavy metals toward less labile forms, and decreased their mobility by 83.7%, 80.3%, and 90.9%. Pb oral bioavailability was reduced by 3.1-times (in each stomach and intestinal phase). After soil leaching, both earthworm species enriched the carbonate soil fraction in their casts with residual Pb, and increased the Pb bioavailability in the simulated intestinal phase by a factor of 2.4 (E. fetida) and 2.8 (O. tyrtaeum). The concentration of Pb in TCLP leachate from E. fetida casts was 6.2-times higher than in the bulk of the remediated soil. These results indicate that the effect of biotic factors on the availability of heavy metals residual in soil after soil leaching requires consideration.     

Atp-measurements in soil: A combination between the TCA and NRB ® extraction methods

The extraction of ATP from soils with the TCA- and NRB ®-methods shows qualitative and quantitative differences. A combination of both methods results in a higher yield of extracted ATP and in a solution of low optical quenching.     

Geofractionation of heavy metals and application of indices for pollution prediction in paddy field soil of Tumpat, Malaysia

The present study investigates the concentration of Pb, Cd, Ni, Zn, and Cu in the paddy field soils collected from Tumpat, Kelantan. Soil samples were treated with sequential extraction to distinguish the anthropogenic and lithogenic origin of Pb, Cd, Ni, Zn, and Cu. ELFE and oxidizable-organic fractions were detected as the lowest accumulation of Pb, Cd, Ni, Zn, and Cu. Therefore, all the heavy metals examined were concentrated, particularly in resistant fraction, indicating that those heavy metals occurred and accumulated in an unavailable form. The utilization of agrochemical fertilizers and pesticides might not elevate the levels of heavy metals in the paddy field soils. In comparison, the enrichment factor and geoaccumulation index for Pb, Cd, Ni, Zn, and Cu suggest that these heavy metals have the potential to cause environmental risk, although they present abundance in resistant fraction. Therefore, a complete study should be conducted based on the paddy cycle, which in turn could provide a clear picture of heavy metals distribution in the paddy field soils.     

Simultaneous mobilization of heavy metals and polychlorinated biphenyl (PCB) compounds from soil with cyclodextrin and EDTA in admixture

This study evaluated the efficacy of a washing process with cyclodextrin in combination with ethylenediaminetetraacetate (EDTA) for the simultaneous mobilization of heavy metals and PCBs from a field contaminated soil. Ultrasonically aided mixing of the field contaminated soil with a combination of cyclodextrin solution (10%, w/v) and a sparing quantity (2 mmol) of EDTA, simultaneously mobilized appreciable quantities of PCBs and much of the analyte metal (Cd, Cr, Cu, Mn, Ni, Pb, Zn) burdens. Relative to the action of individual reagents, a combination of randomly methylated (RAMEB) or hydroxypropyl beta-cyclodextrin (HPCD) with EDTA did not alter the PCB extraction efficiency nor did the presence of cyclodextrin change the efficiency of mobilization of most heavy metals (Al, Cd, Cr, Fe, Mn, Ni, and Zn) but did increase the recovery of Cu and Pb modestly. Three sonication-washes with the same charge of reagents mobilized appreciable quantities of PCBs (40-76%) and quantitatively extracted the labile fraction of Cd, Cu, Mn, and Pb. RAMEB proved to be more efficient than HPCD for PCB extractions. Three successive extractions with a single charge of cyclodextrin mobilized almost as much PCB (RAMEB, 76%; HPCD, 40%) as did the companion extractions that used fresh reagents each time (RAMEB, 78%; HPCD, 42%). Collectively, these studies demonstrated that PCB compounds and selected heavy metals can be co-extracted efficiently from soil with three successive washes with the same washing suspension containing EDTA and cyclodextrin.     

