Influence of EDDS on metal speciation in soil extracts: measurement and mechanistic multicomponent modeling

The use of the [S,S]-isomer of EDDS to enhance phytoextraction has been proposed for the remediation of heavy metal contaminated soils. Speciation of metals in soil solution in the presence of EDDS and dissolved organic matter (DOM) received, however, almost no attention, whereas metal speciation plays an important role in relation to uptake of metals by plants. We investigated the influence of EDDS on speciation of dissolved metals in batch extraction experiments using fourfield-contaminated soils with pH varying between 4.7 and 7.2. Free metal concentrations were determined with the Donnan membrane technique, and compared with results obtained with the chemical speciation program ECOSAT and the NICA-Donnan model using a multicomponent approach. Addition of EDDS increased total metal concentrations in our soil extracts by a factor between 1.1 and 32 (Al), 2.1-48 (Cu), 1.1-109 (Fe), 1.1-5.5 (Ni), and 1.3-17 (Zn). In general, Al, Cu, Fe, and Zn had the largest total concentrations in the EDDS-treated extracts, but the contribution of these metals to the sum of total metal concentrations varied significantly between our soils. Free metal concentrations varied between 7.0 and 8.9 (pCd2+), 3.9-9.9 (pCu2+), 6.3-10.2 (pNi2+), and 5.2-7.0 (pZn2+). Addition of EDDS decreased free metal concentrations by a factor between 1.4 and 1.9 (Cd), 3.4-216 (Cu), 1.3-186 (Ni), and 1.3-3.3 (Zn). Model predictions of free metal concentrations were very good, and predicted values were mostly within 1 order of magnitude difference from the measured concentrations. A multicomponent approach had to be used in our model calculations, because competition between Fe and other metals for binding with EDDS was important. This was done by including the solubility of metal oxides in our model calculations. Multicomponent models can be used in chelant-assisted phytoextraction experiments to predict the speciation of dissolved metals and to increase the understanding of metal uptake by plants.     

Chemical speciation of Zn,Cd, Cu,and Pb in pore waters of agricultural and contaminated soils using Donnan dialysis

Knowledge of trace metal speciation in soil pore waters is important in addressing metal bioavailability and risk assessment of contaminated soils. Numerous analytical methods have been utilized for determining trace metal speciation in aqueous environmental matrixes; however, most of these methods suffer from significant interferences. The Donnan dialysis membrane technique minimizes these interferences and has been used in this study to determine free Zn2+, Cd2+, Cu2+, and Pb2+ activities in pore waters from 15 agricultural and 12 long-term contaminated soils. The soils vary widely in their origin, pH, organic carbon content, and total metal concentrations. Pore water pM2+ activities also covered a wide range and were controlled by soil pH and total metal concentrations. For the agricultural soils, most of the free metal activities were below detection limit, apart from Zn2+ for which the fraction of free Zn2+ in soluble Zn ranged from 2.3 to 87% (mean 43%). Five of the agricultural soils had detectable free Cd2+ with fractions of free metal ranging from 59 to 102% (mean 75%). For the contaminated soils with detectable free metal concentrations, the fraction of free metal as a percentage of soluble metal varied from 9.9 to 97% (mean 50%) for Zn2+, from 22 to 86% (mean 49%) for Cd2+, from 0.4 to 32.1% (mean 5%) for Cu2+, and from 2.9 to 48.8% (mean 20.1%) for Pb2+. For the contaminated soils, the equilibrium speciation programs GEOCHEM and WHAM Model VI provided reasonable estimates of free Zn2+ fractions in comparison to the measured fractions (R2 approximately 0.7), while estimates of free Cd2+ fractions were less agreeable (R2 approximately 0.5). The models generally predicted stronger binding of Cu2+ to DOC and hence lower fractions of free Cu2+ as compared with the observed fractions. The binding of Cu2+ and Pb2+ to DOC predicted by WHAM Model VI was much strongerthan that predicted by GEOCHEM.     

