A model for evaluation of the phytoavailability of trace elements to vegetables under the field conditions

Currently, several single extraction methods are used for the evaluation of the phytoavailability of metals using pot experiments. A systematic comparison, however, is lacking. It is especially true for the field studies. This study was to investigate the phytoavailability of trace elements to vegetables grown on metal-contaminated soils under the field conditions. All soils collected were typical calcareous soils in northern China. Four frequently used methods using CaCl2, diethylenetriaminepentaacetic acid (DTPA), CH3COOH, and water as extractants were compared for phyto-availability. The concentrations of metals extracted by these four extraction methods ranged from 3.42 to 815, 1.51- 6965, 0.732-24473, 0.688-7863, 0.246-685, 1.99-5337 0.203-4649 ng/g for Cr, Ni, Zn, Cu, Cd, Pb and REEs, respectively. Simple correlation analysis indicated that a significant correlation (Cr: r = 0.5411**; Zn: r = 0.6352**; Cd: r = 0.6979**; Pb: r = 0.5537** and REEs: r = 0.5185** -0.6684**) was observed between the CaCl2-extractable metals in soil solution and that in Chinese cabbage. In addition, soil pH, organic matter (OM), and cation exchange capacity (CEC) also affect the phytoavailability. An empirical model was developed to express the combined effect of soil properties on the phytoavailability. The stepwise multiple regression analysis demonstrated that the phytoavailability of trace elements strongly correlated with the extractable fraction by CaCl2, total metal concentration in soils, and soil pH, OM, CEC. This model can describe approximately 75-95% of the variability of metal uptake and the r2 values ranged from 0.741** to 0.954**, which were much better than the single correlation analysis. For celery and cole, a strong correlation was obtained for Cr, Ni, Zn, Cu, Cd, La, Ce, Pr and Nd. For spinach and Chinese cabbage, however, a positive correlation was only observed for 1 and 3 metals, respectively. Generally, the developed empirical model can integrate the combined effects of soil properties, extractable metal fractions in soil solutions and plant species on the phytoavailability of metals to vegetables in the field conditions.     

A root exudates based approach to assess the long-term phytoavailability of metals in biosolids-amended soils

Organic acids present in the rhizosphere of growing plants are widely recognized to be responsible for dissolving the solid phase metals in the soil and making them available for plant absorption. We proposed a root exudates-based model to assess the long-term phytoavailability of metals in biosolids-amended soils. The phytoavailability of biosolids-borne metals was defined in terms of a capacity factor and an intensity factor. The plant available metal pool, C₀ (capacity factor, mg kg⁻¹), can be estimated by fitting the successive organic acids extraction data to an exponential decay kinetic equation. The field metal removal rate, k (intensity factor, yr⁻¹), can be estimated from the successive extraction-based metal release rate through an effective annual organic acid production in the rhizosphere which was found to be characteristic of plant species. The protocol was successfully used to assess the long-term phytoavailability of metals in biosolids-amended soil from two biosolids land application sites.     

Copper uptake by Elsholtzia splendens and Silene vulgaris and assessment of copper phytoavailability in contaminated soils

Tolerance and metal uptake are two essential characteristics required for phytoextraction of metals from contaminated soils. We compared tolerance and Cu uptake of Elsholtzia splendens (reported previously to be a Cu hyperaccumulator) with Silene vulgaris (the Imsbach population, a well-known Cu-tolerant excluder species), using 30 soils varying widely in total Cu concentration (19-8645 mg kg(-1)). We further investigated the effectiveness of different soil testing methods for predicting plant metal uptake. The results showed that both Elsholtzia splendens and Silene vulgaris were tolerant to Cu, especially Silene vulgaris. However, Elsholtzia splendens did not hyperaccumulate Cu, but behaved as a typical Cu excluder like Silene vulgaris. The concentrations of Cu in both plants correlated more closely with 1 M NH4NO3 extractable Cu, soil solution Cu, or effective Cu concentration determined using DGT, than with soil total Cu, EDTA extractable Cu or free Cu2+ activity. The relationships between soil solution properties and root Cu concentrations were further investigated using multiple regression. The results showed that increasing soil solution pH increased root Cu concentration when free Cu2+ activity was held constant, suggesting a higher phytoavailability of free Cu2+ at a higher pH. Soil solution DOC appeared to play two contrasting roles on the phytoavailability of Cu: (1) reducing Cu availability by complexing Cu; and (2) increasing Cu availability at the same level of free Cu2+ activity by providing a strong buffer for free Cu2+. The results are consistent with the intensity/capacity concept for phytoavailability of metals in soils.     

