Source apportionment of bioavailable trace metals in soil based on chemical fractionation and its environmental implications

Environmental Science and Pollution Research - The bioavailable trace metals are closely related to environmental safety and human health, which might have different source characteristics from the...     

Assessment of the bioavailability of rare earth elements in soils by chemical fractionation and multiple regression analysis

The bioavailability of rare earth elements (REEs) in soils was evaluated, based on the combination of chemical fractionation and multiple regression analysis. REEs in soils were partitioned by a sequential extraction procedure into water soluble (F(ws)), exchangeable (F(ec)), bound to carbonates (F(cb)), bound to organic matter (F(om)), bound to Fe-Mn oxides (F(fm)) and residual (F(rd)) fractions. Alfalfa (Medicago Staiva Linn.) had been grown on the soils in a pot-culture experiment under greenhouse conditions for 35 days. The concentrations of REEs in fractions and plant were determined by inductively coupled plasma-mass spectrometry (ICP-MS). Chemical fractionation showed that (F(ws)) fraction of REEs was less than 0.1% and residual (F(rd)) was the dominant form, more than 60% in soils. Bioaccumulation of REEs was observed in Alfalfa. REE availability to the plant was evaluated by multiple regression analysis. F(ws), F(ec), F(cb) and F(om) fractions were significantly correlated with REE uptake by alfalfa. But the exchangeable Pr(F(ec)) was significantly correlated with Pr concentration in alfalfa. F(ec), F(cb) and F(om) greatly contributed to La and Nd bioavailability; F(ec) and F(om) to Ce, Gd and Dy; F(ec) and F(cb) to Yb; and F(ws), F(ec) and F(om) to total REEs. This meant that the bioavailability of different species of REEs varied with individual REE. The results of this study indicated that the sequential extraction procedure, in conjunction with multiple regression analysis, may be useful for the prediction of plant uptake of REEs from soils.     

Evaluation of metal mobility, plant availability and immobilization by chemical agents in a limed-silty soil

Metal-contaminated soils in the vicinity of industrial sites become of ever-increasing concern. Diagnostic criteria and ecological technologies for soil remediation should be calibrated for various soil conditions; actually, our knowledge of calcareous soil is poor. Silty soils near smelters at Evin (Pas de Calais, France) have been contaminated by non-ferrous metal fallout and regularly limed using foams. Therefore, the mobility, bioavailability, and potential phytotoxicity of Cd, Pb and Zn, were investigated using single soil extractions (i.e. water, 0.1 n Ca(NO(3))(2), and EDTA pH 7), and vegetation experiments, in parallel with a biological test based on (iso)-enzymes in leaves and roots, before and following soil treatment with chemical agents, i.e. Thomas basic slags (TBS), hydrous manganese oxide (HMO), steel shots (ST) and beringite. No visible toxicity symptoms developed on the above-ground parts of ryegrass, tobacco and bean plants grown in potted soil under controlled environmental conditions. Cd, Zn and Pb uptake resulted in high concentrations in the above-ground plant parts, but the enzyme capacities in leaves and roots, and the peroxidase pattern indicated that these metal concentrations were not phytotoxic for beans as test plants. The addition of chemical agents to the soil did not increase biomass production, but treatment with either HMO, ST or beringite markedly decreased the mobility of Cd, Zn and Pb. These agents were proven to be effective in mitigating the Cd uptake by plants. HMO and ST decreased either Pb or Zn uptake by ryegrass. TBS was effective in lowering Pb uptake by the same species. Beringite decreased Cd uptake by beans. If fallout could be restricted, the metal content of food crops in this area should be lowered by soil treatment. However, the differences in Cd uptake between plant species were not suppressed, regardless of the type of agents applied to the soil.     

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.     

Insight into soil nitrogen and phosphorus availability and agricultural sustainability by plant growth-promoting rhizobacteria

Environmental Science and Pollution Research - Nitrogen and phosphorus are critical for the vegetation ecosystem and two of the most insufficient nutrients in the soil. In agriculture practice,...     