The influence of EDDS and EDTA on the uptake of heavy metals of Cd and Cu from soil with tobacco Nicotiana tabacum

Phytoextraction, the use of plants to extract contaminants from soils and groundwater, is a promising approach for cleaning up soils contaminated with heavy metals. In order to enhance phytoextraction the use of chelating agents has been proposed. This study aims to assess whether ethylene diamine disuccinate (EDDS), a biodegradable chelator, can be used for enhanced phytoextraction purposed, as an alternative to ethylene diamine tetraacetate (EDTA). EDDS revealed a higher toxicity to tobacco (Nicotiana tabacum) in comparison to EDTA, but no toxicity to microorganisms. The uptake of Cu was increased by the addition of EDTA and EDDS, while no increase was observed in the uptake of Cd. Both chelating agents showed a very low root to shoot translocation capability and the translocation factor was lower than the one of the control. Heavy metals where significantly more phytoavailable than in the control, even after harvesting, resulting in a high heavy metal leaching possibility, probably owing to a low biodegradation rate of EDDS. New seedlings which were transplanted into the EDDS treated pots 7d after the phytoextraction experiment, showed signs of necrosis and chlorosis, which resulted in a significantly lower biomass in comparison to the control. The seedlings on the EDTA treated pots showed no toxicity signs. Contrary to previous opinions the results of this study revealed the chelating agents EDTA and EDDS as unsuitable for enhanced phytoextraction using tobacco.     

Chemometric evaluation for the relation of BCR sequential extraction method and in vitro gastro-intestinal method for the assessment of metal bioavailability in contaminated soils in Turkey

Introduction  

A chemometric evaluation has been done to classify metal ions in soils and to determine whether or not the gastric and intestinal phases of a physiologically based extraction test bear any relation to any of the phases of the four-stage Community Bureau of Reference (BCR) extraction protocol.     

Use of the physiologically-based extraction test to assess the oral bioaccessibility of metals in vegetable plants grown in contaminated soil

The oral bioaccessibility of metals in vegetable plants grown on contaminated soil was assessed. This was done using the physiologically-based extraction test (PBET) to simulate the human digestion of plant material. A range of vegetable plants, i.e. carrot, lettuce, radish and spinach, were grown on metal contaminated soil. After reaching maturity the plants were harvested and analysed for their total metal content (i.e. Cr, Cd, Cu, Fe, Mn, Mo, Ni, Pb and Zn) by inductively coupled plasma-mass spectrometry (ICP-MS). The plant samples were then subsequently extracted using an in vitro gastrointestinal approach or PBET to assess the likelihood of oral bioaccessibility if the material was consumed by humans.     

A comparison of biochemical responses to oxidative and metal stress in seedlings of barley, Hordeum vulgare L

Biochemical responses on the bases of activities of antioxidant enzymes; peroxidase, catalase, superoxide dismutase and glutathione reductase as well as estimations of total protein, lipid peroxidation and thiols in the form of protein, non-protein, glutathione and phytochelatin measured in growing seedlings of barley, Hordeum vulgare L., from Day 2 through 8 were compared following treatment of seeds for 2 h with oxidative agents, paraquat 5 x 10(-5), 10(-4), 10(-3) M, H2O2 10(-3), 5 x 10(-3), 10(-2) M and a metal salt, CdSO4 10(-5), 10(-4), 10(-3) M. A significant induction of all antioxidant enzymes along with an increase in the levels of protein, lipid peroxidation and glutathione was noted in response to oxidative stress, CdSO4 induced significant peroxidase and catalase activities but not superoxide dismutase. In a marked contrast from oxidative stress, CdSO4 decreased glutathione reductase activity as well as glutathione levels but increased phytochelatin level. The differential biochemical responses thus underlined the crucial involvement of glutathione and phytochelatin in the oxidative and metal-induced adaptive responses, respectively.     

Easy and fast extraction methods to determine organochlorine pesticides in sewage sludge,soil, and water samples based at low temperature

Organochlorine pesticides present in sewage sludge can contaminate soil and water when they are used as either fertilizer or agricultural soil conditioner. In this study, the technique solid–liquid extraction with low temperature purification was optimized and validated for determination of ten organochlorine pesticides in sewage sludge and soil samples. Liquid–liquid extraction with low temperature purification was also validated for the same compounds in water. Analyses were performed by gas chromatography-mass spectrometry operating in the selective ion monitoring mode. After optimization, the methods showed recoveries between 70% and 115% with relative standard deviation lower than 13% for all target analytes in the three matrices. The linearity was demonstrated in the range of 20 to 70 µg L^?1, 0.5 to 60 µg L^?1, and 3 to 13 µg L^?1, for sludge, soil, and acetonitrile, respectively. The limit of quantification ranged between 2 and 40 µg kg^?1, 1 and 6 µg kg^?1, and 0.5 µg L^?1 for sludge, soil, and water, respectively. The methods were used in the study of pesticide lixiviation carried out in a poly vinyl chlorine column filled with soil, which had its surface layer mixed with sludge. The results showed that pesticides are not leached into soil, part of them is adsorbed by the sewage sludge (4–40%), and most pesticides are lost by volatilization.     