Heap leaching of Pb and Zn contaminated soil using ozone/UV treatment of EDTA extractants

The feasibility of a novel EDTA-based soil heap leaching method with treatment and reuse of extractants in a closed process loop was evaluated on a laboratory scale. Ozone and UV irradiation were used for oxidative decomposition of EDTA-metal complexes in extractants from Pb (1243 mg kg(-1)) and Zn (1190 mg kg(-1)) contaminated soil. Released metals were absorbed in a commercial metal absorbent Slovakite. Six-consecutive additions of 2.5 mmol kg(-1) EDTA (total 15 mmol kg(-1) EDTA) removed 49.6 +/- 0.6% and 19.7 +/- 1.7% of initial total Pb and Zn from soil (4.6 kg) packed in 22 cm high columns. The efficiency of extraction was similar to small-scale simulations of heap leaching (15 0 g of soil), where EDTA used in the same manner removed 49.7 +/- 1.0% and 13.7 +/- 0.4% of Pb and Zn. The new heap leaching method produced discharge extractant with fairly low final concentrations of Pb, Zn and EDTA (1.98 +/- 2.17 mg l(-1), 4.55 +/- 2.36 mg l(-1), and 0.05 +/- 0.04 mM, respectively), which could presumably be reduced even further with continuation of treatment. The results of our study indicate that for soils contaminated primarily with Pb, treating the EDTA extractants with ozone/UV and reuse of extractants enables efficient soil heap leaching with very little or no wastewater generation, easy control over emissions, and lowers the requirements for process water.     

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.     

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.     

Is an adjusted rhizosphere-based method valid for field assessment of metal phytoavailability? Application to non-contaminated soils

Previously recommended rhizosphere-based method (RHIZO) applied to moist rhizosphere soils was integrated with moist bulk soils, and termed adjusted-RHIZO method (A-RHIZO). The A-RHIZO and RHIZO methods were systematically compared with EDTA, DTPA, CaCl2 and the first step of the Community Bureau of Reference (BCR1) methods for assessing metal phytoavailability under field conditions. Results suggested that moist bulk soils are equally suited or even better than rhizosphere soils to estimate metal phytoavailability. The A-RHIZO method was preferred to other methods for predicting the phytoavailability of Ni, Cu, Zn, Cd, Pb and Mn to wheat roots with correlation coefficients of 0.730 (P<0.001), 0.854 (P<0.001), 0.887 (P<0.001), 0.739 (P<0.001), 0.725 (P<0.001) and 0.469 (P<0.05), respectively. When including soil properties, other extraction methods were also able to predict phytoavailability reasonably well for some metals. Soil pH, organic matter and Fe-Mn oxide contents, and cation-exchange capacity mostly influenced the extraction and phytoavailability of metals.     

Bioaccumulation in Porcellio scaber (Crustacea, Isopoda) as a measure of the EDTA remediation efficiency of metal-polluted soil

Leaching using EDTA applied to a Pb, Zn and Cd polluted soil significantly reduced soil metal concentrations and the pool of metals in labile soil fractions. Metal mobility (Toxicity Characteristic Leaching Procedure), phytoavailability (diethylenetriaminepentaacetic acid extraction) and human oral-bioavailability (Physiologically Based Extraction Test) were reduced by 85-92%, 68-91% and 88-95%, respectively. The metal accumulation capacity of the terrestrial isopod Porcellio scaber (Crustacea) was used as in vivo assay of metal bioavailability, before and after soil remediation. After feeding on metal contaminated soil for two weeks, P. scaber accumulated Pb, Zn and Cd in a concentration dependent manner. The amounts of accumulated metals were, however, higher than expected on the basis of extraction (in vitro) tests. The combined results of chemical extractions and the in vivo test with P. scaber provide a more relevant picture of the availability stripping of metals after soil remediation.     