Phytostabilization of a metal contaminated sandy soil. I: Influence of compost and/or inorganic metal immobilizing soil amendments on phytotoxicity and plant availability of metals

In a lysimeter set-up, compost addition to an industrial contaminated soil slightly reduced phytotoxicity to bean seedlings. The "Phytotoxicity Index" (on a scale from 1 to 4) decreased from 3.5 to 2.8. The same treatment also reduced metal accumulation in grasses: mean Zn, Cd and Pb concentrations decreased respectively from 623 to 135, from 6.2 to 1.3 and from 10.7 to <6 mg kg-1 dry weight. When combined with inorganic metal immobilizing amendments, compost had a beneficial effect on plant responses additional to the inorganic amendments alone. Best results were obtained when using compost (C)+cyclonic ashes (CA)+steel shots (SS). The "Phytotoxicity Index" decreased to 1.7, highest diversity of spontaneously colonizing plants occurred, and metal accumulation in grasses reduced to values for uncontaminated soils. Based on the first year evaluation, C+CA+SS showed to be an efficient treatment for amendment assisted phytostabilization of the contaminated Overpelt soil.     

Octanol-solubility of dissolved and particulate trace metals in contaminated rivers: implications for metal reactivity and availability

The lipid-like, amphiphilic solvent, n-octanol, has been used to determine a hydrophobic fraction of dissolved and particulate trace metals (Al, Cd, Co, Cu, Mn, Ni, Pb, Zn) in contaminated rivers. In a sample from the River Clyde, southwest Scotland, octanol-solubility was detected for all dissolved metals except Co, with conditional octanol-water partition coefficients, D(ow), ranging from about 0.2 (Al and Cu) to 1.25 (Pb). In a sample taken from the River Mersey, northwest England, octanol-solubility was detected for dissolved Al and Pb, but only after sample aliquots had been spiked with individual ionic metal standards and equilibrated. Spiking of the River Clyde sample revealed competition among different metals for hydrophobic ligands. Metal displacement from hydrophobic complexes was generally most significant following the addition of ionic Al or Pb, although the addition of either of these metals had little effect on the octanol-solubility of the other. In both river water samples hydrophobic metals were detected on the suspended particles retained by filtration following their extraction in n-octanol. In general, particulate Cu and Zn (up to 40%) were most available, and Al, Co and Pb most resistant (<1%) to octanol extraction. Distribution coefficients defining the concentration ratio of octanol-soluble particle-bound metal to octanol-soluble dissolved metal were in the range 10(3.3)-10(5.3)mlg(-1). The presence of hydrophobic dissolved and particulate metal species has implications for our understanding of the biogeochemical behaviour of metals in aquatic environments. Specifically, such species are predicted to exhibit characteristics of non-polar organic contaminants, including the potential to penetrate the lipid bilayer. Current strategies for assessing the bioavailability and toxicity of dissolved and particulate trace metals in natural waters may, therefore, require revision.     

复配钝化剂对稻田重金属有效性及其水稻吸收的影响

针对红壤稻米中重金属Cd超标的问题,通过筛选钝化剂并将其复配用于大田实验,以研究复配钝化剂对土壤有效态重金属(Cd、Pb和Cu)及水稻吸收重金属的影响及其作用机理。室内筛选实验表明,在11种无机和有机钝化剂中,海泡石、生石灰和聚丙烯酰胺对土壤重金属钝化效果较好,使有效态Cd、Pb和Cu分别降低了32.4% ~ 89.2%、19.5% ~ 99.1%和49.4% ~ 92.4%,并将它们确定为复配钝化剂的成分。大田实验结果表明,生石灰、聚丙烯酰胺和海泡石复配对土壤中重金属钝化效果最佳,使有效态Cd、Pb和Cu分别降低了28.6%、20.2%和23.5%(p<0.05),其钝化机制为离子交换和络合作用。而且,该复配钝化剂对土壤化学性质影响最小。复配钝化剂使稻米中Cd的质量分数降低了21.7% ~ 93.1%(p<0.05)。另外,复配钝化剂对土壤微生物丰度和多样性没有显著影响。考虑到土壤的安全性和稳定性,推荐将生石灰、聚丙烯酰胺和海泡石复配钝化剂用于降低红壤稻米对Cd的吸收以确保粮食安全生产。本研究结果可为重金属污染红壤稻田的安全利用提供参考。     