Column extraction of heavy metals from soils using the biodegradable chelating agent EDDS

A possible remediation strategy for metal polluted soils is washing with chelants. Here, we compare the efficiency of batch and column extraction of Cu, Zn, and Pb from three soils using the biodegradable chelant EDDS. A total of 53-80% of Cu was extracted in batch and 18-26% in column extraction. For Zn, the extractability was 16-50% in batch and 20-64% in columns and for Pb 25-52 and 18-91%, respectively. Column leaching was therefore equally or better suited for Zn and Pb removal. The longer extraction time in the column resulted in more formations of Fe(III)EDDS by slow dissolution of iron oxides. Zn was uniformly washed from the column, while Cu and Pb were extracted in the top layers and deposited in the bottom layers, presumably by biodegradation of the metal-EDDS complexes and slow dissolution of iron oxides. Between 18 and 42% of the applied EDDS was lost through biodegradation after 7 weeks. In short time experiments, only 6% of EDDS was degraded. Using EDDS concentrations in excess of available heavy metals caused pronounced leaching of organic matter and clogging of the column. Our results prove that heap leaching using EDDS is a promising approach to reduce the heavy metal content of polluted soils.     

Uptake of heavy metals by vegetable plants grown on contaminated soil and their bioavailability in the human gastrointestinal tract.

Lettuce, spinach, radish and carrot were grown on compost that had previously been contaminated at different concentrations of Cd, Cu, Mn, Pb and Zn. Control plants of each vegetable were also grown on unadulterated compost. The experiment was carried out under greenhouse conditions. Mature plants were harvested and their roots and leaves collected. Soil samples from each growing pot and plant materials were acid digested and analysed to determine total metal concentration. Flame-Atomic Absorption Spectroscopy (FAAS) was employed to determine metal concentrations in soil and plant samples (Mn and Zn), while Cd, Cu and Pb in plant materials were analysed by Differential Pulse Anodic Stripping Voltammetry (DP-ASV). Soil (BCR 146R and GBW 07310) and plant (tea leaves, INCT-TL-1) certified reference materials were used to assess accuracy and precision. The edible part of plants, i.e. the leaves of lettuce and spinach and the roots of radish and carrot, were also extracted using an in vitro gastrointestinal (GI) extraction to assess metal bioavailability. The results showed that the uptake of Cd, Cu, Mn and Zn by plants corresponded to the increasing level of soil contamination, while the uptake of Pb was low. Soil-to-plant transfer factor (TF) values decreased from Mn > Zn > Cd > Cu > Pb. Moreover, it was observed from this investigation that individual plant types greatly differ in their metal uptake, e.g. spinach accumulated a high content of Mn and Zn, while relatively lower concentrations were found for Cu and Pb in their tissues. From the in vitro gastrointestinal (GI) study, results indicate that metal bioavailability varied widely from element to element and according to different plant types. The greatest extent of metal releasing was found in lettuce (Mn, 63.7%), radish (Cu, 62.5%), radish (Cd, 54.9%), radish (Mn, 45.8%) and in lettuce (Zn, 45.2%).     

Induced phytoextraction/soil washing of lead using biodegradable chelate and permeable barriers

Chelate-induced remediation has been proposed as an effective tool for the extraction of lead (Pb) from contaminated soils by plants. However, side-effects, mainly mobilization and leaching of Pb, raise environmental concerns. Biodegradable, synthetic organic chelate ethylenediaminedisuccinic acid (EDDS), and commonly used ethylenedimanetetraacetic acid (EDTA) were used for induced phytoextraction with a test plant Brassica rapa and in situ washing of soil contaminated with 1350 mg/kg of Pb. Horizontal permeable barriers were placed 20 cm deep in soil columns and tested for their ability to prevent leaching of Pb. The reactive materials in the barriers were nutrient enriched vermiculite, peat or agricultural hydrogel, and apatite. EDTA and EDDS addition increased Pb concentrations in the test plant by 158 and 89 times compared to the control, to 817 and 464 mg/kg, respectively. In EDTA treatments, approximately 25% or more of total initial soil Pb was leached in single cycle of chelate addition. In EDDS treatments, 20% of the initial Pb was leached from columns with no barrier, while barriers with vermiculite or hydrogel and apatite decreased leaching by more than 60 times, to 0.35%. 11.6% of total initial Pb was washed from the soil above the barrier with vermiculite and apatite, where almost all leached Pb was accumulated. Results indicate that use of biodegradable chelate EDDS and permeable barriers may lead to environmentally safe induced Pb phytoextraction and in situ washing of Pb.     