Challenges with tracing the fate and speciation of mine-derived metals in turbid river systems: implications for bioavailability

The fast-flowing and highly turbid Lagaip River (0.5–10 g/L suspended solids) in the central highlands of Papua New Guinea receives mine-derived metal inputs in both dissolved and particulate forms. Nearest the mine, metal concentrations in suspended solids were 360, 9, 90, 740 and 1,300 mg/kg for As, Cd, Cu, Pb and Zn, while dissolved concentrations were 2.7, 0.6, 3.1, 0.1 and 25 μg/L, respectively. This creates a significant metal exposure source for organisms nearer the mine. However, because the Lagaip River is diluted by a large number of tributaries, the extent to which mine-derived metals may affect biota in the lower catchments is uncertain. To improve our understanding of the forms of potentially bioavailable metals entering the lower river system, we studied the partitioning and speciation of metals within the Lagaip River system. Dissolved and particulate metal concentrations decreased rapidly downstream of the mine due to dilution from tributaries. As a portion of the particulate metal concentrations, the more labile dilute acid-extractable forms typically comprised 10–30 % for As and Pb, 50–75 % for Cu and Zn, and 50–100 % for Cd. Only dissolved Cd, Cu and Zn remained elevated relative to the non-mine-impacted tributaries (<0.03, 0.5 and 0.3 μg/L), but the concentrations did not appreciably change with increasing dilution downriver. This indicated that release of Cd, Cu and Zn was likely occurring from the more labile metal phases of the mine-derived particulates. Chelex-labile metal analyses and speciation modelling indicated that dissolved copper and lead were largely non-labile and likely complexed by naturally occurring organic ligands, while dissolved cadmium and zinc were predominantly present in labile forms. The study confirmed that mine-derived particulates may represent a significant source of dissolved metals in the lower river system; however, comparison with water quality guidelines indicates the low concentrations would not adversely affect aquatic life.     

Chronic toxicity of ZnO nanoparticles, non-nano ZnO and ZnCl2 to Folsomia candida (Collembola) in relation to bioavailability in soil

The chronic toxicity of zinc oxide nanoparticles (ZnO-NP) to Folsomia candida was determined in natural soil. To unravel the contribution of particle size and free zinc to NP toxicity, non-nano ZnO and ZnCl₂ were also tested. Zinc concentrations in pore water increased with increasing soil concentrations, with Freundlich sorption constants K_f of 61.7, 106 and 96.4 l/kg (n = 1.50, 1.34 and 0.42) for ZnO-NP, non-nano ZnO and ZnCl₂ respectively. Survival of F. candida was not affected by ZnO-NP and non-nano ZnO at concentrations up to 6400 mg Zn/kg d.w. Reproduction was dose-dependently reduced with 28-d EC50s of 1964, 1591 and 298 mg Zn/kg d.w. for ZnO-NP, non-nano ZnO and ZnCl₂, respectively. The difference in EC50s based on measured pore water concentrations was small (7.94-16.8 mg Zn/l). We conclude that zinc ions released from NP determine the observed toxic effects rather than ZnO particle size.     

Adsorption, transformation, and bioavailability of the fungicides carbendazim and iprodione in soil, alone and in combination

When studying the effect of mixtures of toxic substances on soil organisms, attention must be paid to peculiarities in exposure to mixtures as opposed to that of single toxicants. The fungicides carbendazim and iprodione compete in the adsorption to soil. The presence of iprodione reduced the adsorption of carbendazim by 30%, while carbendazim reduced the adsorption of iprodione by 70%. Iprodione had little effect on the transformation rate of carbendazim in soil. However, carbendazim retarded the transformation of iprodione in soil by 26%. The concentration of the fungicides in pore water was found to be substantially higher for mixtures than when a fungicide alone was present in the soil. The effect of the additional fungicide on the concentration is especially apparent in the period following the first 1 to 2 weeks of the incubation. The inclusion of copper in the mixture has little additional effect on the concentration of the fungicides in pore water.     