Mitigation effects of silicon rich amendments on heavy metal accumulation in rice (Oryza sativa L.) planted on multi-metal contaminated acidic soil

The mechanisms of stabilization by silicon-rich amendments of cadmium, zinc, copper and lead in a multi-metal contaminated acidic soil and the mitigation of metal accumulation in rice were investigated in this study. The results from a pot experiment indicated that the application of fly ash (20 and 40 g kg⁻¹) and steel slag (3 and 6 g kg⁻¹) increased soil pH from 4.0 to 5.0-6.4, decreased the phytoavailability of heavy metals by at least 60%, and further suppressed metal uptake by rice. Diffusion gradient in thin-film measurement showed the heavy metal diffusion fluxes from soil to solution decreased by greater than 84% after remediation. X-ray diffraction analysis indicated the mobile metals were mainly deposited as their silicates, phosphates and hydroxides in amended treatments. Moreover, it was found metal translocation from stem to leaf was dramatically restrained by adding amendments, which might be due to the increase of silicon concentration and co-precipitation with heavy metals in stem. Finally, a field experiment showed the trace element concentrations in polished rice treated with amendments complied with the food safety standards of China. These results demonstrated fly ash and steel slag could be effective in mitigating heavy metal accumulation in rice grown on multi-metal contaminated acidic soils.     

Eisenia fetida avoidance behavior as a tool for assessing the efficiency of remediation of Pb, Zn and Cd polluted soil

Remediation by means of soil leaching with ethylenediaminetetraacetic acid (EDTA) is capable of extracting the most labile soil fractions, leaving the residual metals in biologically non-available forms. We evaluated the feasibility of the standardized earthworm (Eisenia fetida) avoidance test for assessing the efficiency of soil remediation of Pb, Zn and Cd polluted soil. Chemical extraction tests (six-step sequential extraction, toxicity characteristic leaching procedure, physiologically based extraction test, diethylenediaminepentaacetic acid extraction) indicated that the mobility, oral bioaccessibility and phytoavailability of Pb, Zn and Cd were consistently reduced. However, the avoidance test showed no significant avoidance of polluted soil in favor of that which had been remediated. Pb, Zn and Cd accumulation in E. fetida mirrored the decreasing pattern of metal potential bioavailability gained by leaching the soil with increasing EDTA concentrations. The calculated bioaccumulation factors indicated the possibility of underestimating the metal bioavailability in soil using chemical extraction tests.     

The significance of (radio-) labile cadmium pools in soil

The radio-labile fraction of cadmium, in a wide range of contaminated soils, was studied in relation to fractions of cadmium defined by traditional extraction procedures. The proportion of labile Cd which was exchangeable was highly pH-dependent, but above pH 5 only about 5% of labile Cd was extractable with 1 m KNO(3). By contrast, EDTA released more than the labile Cd pool into solution, suggesting that significant dissolution of metal adsorbents may occur when chelating agents are utilised as trace metal extractants. The effect of time in immobilising Cd added to soil was also illustrated by following changes in the radio-labile Cd concentration. In calcareous soils, an instantaneous 'fixation' reaction as well as a time-dependent transfer to non-labile pools was identified. It is suggested that radio-labile Cd represents a relatively unambiguous assessment of the chemical and biological reactivity of Cd in soil compared with the fractions isolated by chemical extractants.     