江西抚州烟区土壤及烟叶重金属污染状况评价

为了弄清江西抚州烟区土壤和烟叶中As、Cd、Cr、Cu、Ni、Pb、Zn和Hg等重金属含量和污染状况,运用内梅罗指数和相关分析法,对这些重金属元素在土壤和烟叶中的含量进行了测定。结果表明,该烟区土壤中重金属含量总体上低于我国土壤二级标准（GB15618-1995）,但其污染程度已处于警戒线水平,Cd和Hg为烟区土壤主要风险因子。土壤和烟叶中重金属含量顺序分别为Zn> Pb> Cr> Cu> Ni> As> Cd> Hg和Zn> Cu> Pb> Cd> Cr> Ni> As> Hg,土壤中Hg、Cd、As和烟叶中Ni、Cr变异系数均较大。烟叶中重金属富集系数顺序为Cd> Zn> Cu> Hg> Ni> Cr> Pb> As,烟叶Cd富集系数高达11.67,表明烟草属于Cd强烈富集作物。     

Thermally induced changes in metal solubility of contaminated soils is linked to mineral recrystallization and organic matter transformations

Soils are biogeochemical systems under continual modification by biological and chemical processes. Trace element solid-solution partitioning is thus influenced by long-term changes to these solid phases. We study Pb, Cd, Zn, and Cu solution speciation and solid-phase dynamics in two soils of volcanic origin (Te Akatea and Egmont, high in noncrystalline aluminosilicates), an oxisol from Brazil (Oxisol, high in oxides of Al and Fe), and several sludge-treated soils (labeled NYS soils, high in organic materials). Total soluble (by ICP) and labile (by ASV) concentrations of Pb, Cd, Zn, and Cu were determined after incubation of the soils for about 1.5 yr at room (23 degrees C) and elevated (70 degrees C) temperatures. Changes occurring to the solid phases were monitored by FTIR and extraction with oxalate and pyrophosphate. It is shown that induced hydrolysis or decomposition of organic materials in soils results in increases in both labile and total soluble concentrations of Pb, Cd, Cu, and Zn in solution. Labile and total soluble concentrations of Cu and Zn increase concomitantly with dissolved organic carbon (DOC); the nonlabile soluble fraction also increases with increasing DOC. Similarly, the concentration of Cd and Pb in solution increases with increasing DOC; however, most soluble Cd and Pb is asv-labile. Only in the Egmont soil (mineralogy dominated by proto-imogolite allophane) was reduced Pb solubility observed after prolonged equilibration and heating. Lead solubility increased after partial crystallization of amorphous minerals in the Te Akatea and the Oxisol. Thus, for most of the metal-soil systems studied, prolonged thermal treatment at 70 degrees C increased total soluble and asv-labile metals, suggesting that aging effects on metals in contaminated soils could release metals to labile forms in some cases.     

冀东典型蔬菜种植区设施土壤重金属特征

目的探究冀东典型蔬菜种植区(唐山市和承德市)设施土壤重金属特征。方法对设施大棚进行调查并采集表层土壤样品,检测其重金属,即镉(Cd)、汞(Hg)、砷(As)、铅(Pb)、铬(Cr)、铜(Cu)、锌(Zn)含量,并依据HJ/T 333—2006《温室蔬菜产地环境质量评价标准》进行了土壤质量评价。结果除As外,其他重金属均超过河北省土壤背景值(国家环境保护局),最高为Hg,为背景值的3.46倍。Cd与棚龄呈显著负相关关系(P<0.05)。从地理分布来看,Hg呈现西高东低的分布特征,而As、Pb则呈现南高北低的分布特征。从重金属单项质量指数来看,Cd、Hg、As、Cr、Zn均未超标;Cu、Pb超标率分别为7.37%和22.11%,属轻度污染。从重金属综合质量指数看,3.16%的土壤为超标土壤,属轻度污染,超标率较高的区县为隆化县、乐亭县、滦平县、宽城县和滦南县,重金属综合质量指数与土壤pH呈极显著负相关关系(P<0.01)。结论冀东典型蔬菜种植区设施土壤存在Cu、Pb的轻度污染现象,后续需要对蔬菜中的Cu、Pb进行调查以评估蔬菜产品的安全性。     