An exploration of the relationship between adsorption and bioavailability of pesticides in soil to earthworm

A study was conducted to determine the adsorption/desorption of butachlor, myclobutanil and chlorpyrifos on five soils using a batch equilibration technique and to study the relationship between bioavailability to Allolobophora caliginosa and the adsorption/desorption of these three pesticides. The results showed that the adsorption/desorption processes of the tested compounds were mainly controlled by soil organic matter content (OM) and octanol/water-partitioning coefficient (K(ow)), and that the bioavailability of the pesticides was dependent on characteristics of pesticides, properties of soils, and uptake routes of earthworms. Bioconcentration of butachlor and myclobutanil was negatively correlated with Freundlich adsorption constant K(af) and K(df). However, only a slightly positive correlation between bioconcentration and K(af) and K(df) was observed for chlorpyrifos due to its high affinity onto soil.     

Integration of toxicological and chemical tools to assess the bioavailability of metals and energetic compounds in contaminated soils

Bioavailability is critical for understanding effects that might result from exposure of biota to contaminated soils. Soils from military range and training areas (RTAs) are contaminated principally by energetic materials (EM) and metals. Their chemical characteristics are relatively well known and toxicity assessment of soils from RTAs are in some cases available. However, bioavailability on these sites needs to be comprehensively characterized. A holistic approach to bioavailability, incorporating both chemical and earthworm toxicological indicators, was applied to soils from an anti-tank firing range at a Canadian Forces Base. Results showed that HMX and the metals Zn, Pb, Bi and Cd, though not consistently the prevailing toxicants, were the most accessible to earthworms. Some metals (notably Cu, Zn, Cr and Bi) were also accumulated in earthworm tissue but those were not necessarily expected given their bioaccessibility (i.e., the chemical availability of contaminants in the environment for the organisms) at the beginning of the exposure. The tested soils impaired earthworm reproduction and reduced adult growth. Measurement of selected sublethal parameters indicated that lysosomal integrity (determined as the neutral red retention time--NRRT) was decreased, while elevated superoxide dismutase (SOD) activity suggested that earthworms experienced oxidative stress. The correspondence between the NRRT and metal contamination pattern suggested that metals may be the main cause of lysosomal disruption in EM-contaminated soils. The approach to bioavailability appraisal adopted in this case appears to be a promising practice for site-specific assessment of contaminated land.     

A comparison of physiologically based extraction test (PBET) and single-extraction methods for release of Cu, Zn, and Pb from mildly acidic and alkali soils

In vitro digestion test can be applied to evaluate the bioaccessibility of soil metals by measuring the solubility of the metals in synthetic human digestive tract. Physiologically based extraction test (PBET), composed of sequential digestion of gastric and intestinal phase, is one of the frequently used in vitro digestion tests. In this study, the PBET was chosen to determine the bioaccessibility of Cu, Zn, and Pb in 14 mildly acidic and alkali (pH 5.87–8.30) soils. The phytoavailability of Cu, Zn, and Pb in the same soils was also measured using six single-extraction methods (0.1 M HNO₃, 0.4 M HOAc, 0.1 M NaNO₃, 0.01 M CaCl₂, 0.05 M EDTA, and 0.5 M DTPA). The extraction efficiencies of the methods were compared. The PBET had a strong ability to extract metals from soil, which was much greater than neutral salt extraction and close to dilute acid and complex extraction in spite of the last 2 h neutral intestinal digestion. The amounts of bioaccessible Cu, Zn, and Pb in the gastric phase and in the gastrointestinal phase were both largely determined by the total content of soil Cu, Zn, and Pb. But the results of gastrointestinal digestion reflected more differences resulting from element and soil types than those of gastric digestion did. It was noticed that most of variations in the amounts of soil Cu, Zn, and Pb extracted by EDTA were well explained by the total soil Cu, Zn, and Pb, as same as the PBET. Moreover, the solubility of Cu, Zn, and Pb in the gastric phase and gastrointestinal phase were all positively linearly correlated with the results of EDTA. It was suggested that EDTA extraction can be used to predict the bioaccessibility of Cu, Zn, and Pb in mildly acidic and alkali (pH?>?5.8) soils, and the PBET and EDTA could be applied to measure, in a certain extent, the bioaccessibility and phytoavailability of Cu, Zn, and Pb in mildly acidic and alkali (pH?>?5.8) soils at the same time.     