Distribution of PAHs and trace metals in urban stormwater sediments: combination of density fractionation,mineralogy and microanalysis

Sediment management from stormwater infiltration basins represents a real environmental and economic issue for stakeholders due to the pollution load and important tonnages of these by-products. To reduce the sediment volumes to treat, organic and metal micropollutant-bearing phases should be identified. A combination of density fractionation procedure and microanalysis techniques was used to evaluate the distribution of polycyclic aromatic hydrocarbons (PAHs) and trace metals (Cd, Cr, Cu, Ni, Pb, and Zn) within variable density fractions for three urban stormwater basin sediments. The results confirm that PAHs are found in the lightest fractions (d?d??3) whereas trace metals are equally distributed within the light, intermediary, and highest fractions (d?d?d?d?>?2.8 g cm^?3) and are mostly in the 2.3?d??3 fraction. The characterization of the five fractions by global analyses and microanalysis techniques (XRD and MEB-EDX) allowed us to identify pollutant-bearing phases. PAHs are bound to the organic matter (OM) and trace metals to OM, clays, carbonates and dense particles. Moreover, the microanalysis study underlines that OM is the main constituent responsible for the aggregation, particularly for microaggregation. In terms of sediment management, it was shown that density fractionation is not suitable for trace metals but could be adapted to separate PAH-enriched phases.     

Kinetic characterizing of soil trace metal availability using Soil/EDTA/Chelex mixture

The kinetic aspects are not usually tackled when mimicking the soil trace metal mobilization. In this work, a simple procedure is developed for measuring the kinetics of Pb, Cu and Cd transfer from the soil solid phase towards a resin sink. A ternary system of Soil/EDTA/Chelex was employed for mimicking the metal transfer from two agricultural soil samples into the Chelex. Two different kinetic regimes (P₁ and P₂) were observed. The kinetic profile of Pb was distinctly different from those of Cd and Cu. Basing on kinetic principles, two kinetic models were proposed for estimating the apparent rate constants of leaching and removal processes in, respectively, two binary mixtures of soil/EDTA and EDTA extracts/Chelex. Contrary to Pb, solid phase pools of Cd and Cu exchanged with the solution on short time scales. The kinetic rate of desorption occurred in following order: Pb < Cu ? Cd. Comparing the kinetics of binary systems, the desorption process was hypothesized to control the metal transfer. The parameters related to the desorption process were extended to the kinetic regimes of Soil/EDTA/Chelex and revealed that the soil to Chelex transfer of Pb is under kinetics control whereas the bulk concentration (affected by the size of particulate reservoir) is likely to control the Cd transfer. Cu presents an intermediate case.     

The effect of earthworms on the fractionation and bioavailability of heavy metals before and after soil remediation

The effect of two earthworm species, Lumbricus rubellus and Eisenia fetida, on the fractionation/bioavailability of Pb and Zn before and after soil leaching with EDTA was studied. Four leaching steps with total 12.5 mmol kg(-1) EDTA removed 39.8% and 6.1% of Pb and Zn, respectively. EDTA removed Pb from all soil fractions fairly uniformly (assessed using sequential extractions). Zn was mostly present in the chemically inert residual soil fraction, which explains its poor removal. Analysis of earthworm casts and the remainder of the soil indicated that L. rubellus and E. fetida actively regulated soil pH, but did not significantly change Pb and Zn fractionation in non-remediated and remediated soil. However, the bioavailability of Pb (assessed using Ruby's physiologically based extraction test) in E. fetida casts was significantly higher than in the bulk of the soil. In remediated soil the Pb bioavailability in the simulated stomach phase increased by 5.1 times.     