Critical assessment of chelant-enhanced metal phytoextraction

Chelant-enhanced phytoextraction has received a lot of attention in the past decade. In theory, this technique could cleanse metal polluted soils by solubilizing contaminating metals, allowing them to be taken up by plants that would subsequently be removed from the site. We review the processes of metal solubilization, uptake by plants, and leaching during chelant-enhanced phytoextraction. A large excess of chelant is required to solubilize the target metal due to the co-solubilization of Ca and Fe. Chelated metals are taken up via the apoplastic pathway. Disruption of the Casparian Band is required to achieve the high shoot concentrations needed for phytoextraction. Therefore, adding chelants to a soil increases not only the total dissolved metal concentration but also changes the primary route of plant metal-uptake from the symplastic to the apoplastic pathway. Depending on metal, plant species, and chelant concentration, significant increases in metal uptake are likely. Soil solution chelate concentrations of at least several mM are required to induce appreciable shoot concentrations. A simple calculation reveals that at such soil solution concentrations plants will remove only a small fraction of the solubilized metals. Leaching, exacerbated by preferential flow processes, is unavoidable. Chelant-enhanced phytoextraction is therefore limited to areas where the connection with groundwater has been broken, orwhere leaching is unimportant. Chelant-enhanced phytoextraction may nonetheless have a role in enhancing the uptake of essential trace metals. Such a role warrants further investigations into the use of biodegradable chelants such as ethylenediaminedisuccinic acid (EDDS).     

Heavy metal concentrations and enzyme activities in soil from a contaminated Korean shooting range

Soil enzyme activities and heavy metal concentrations (Cd, Zn, Cu and Pb) were measured at a general shooting range in South Korea. Total heavy metal concentrations varied with pH, and were negatively correlated with moisture content and organic matter. Most enzyme activities (dehydrogenase, acid phosphatase and beta-glucosidase) and ATP values (measure of biomass) were lower in polluted soils, especially in bald spots contaminated by heavy metals and TNT (2,4,6-trinitrotoluene). These data indicate that concentrated shooting activity inhibits enzyme activity and microbial growth. Soil enzyme activities in richly vegetated spots around the general shooting range were higher (2- to 3-fold) than in bald spots, but lower in areas of heavy metal contamination. Our results demonstrate that the dominant plant species in richly vegetated spots accumulated heavy metals from soils, and suggest certain plants may be useful for decontaminating polluted soil.     

Electrodialytic removal of Cu, Zn, Pb, and Cd from harbor sediment: influence of changing experimental conditions

Electrodialytic remediation (EDR) was used to remove Cu, Zn, Pb, and Cd from contaminated harbor sediment. Extraction experiments were made prior to EDR, and the metal desorption was pH dependent but not liquid-to-solid ratio (L/S) dependent. The desorption order was Cd > Zn > Pb > Cu. Electrodialytic experiments were made with HCl as desorbing agent in a sediment suspension, which was stirred during EDR. Effects of different current strengths and L/S ratios on the heavy metal removal were investigated on wet and air-dried sediment. The effects of drying the sediment were negligible for the removal of Cu, Zn, and Pb, probably due to oxidation of the sediments during stirring. Contrary, Cd removal was lower in the wet sediment as compared to the air-dried. The heavy metal removal was influenced by higher current strengths and varying L/S ratios. The highest removal obtained was in an experiment with dry sediment (L/S 8) and a 70 mA applied current that lasted 14 days. These experimental conditions were thereafter used to remediate more strongly contaminated sediments. Regardless of the initial heavy metal concentrations in the sediments, 67-87% Cu, 79-98% Cd, 90-97% Zn, and 91-96% Pb were removed.     