Application of surrogate methods for assessing the bioavailability of PAHs in sediments to a sediment ingesting bivalve

The usefulness of two surrogate methods for rapidly determining the bioavailability of PAHs in hydrocarbon-contaminated marine sediments was assessed. Comparisons are made between the PAHs accumulated by the benthic bivalve, Tellina deltoidalis, and the extractable-PAHs determined using a 6-h XAD-2 resin desorption method and a 4-h gut fluid mimic (GFM) extraction method. There were significant positive relationships between PAH bioaccumulation by the bivalves and sediment PAH concentrations. These relationships were not improved by normalising the sediment PAH concentrations to the organic carbon concentration. The average percentage lipid content of the bivalves was 1.47 ± 0.22% and BSAFs for total-PAHs ranged from 0.06 to 0.80 (kg OC/kg lipid). The XAD-2 and GFM methods both extracted varying amounts of PAHs from the sediments. Low concentrations of PAHs were extracted by the GFM method (0.2–3.6% of total-PAHs in sediments) and the GFM results were inadequate for generalising about the bioavailability of the PAHs in the sediments. The XAD-2 method extracted greater amounts of PAHs (3–34% of total-PAHs in sediments), however, the total-PAH concentrations in the sediments provided a better, or equally good, prediction of PAH bioaccumulation by T. deltoidalis. The results indicated that these methods required further development before they can be applied routinely as surrogate methods for assessing the bioavailability of PAHs in sediments. Future research should be directed towards lowering detection limits and obtaining comparative data for a greater range of sediment types, contaminant classes and concentrations, and organisms of different feeding guilds and with different gut chemistry.     

Influence of bacteria on Pb and Zn speciation, mobility and bioavailability in soil: A laboratory study

A soil column experiment was carried out to investigate the effects of inoculation of bacteria on metal bioavailability, mobility and potential leachability through single chemical extraction, consequential extraction and in situ soil solution extraction technologies. Results showed that bacteria inoculated, including Azotobacter chroococcum, Bacillus megaterium and Bacillus mucilaginosus, may pose both positive and negative impacts on bioavailability and mobility of heavy metals in soil, depending on the chemical nature of the metals. The activities of bacteria led to an increase of water dissolved organic carbon (DOC) concentration and a decrease of pH value, which enhanced metal mobility and bioavailability (e.g. an increase of water-soluble and HOAc-soluble Zn). On the other hand, bacteria could immobilize metals (e.g. a great reduction of water-soluble Pb) due to the adsorption by bacterial cell walls and possible sedimentation reactions with phosphate or other anions produced through bacterial metabolism.     

Kinetic extractions to assess mobilization of Zn, Pb, Cu, and Cd in a metal-contaminated soil: EDTA vs. citrate

Kinetic EDTA and citrate extractions were used to mimic metal mobilization in a soil contaminated by metallurgical fallout. Modeling of metal removal rates vs. time distinguished two metal pools: readily labile (QM1) and less labile (QM2). In citrate extractions, total extractability (QM1+QM2) of Zn and Cd was proportionally higher than for Pb and Cu. Proportions of Pb and Cu extracted with EDTA were three times higher than when using citrate. We observed similar QM1/QM2 ratios for Zn and Cu regardless of the extractant, suggesting comparable binding energies to soil constituents. However, for Pb and Cd, more heterogeneous binding energies were hypothesized to explain different kinetic extraction behaviors. Proportions of citrate-labile metals were found consistent with their short-term, in-situ mobility assessed in the studied soil, i.e., metal amount released in the soil solution or extracted by cultivated plants. Kinetic EDTA extractions were hypothesized to be more predictive for long-term metal migration with depth.