Study of metal fractionation in river sediments. A comparison between kinetic and sequential extraction procedures

The extraction kinetic of trace metals (Cd, Cu, Pb, and Zn) in river sediments by four extraction agents was studied. As extractants ammonium acetate, acetic acid, hydroxylamine and EDTA solutions were assayed. These reagents can leach the metals more or less selectively from several metal compartments of sediments. The metal leaching kinetic model permits classification of the metal species in labile and moderately-labile ones. The combination of two or more non specific reagents permits a high characterisation of metal distribution and leachability. The results obtained with this model in four river sediments were compared with data obtained by the SM&T sequential extraction procedure, in order to characterise the chemical nature of leached metal.     

Effect of sludge-processing mode, soil texture and soil pH on metal mobility in undisturbed soil columns under accelerated loading

The effect of sludge processing (digested dewatered, pelletized, alkaline-stabilized, composted, and incinerated), soil type and initial soil pH on trace metal mobility was examined using undisturbed soil columns. Soils tested were Hudson silt loam (Glossaquic Hapludalf) and Arkport fine sandy loam (Lamellic Hapludalf), at initial pH levels of 5 and 7. Sludges were applied during four accelerated cropping cycles (215 tons/ha cumulative application for dewatered sludge; equivalent rates for other sludges), followed by four post-application cycles. Also examined (with no sludge applications) were Hudson soil columns from a field site that received a heavy loading of sludge in 1978. Romaine (Lactuca sativa) and oats (Avena sativa) were planted in alternate cycles, with oats later replaced by red clover (Trifolium pratense). Soil columns were watered with synthetic acid rainwater, and percolates were analyzed for trace metals (ICP spectroscopy), electrical conductivity and pH. Percolate metal concentrations varied with sludge and soil treatments. Composted sludge and ash had the lowest overall metal mobilities. Dewatered and pelletized sludge had notable leaching of Ni, Cd and Zn in Arkport soils, especially at low pH. Alkaline-stabilized sludge had the widest range of percolate metals (relatively insensitive to soils) including Cu, Ni, B and Mo. Old site column percolate concentrations showed good agreement with previous field data. Little leaching of P was observed in all cases. Cumulative percolate metal losses for all treatments were low relative to total applied metals. Leachate and soil pH were substantially depressed in dewatered and pelletized sludge soil columns and increased for alkaline-stabilized and ash treatments.     

Chemical speciation and extractability of Zn,Cu and Cd in two contrasting biosolids-amended clay soils

An incubation experiment was conducted to study the chemical speciation and extractability of three heavy metals in two contrasting biosolids-amended clay soils. One was a paddy soil of pH 7.8 and the other was a red soil of pH 4.7 collected from a fallow field. Anaerobically digested biosolids were mixed with each of the two soils at three rates: 20, 40 and 60 g kg(-1) soil (DM basis), and unamended controls were also prepared. The biosolids-amended and control soils were incubated at 70% of water holding capacity at 25 degrees C for 50 days. Separate subsamples were extracted with three single extractants and a three-step sequential extraction procedure representing acetic acid (HOAc)-soluble, reducible and oxidisable fractions to investigate the extractability and speciation of the heavy metals. As would be expected, there were good relationships between biosolids application rate and metal concentrations in the biosolids-amended soils. The three heavy metals had different extractabilities and chemical speciation in the two biosolids-amended soils. Ethylene diamine tetraacetic acid extracted more Cu, Zn and Cd than did the other two single extractants. The oxidisable fraction was the major fraction for Cu in both biosolids-amended soils and the HOAc-soluble and reducible fractions accounted for most of the Zn. In contrast, Cd was present mainly in the reducible fraction. The results are discussed in relation to the mobility and bioavailability of the metals in polluted soils.     