Extraction of heavy metals from soils using biodegradable chelating agents

Metal pollution of soils is widespread across the globe, and the clean up of these soils is a difficulttask. One possible remediation technique is ex-situ soil washing using chelating agents. Ethylenediaminetetraacetic acid (EDTA) is a very effective chelating agent for this purpose but has the disadvantage that it is quite persistent in the environment due to its low biodegradability. The aim of our work was to investigate the biodegradable chelating agents [S,S]-ethylenediaminedisuccinic acid (EDDS), iminodisuccinic acid (IDSA), methylglycine diacetic acid (MGDA), and nitrilotriacetic acid (NTA) as potential alternatives and compare them with EDTA for effectiveness. Kinetic experiments showed for all metals and soils that 24 h was the optimum extraction time. Longer times only gave minor additional benefits for heavy metal extraction but an unwanted increase in iron mobilization. For Cu at pH 7, the order of the extraction efficiency for equimolar ratios of chelating agent to metal was EDDS > NTA> IDSA > MGDA > EDTA and for Zn it was NTA > EDDS > EDTA >MGDA > IDSA. The comparatively low efficiency of EDTA resulted from competition between the heavy metals and co-extracted Ca. For Pb the order of extraction was EDTA > NTA >EDDS due to the much stronger complexation of Pb by EDTA compared to EDDS. At higher concentration of complexing agent, less difference between the agents was found and less pH dependence. There was an increase in heavy metal extraction with decreasing pH, but this was offset by an increase in Ca and Fe extraction. In sequential extractions EDDS extracted metals almost exclusively from the exchangeable, mobile, and Mn-oxide fractions. We conclude that the extraction with EDDS at pH 7 showed the best compromise between extraction efficiency for Cu, Zn, and Pb and loss of Ca and Fe from the soil.     

Evaluation of in Situ DGT Measurements for Predicting the Concentration of Cd in Chinese Field-Cultivated Rice: Impact of Soil Cd:Zn Ratios

DGT (diffusive gradients in thin-films) has been proposed as a tool for predicting Cd concentrations in rice grain, but there is a lack of authenticating data. To further explore the relationship between DGT measured Cd and concentrations in rice cultivated in challenging, metal degraded, field locations with different heavy metal pollutant sources, 77 paired soil and grain samples were collected in Southern China from industrial zones, a "cancer village" impacted by mining waste and an organic farm. In situ deployments of DGT in flooded paddy rice rhizospheres were compared with a laboratory DGT assay on dried and rewetted soil. Total soil concentrations were a very poor predictor of plant uptake. Laboratory and field deployed DGT assays and porewater measurements were linearly related to grain concentrations in all but the most contaminated samples where plant toxicity occurred. The laboratory DGT assay was the best predictor of grain Cd concentrations, accommodating differences in soil Cd, pollutant source, and Cd:Zn ratios. Field DGT measurements showed that Zn availability in the flooded rice rhizospheres was greatly diminished compared to that of Cd, resulting in very high Cd:Zn ratios (0.1) compared to commonly observed values (0.005). These results demonstrate the potential of the DGT technique to predict Cd concentrations in field cultivated rice and demonstrate its robustness in a range of environments. Although, field deployments provided important details about in situ element stoichiometry, due to the inherent heterogeneity of the rice rhizosphere soils, deployment of DGT in dried and homogenized soils offers the best possibility of a soil screening tool.     

Modeling metal binding to soils: the role of natural organic matter

The use of mechanistically based models to simulate the solution concentrations of heavy metals in soils is complicated by the presence of different sorbents that may bind metals. In this study, the binding of Zn, Pb, Cu, and Cd by 14 different Swedish soil samples was investigated. For 10 of the soils, it was found that the Stockholm Humic Model (SHM) was able to describe the acid-base characteristics, when using the concentrations of "active" humic substances and Al as fitting parameters. Two additional soils could be modeled when ion exchange to clay was also considered, using a component additivity approach. For dissolved Zn, Cd, Ca, and Mg reasonable model fits were produced when the metal-humic complexation parameters were identical for the 12 soils modeled. However, poor fits were obtained for Pb and Cu in Aquept B horizons. In two of the soil suspensions, the Lund A and Romfartuna Bhs, the calculated speciation agreed well with results obtained by using cation-exchange membranes. The results suggest that organic matter is an important sorbent for metals in many surface horizons of soils in temperate and boreal climates, and the necessity of properly accounting for the competition from Al in simulations of dissolved metal concentrations is stressed.     