Monitoring historical changes in soil and atmospheric trace metal levels by dendrochemical analysis

The use of dendrochemistry for monitoring historical changes in trace metal deposition and mobilisation of metals in soils is evaluated. In experimental studies, mobilisation of trace metals in surface soil following deliberate acidification was recorded in sugar maple (Acer saccharum) tree-rings with minimal lateral movement between rings. Furthermore, positive correlations between wood (3 year section 1993-95) and foliar chemistry (mean concentration 1993-95) were found for Cd and Zn, but not for Cu and Ni, showing that mobility up the tree bole differs between metals. Even so, substantial lateral movement of elements between rings occurs in some species. Stable Pb isotope ratios in tree-rings were used to show that sacred fir (Abies religeosa) is not a useful monitor of Pb deposition because Pb accumulates in the heartwood. Numerous sophisticated analytical techniques are now used in dendrochemical studies, including laser ablation sampling in conjunction with inductively coupled plasma mass spectrometry that enable the multi-element analysis of extremely small tree-rings with low detection limits. Clearly, not all tree species are suitable for dendrochemical studies, but if careful sampling strategies are used and suitable tree species are chosen, the chemical analysis of tree-rings can provide information concerning historical changes in soil and atmospheric trace metal levels unavailable from any other source.     

Evaluation of extractants for estimation of the phytoavailable trace metals in soils

Despite its environmental (and financial) importance, there is no agreement in the literature as to which extractant most accurately estimates the phytoavailability of trace metals in soils. A large data set was taken from the literature, and the effectiveness of various extractants to predict the phytoavailability of Cd, Zn, Ni, Cu, and Pb examined across a range of soil types and contamination levels. The data suggest that generally, the total soil trace metal content, and trace metal concentrations determined by complexing agents (such as the widely used DTPA and EDTA extractants) or acid extractants (such as 0.1M HCl and the Mehlich 1 extractant) are only poorly correlated to plant phytoavailability. Whilst there is no consensus, it would appear that neutral salt extractants (such as 0.01 M CaCl(2) and 0.1 M NaNO(3)) provide the most useful indication of metal phytoavailability across a range of metals of interest, although further research is required.     

Evaluation of pollution by heavy metals of an abandoned Pb-Zn mine in northern Tunisia using sequential fractionation and geostatistical mapping

This study investigates the contents of lead, zinc, and cadmium in 109 near-surface soil samples collected around the abandoned mine of Fedj Lahdoum, northern Tunisia, to assess the risk of pollution they generate. The study involved some analytical procedures such as pH measurements, X-ray diffraction techniques, sequential fractionation, and geostatistical mapping using the ordinary Kriging techniques. The sequential fractionation revealed that the bioavailability of Pb, Zn, and Cd follows the orders F5?>?F3 » F4?>?F2 » F1, F5?>?F3 » F4 » F2?>?F1 and F5?>?F2 » F4?>?F1, respectively; their associations with organic matter and residual sulfides (F4) are relatively low. However, their high cumulated contents are dominantly associated with the residual (F5) and reducible (F3) fractions. The geostatistical mapping was endeavored to predict the spatial distribution of the studied heavy metals at unsampled sites and to produce a cumulated risk map of soil pollution. The latter is discussed with emphasis of the main factors responsible for the scattering of the pollution as much as the landscape conditions, the chemical composition of the mine tailings, the surface drainage of meteoric water and the wind. This study provides insight into the delineation of the spatial spreading of Pb, Zn, and Cd around the abandoned mine Fedj Lahdoum and their surrounding urban areas. It reveals that the mine infrastructure areas encompassing both extraction and processing and tailing deposition areas are the main sources of contamination. And the landscape conditions together with the surface drainage of meteoric water and the wind are the main factors responsible for the scattering of the pollution.