Survey on composition and bioconcentration potential of 12 metallic elements in King Bolete (Boletus edulis) mushroom that emerged at 11 spatially distant sites

This paper provides data on baseline concentrations, interrelationships and bioconcentration potential of 12 metallic elements by King Bolete collected from 11 spatially distant sites across Poland. There are significant differences in concentrations of metals (Al, Ba, Ca, Cd, Cu, Fe, K, Mg, Mn, Na, Sr, Zn) and their bioconcentration potential in King Bolete Boletus edulis at 11 spatially distant sites surveyed across Poland. These have resulted from significant geographical differences in trace metal concentrations in a layer (0-10 cm) of organic and mineral soil underneath to fruiting bodies and possible local bioavailabilities of macro- (Ca, K, Mg, Na) and trace metals (Al, Ba, Cd, Cu, Fe, Mn, Sr, Zn) to King Bolete. The use of highly appreciated wild-grown edible King Bolete mushroom has established a baseline measure of regional minerals status, heavy metals pollution and assessment of intake rates for wild mushroom dish fanciers against which future changes can be compared. Data on Cd, Cu and Zn from this study and from literature search can be useful to set the maximum limit of these metals in King Bolete collected from uncontaminated (background) areas. In this report also reviewed are data on Al, Ba, Ca, Cd, Cu, Fe, K, Mg, Mn, Na, Sr and Zn accumulation in King Bolete.     

Potential of Brassic rapa, Cannabis sativa, Helianthus annuus and Zea mays for phytoextraction of heavy metals from calcareous dredged sediment derived soils

Remediation of soil pollution is one of the many current environmental challenges. Anthropogenic activity has resulted in the contamination of extended areas of land, the remediation of which is both invasive and expensive by conventional means. Phytoextraction of heavy metals from contaminated soils has the prospect of being a more economic in situ alternative. In addition, phytoextraction targets ecotoxicologically the most relevant soil fraction of these metals, i.e. the bioavailable fraction. Greenhouse experiments were carried out to evaluate the potential of four high biomass crop species in their potential for phytoextraction of heavy metals, with or without with the use of soil amendments (EDTA or EDDS). A calcareous dredged sediment derived surface soil, with high organic matter and clay content and moderate levels of heavy metal pollution, was used in the experiments. No growth depression was observed in EDTA or EDDS treated pots in comparison to untreated controls. Metal accumulation was considered to be low for phytoextraction purposes, despite the use of chelating agents. The low observed shoot concentrations of heavy metals were attributed to the low phytoavailability of heavy metals in this particular soil substrate. The mobilising effects induced by EDTA in the soil were found to be too long-lived for application as a soil amendment in phytoextraction. Although EDDS was found to be more biodegradable, higher effect half lives were observed than reported in literature or observed in previous experiments. These findings caution against the use of any amendment, biodegradable or otherwise, without proper investigation of its effects and the longevity thereof.     

Wash effect of atmospheric trace metals wet deposition and its source characteristic in subtropical watershed in China

In order to better understand air pollution in deve-loping regions, such as China, it is important to investigate the wet deposition behavior of atmospheric trace metals and its sources in the subtropical watershed. This paper studies the seasonal change of trace metal concentrations in precipitation and other potential sources in a typical subtropical watershed (Jiazhuhe watershed) located in the downstream of the Yangtze River of China. The results show that typical crustal elements (Al, Fe) and trace element (Zn) have high seasonal variation patterns and these elements have higher contents in precipitation as compared to other metals in Jiazhuhe watershed. In addition, there is no observed Pb in base flow in this study, and the concentration magnitudes of Al, Ba, Fe, Mn, Sr, and Zn in base flow are significantly higher than that of other metals. During different rainfall events, the dynamic export processes are also different for trace metals. The various trace metals dynamic export processes lead to an inconsistent mass first flush and a significant accumulative variance throughout the rainfall events. It is found that in this region, most of the trace metals in precipitation are from anthropogenic emission and marine aerosols brought by typhoon and monsoon.