Plant Availability of Heavy Metals in Soils Previously Amended with Heavy Applications of Sewage Sludge

Plant uptake is one of the major pathways by which sludge-borne potentially toxic metals enter the food chain. This study examined the accumulation of Cd, Cu, Ni, Pb and Zn in wheat, carrots and spinach grown on soils from 13 sites previously amended with sewage sludge. Winter wheat, carrots and spinach were grown consecutively under field like conditions. The results showed that plant availability of heavy metals differed widely among the crop species. The accumulation of Cd, Ni and Zn in the plants showed the greatest increases compared to their background levels. The Cu and Pb accumulation in the plants grown on sludge-amended soils showed only small increases compared to those grown on uncontaminated soils. Multiple regression analysis of various soil properties showed that the surest way to control the accumulation of metals in food plants is by controlling their concentrations in the soils. Furthermore, soils with a non-acidic pH and a clayey texture tended to achieve better control of metal accumulation in food plants compared to those with an acidic reaction and a coarse texture. Metal concentrations in the plants generally correlated well with those extracted from soils in 0·005 M DTPA, 0·05 M EDTA-(Na)₂, 1 M NH₄NO₃ and 0·05 M CaCl₂. The EDTA, however, proved to be a more reliable and consistent test in predicting the accumulation of metals in the plants. The results also showed that liming soils to pH 7 effectively reduced the metal contents in carrots and spinach, but liming to pH 6·5 had little effect on metal concentrations in wheat grain. © 1997 SCI.     

Accumulation of Cu, Pb, Ni and Zn in the halophyte plant Atriplex grown on polluted soil

BACKGROUND: Three annual Atriplex species—A. hortensis var. purpurea, A. hortensis var. rubra and A. rosea—growing on soil with various levels of the heavy metals copper, lead, nickel, and zinc, have been investigated. RESULTS: Metal accumulation by Atriplex plants differed among species, levels of polluted soil and tissues. Metals accumulated by Atriplex were mostly distributed in root tissues, suggesting that an exclusion strategy for metal tolerance widely exists in them. The increased concentration of heavy metals in soil led to increases in heavy metal shoot and root concentrations of Ni, Cu, Pb and Zn in plants as compared to those grown on unpolluted soil. Accumulation was higher in roots than shoots for all the heavy metals. None of the plants were suitable for phytoextraction because no hyperaccumulator was identified. However, plants with a high bioconcentration factor and low translocation factor have the potential for phytostabilization. Similarly, the correlation between metal concentrations and translocations in plants (BCFs and TFs) using a linear regression was also statistically significant. CONCLUSION: Among the plants studied, var. purpurea was the most efficient in accumulating Pb and Zn in its shoots, whereas var. rubra was most suitable for phytostabilization of sites contaminated with Cu and Ni. Copyright © 2011 Society of Chemical Industry     

Multielementary (Cd, Cu, Pb, Zn, Ni) Stable Isotopic Exchange Kinetic (SIEK) method to characterize polymetallic contaminations

A new method is proposed to precisely and simultaneously quantify the exchangeable pool of metals in soils and to describe its reactivity at short- and long-term. It is based on multielementary Stable Isotopic Exchange Kinetics (multi-SIEK), first validated by a comparison between two monoelementary radioactive ((109)Cd*, (65)Zn*) IEK experiments, a mono- ((106)Cd) and multi- ((62)Ni, (65)Cu, (67)Zn, (106)Cd, (204)Pb) SIEK. These experiments were performed on a polluted soil located near the Zn smelter plant of Viviez (Lot watershed, France). The IEK results obtained for Cd and Zn were consistent across the experiments. (109)Cd*, (65)Zn* IEK, and multi-SIEK were then applied on 3 non- and moderate impacted soils that also provided consistent results for Cd and Zn. Within these experimental conditions, it can be concluded that no competition occurs between Cd, Zn, and the other metals during SIEK. Multi-SIEK results indicate that the isotopically exchangeable pool of Ni, Zn, and Cu are small (E(Ni), E(Zn), and E(Cu) values up to 17%) whatever the pollution degree of the soils considered in this study and whatever the duration of the interaction. On the contrary, Cd displays the highest E values (from 35% to 61% after 1 week), and E(Pb) displays a maximum value of 26% after 1 week. The multi-SIEK provides useful information on metal sources and reactivity relationship. Ni would be located in stable pedogenic phases according to its very low enrichment factor. The low E(Zn) and E(Cu) are consistent with location of Zn and Cu in stable phases coming from tailings erosion. Though Pb enrichments in soils may also be attributed to tailings particles, its larger exchangeable pool suggests that the Pb-bearing phases are more labile than those containing Zn and Cu. The high mobility of Cd in upstream soils indicates that it has been mostly emitted as reactive atmospheric particles during high temperature ore-treatment.     