     

Determination of chemical availability of cadmium and zinc in soils using inert soil moisture samplers

A rapid method for extracting soil solutions using porous plastic soil-moisture samplers was combined with a cation resin equilibration based speciation technique to look at the chemical availability of metals in soil. Industrially polluted, metal sulphate amended and sewage sludge treated soils were used in our study. Cadmium sulphate amended and industrially contaminated soils all had > 65% of the total soil solution Cd present as free Cd2+. However, increasing total soil Cd concentrations by adding CdSO4 resulted in smaller total soil solution Cd. Consequently, the free Cd2+ concentrations in soil solutions extracted from these soils were smaller than in the same soil contaminated by sewage sludge addition. Amendment with ZnSO4 gave much greater concentrations of free Zn2+ in soil solutions compared with the same soil after long-term Zn contamination via sewage sludge additions. Our results demonstrate the difficulty in comparing total soil solution and free metal ion concentrations for soils from different areas with different physiochemical properties and sources of contamination. However, when comparing the same Woburn soil, Cd was much less available as Cd2+ in soil solution from the CdSO4 amended soils compared with soil contaminated by about 36 years of sewage sludge additions. In contrast, much more Zn was available in soil solution as free Zn2+ in the ZnSO4 amended soils compared with the sewage sludge treated soils.     

Mobility and plant availability of risk elements in soil after long-term application of farmyard manure

Crop rotation long-term field experiments were established in 1955 and 1956 at three locations in the Czech Republic (?áslav, Ivanovice, and Lukavec) differing in their climatic and soil physicochemical properties. The effect of long-term application of farmyard manure and farmyard manure + NPK treatments on plant-available, easily mobilizable, potentially mobilizable, and pseudo-total contents of arsenic (As), cadmium (Cd), copper (Cu), lead (Pb), and zinc (Zn) contents in soils (in 2013) as well as the uptake of these elements by winter wheat (Triticum aestivum L.) grain and straw were analyzed in the two following seasons: 2012 and 2013. The treatments resulted in increasing the soil pH level when compared to the control, but the cation exchange capacity remained unchanged. Although all fertilizers were applied for six decades, the pseudo-total concentration elements in both the soil and wheat plants stayed far below those of the Czech and European threshold limits for agricultural soils and cereals for human nutrition and feedstuff. Although the mobile pools of As, Cu, and Zn were slightly changed at the treated soils, these changes were not related to the element uptake by the wheat plants. Moreover, the effect of the location and growing season was more decisive for the differences in soil and plant element contents than for the individual treatments. Thus, the long-term application of farmyard manure did not result in any substantial change in risk element contents in both soils and winter wheat plants.     

In situ stabilization of trace metals in a copper-contaminated soil using P-spiked Linz-Donawitz slag

Purpose  

A former wood exploitation revealing high Cu and As concentration of the soils served as a case study for assisted phytoextraction.     

2种分步浸提方法对土壤中Cr形态提取效果的比较

实验模拟了受铬渣污染的土壤环境,比较在不同活性炭加入量下2种典型分步浸提方法:Tessier 5步法和改进的7步分离方法得到的不同结果,探究适合于铬渣污染对土壤环境的铬形态浸提方法。实验结果表明,2种方法的浸提数据虽有较大差异,但能得到相对一致的变化趋势;七步法形态分类更为细致,99%以上的铬都分布在2~3个结合形态,Tessier五步法的物料衡算结果更为准确(96%~103%),相比七步法形态分类更具包容性,数据更具重现性;随着活性炭的加入,土壤环境中游离铬离子明显减少,转化为有机结合态等更稳定的结合形态,说明活性炭能有效固定土壤环境中游离的铬离子,增加其迁移稳定性。     

Combined source apportionment,using positive matrix factorization–chemical mass balance and principal component analysis/multiple linear regression–chemical mass balance models

The methods of positive matrix factorization–chemical mass balance and principal component analysis/multiple linear regression–chemical mass balance were studied in this paper, for combined source apportionment. Due to the high similarity among the source profiles, several problems would raised when only one receptor model was applied. For example, the collinearity problem would result in the negative contributions when applying CMB model; certain sources would not to be separated out when applying PCA or PMF model. In this study, PCA/MLR–CMB model and PMF–CMB were attempted to resolve the problem, where the combined models were applied to study the synthetic and ambient datasets. In synthetic dataset, there were seven sources (six actual sources from real world, and one unknown source). The results obtained by the combined models show that the combined source apportionment technique is feasible. In addition, an ambient dataset from a northern city in China was analyzed by PCA/MLR–CMB model and PMF–CMB model, and these two models got the similar results. The results show that coal combustion contributed the largest fraction to the total mass.