     

Effect of amendments on the extractability, retention and plant uptake of metals on a sewage-irrigated soil

Laboratory and greenhouse experiments were conducted to evaluate the effects of farmyard manure (FYM), CaCO(3) and single superphosphate (SSP) on retention and availability of Zn, Cu and Ni in sewage-irrigated soil. We also assessed the suitability of 0.05M EDTA for predicting the effectiveness of these amendments in reducing the phytoavailability of metals. Results indicated that EDTA could successfully predict the phytoavailability of Zn and Ni in amended soil, whereas it failed in case of Cu. By and large, application of CaCO(3), either alone or in combination with FYM had a positive effect on the retention of Zn, Cu and Ni in soil. Application of CaCO(3) alone or in combination with FYM was equally effective in reducing the Zn content in lettuce, whereas sole application of CaCO(3) significantly reduced Ni content. However, only SSP was found to be effective in reducing the Cu content in lettuce.     

Metal availability and soil toxicity after repeated croppings of Thlaspi caerulescens in metal contaminated soils

Metal phytoextraction with hyperaccumulating plants could be a useful method to decontaminate soils, but it is not fully validated yet. In order to quantify the efficiency of Cd and Zn extraction from a calcareous soil with and without Fe amendment and an acidic soil, we performed a pot experiment with three successive croppings of Thlaspi caerulescens followed by 3 months without plant and 7 weeks with lettuce. We used a combined approach to assess total extraction efficiency (2 M HNO3-extractable metals), changes in metal bio/availability (0.1 M NaNO3-extractable metals and lettuce uptake) and toxicity (lettuce biomass and the BIOMET biosensor). The soil solution was monitored over the whole experiment. In the calcareous soil large Cu concentrations were probably responsible for chlorosis symptoms observed on T. caerulescens. When this soil was treated with Fe, the amount of extracted metal by T. caerulescens increased and metal availability and soil toxicity decreased when compared to the untreated soil. In the acidic soil, T. caerulescens was most efficient: Cd and Zn concentrations in plants were in the range of hyperaccumulation and HNO3-extractable Cd and Zn, metal bio/availability, soil toxicity, and Cd and Zn concentrations in the soil solution decreased significantly. However, a reduced Cd concentration measured in the third T. caerulescens cropping indicated a decrease in metal availability below a critical threshold, whereas the increase of dissolved Cd and Zn concentrations after the third cropping may be the early sign of soil re-equilibration. This indicates that phytoextraction efficiency must be assessed by different approaches in order not to overlook any potential hazard and that an efficient phytoextraction scheme will have to take into account the different dynamics of the soil-plant system.     

Metal partitioning in river sediments measured by sequential extraction and biomimetic approaches

We quantified the concentrations and distributions of metals (Cd, Cr, Cu, Ni, Pb, and Zn) in the sediments of Tuen Mun River, Hong Kong. The potential bioavailability of metals was assessed with a biomimetic extraction method using the sipunculan gut juices. The sediments were characterized by relatively high concentrations of trace metals. Field collected sediments were highly anoxic and the ratio of simultaneously extractable metal (sigmaSEM) to acid volatile sulfide (AVS) was much less than one in these sediments. The majority (>67%) of Cd, Pb, and Zn were bound to AVS, thus their concentrations in the sediment porewater were low. In contrast, Ni was little bound to AVS due to its lower ratios of SEM-Ni to total Ni concentrations. For Cu, relatively high concentrations in the sediment porewater was found, and total organic carbon, AVS and other resistant sulfide phase were the controlling factors for sedimentary Cu partitioning. Net metal adsorption from gut juices to anoxic sediments was observed in metal extraction experiments, suggesting that AVS determined the bioaccumulation and potential bioavailability of most metals in these sediments. Extraction of metals from the oxidized sediments by the gut juices was mainly attributed to metal redistribution from AVS to other geochemical phases. The gut juices were the most effective solvent or extractant than the simple electrolyte solution [I (NaNO(3)) = 0.01 M] and the natural overlying water. Cd was more easily extracted from the oxidized sediments than Zn that tended to have a stronger binding affinity with Fe-Mn oxide, clay and organic matter. The application of partial removal techniques in metal extraction experiments further demonstrated the differential controls of various sediment geochemical phases in affecting metal bioavailability, with the order of TOC > Fe-Mn oxides > carbonate.