Kinetics of Zn release in soils and prediction of Zn concentration in plants using diffusive gradients in thin films

Effective concentrations (CE) of Zn measured by the technique of DGT (diffusive gradients in thin films) were compared, along with total concentrations of Zn and the concentrations of Zn in soil solutions, to Zn concentrations in plants. Soils variously contaminated with Zn were collected in the vicinity of two galvanized electrical transmission towers (pylons) and two motorway crash barriers. Lepidium sativum was grown in each soil and in corresponding control soils amended with ZnCl2 to similar total Zn concentrations. CE, concentrations in soil solution, and total Zn were measured in all soils, and total Zn was measured in the plant shoots. The CE values, soil solution Zn, and shoot Zn concentrations were all larger in ZnCl2 amended soils than in field contaminated soils at corresponding total Zn. Correlations between the concentration of Zn in the plants and the measured soil parameter followed the order CE > soil solution > total Zn. The low scatter in the plot of log plant concentration versus log CE revealed a relationship with two distinct features. Plant Zn was between 100 and 300 mg/kg up to an effective Zn concentration of about 2 mg/L, above which plant Zn increased steadily with increasing CE. Use of a dynamic model to interpret the DGT measurement suggests that the intrinsic rate of release of Zn from solid phase to solution, expressed as a rate constant, is much higher for soils that receive fresh supplies of Zn. This finding provides a mechanistic basis for reconciling laboratory experiments, where metal is freshly amended, to data obtained in the field. The potential of DGT as a surrogate for metal availability to plants is further confirmed by this work.     

Adaptation of soil biological nitrification to heavy metals

The adaptive response of soil biological nitrification to Zn and Pb was assessed using an in situ method we have developed. The method is based on reinoculating a sterilized metal contaminated soil with the same soil that is either uncontaminated or has been incubated with metal. This approach excludes the potentially confounding effects of metal aging reactions in soils. We found added Zn concentrations which gave rise to a decrease in nitrification to 50% that of the uncontaminated soil (i.e. EC50) of 210 mg/kg for communities not previously exposed to Zn and 850 mg/kg for communities exposed to Zn for 17 months, indicating that significant adaptation of the community to Zn had occurred. Similarly, this protocol was able to demonstrate adaptation of soil biological nitrification to Pb, with EC50 values of 1960 and 3150 mg/kg for the unexposed and exposed treatments, respectively. Exposure of unadapted and adapted microbial communities to a combination of Zn and Cd showed that the presence of Cd did not lead to greater toxicity in either community. Adapted communities were not more sensitive to decreases in soil pH than unadapted communities. Prior exposure to Zn was found to confer significantly greater tolerance of the community to Pb. Prior exposure to Pb similarly conferred significantly greater tolerance of the community to Zn. Implications of the adaptive capacity of soil microbes to the development of critical threshold values for heavy metals in soil based on ecotoxicity assessments are discussed.     

Complexation with dissolved organic matter and solubility control of heavy metals in a sandy soil

The complexation of heavy metals with dissolved organic matter (DOM) in the environment influences the solubility and mobility of these metals. In this paper, we measured the complexation of Cu, Cd, Zn, Ni, and Pb with DOM in the soil solution at pH 3.7-6.1 using a Donnan membrane technique. The results show that the DOM-complexed species is generally more significant for Cu and Pb than for Cd, Zn, and Ni. The ability of two advanced models for ion binding to humic substances, e.g., model VI and NICA-Donnan, in the simulation of metal binding to natural DOM was assessed by comparing the model predictions with the measurements. Using the default parameters of fulvic and humic acid, the predicted concentrations of free metal ions from the solution speciation calculation using the two models are mostly within 1 order of magnitude difference from the measured concentrations, except for Ni and Pb in a few samples. Furthermore, the solid-solution partitioning of the metals was simulated using a multisurface model, in which metal binding to soil organic matter, dissolved organic matter, clay, and iron hydroxides was accounted for using adsorption and cation exchange models (NICA-Donnan, Donnan, DDL, CD-MUSIC). The model estimation of the dissolved concentration of the metals is mostly within 1 order of magnitude difference from those measured except for Ni in some samples and Pb. The solubility of the metals depends mainly on the metal loading over soil sorbents, pH, and the concentration of inorganic ligands and DOM in the soil solution.