Enhanced multi-metal extraction with EDDS of deficient and excess dosages under the influence of dissolved and soil organic matter

This study investigated the influence of dissolved and soil organic matter on metal extraction from an artificially contaminated soil. With high concentration of DOM, the extraction of Cu, Zn and Pb was enhanced by forming additional metal-EDDS complexes under EDDS deficiency. However, the enhancement of metal extraction under EDDS excess was probably due to the soil structure being disrupted owing to humic acid enhanced Al and Fe dissolution, which induced more metals dissolving from the soils. Fulvic acid was found to enhance metal extraction to a greater extent compared with humic acid because of its high content of the carboxylic functional group. Cu extraction from the soil with high organic matter content using EDDS was the lowest due to the high binding affinity of Cu to SOM, whereas Zn extraction became the highest because of a preference for EDDS to extract Zn due to the high stability constant of ZnEDDS.     

Increased retention of polycyclic aromatic hydrocarbons in soils induced by soil treatment with humic substances

The analytical recovery of a mixture of polycyclic aromatic hydrocarbons (PAHs) was determined from a soil before and after oxidation with hydrogen peroxide, and subsequently treated with increasing amounts of an exogenous humic acid and subjected to different incubation periods. The release of PAHs from soil depended on the specific structure and physico-chemical properties of each PAH, and increased with additions of exogenous humic materials for both the oxidized and non-oxidized soil as well as with time of PAH permanence in soil. PAH recoveries were lower in the non-oxidized soil, thereby revealing the importance of native organic matter in increasing PAH retention in soils. This study shows that mobility of PAHs in soils can be controlled by soil conditioning with humic substances.     

Oxidation of chlorophenols in soil at natural pH by catalyzed hydrogen peroxide: the effect of soil organic matter.

This investigation reports on the effects of soil organic matter (SOM) during the oxidation of chlorophenols with Fe2+-catalyzed H2O2 (Fenton oxidation) system. The soil pH was 7.1 and was not altered. Sorption experiments of soil pre-treated under various oxidation conditions were performed. Concentrations of organic matter in the liquid phase and soil before and after oxidation were analyzed. The results were correlated to the observation in batch Fenton oxidation tests. They showed that the oxidation of chlorophenols at natural soil pH depended on the dose of H2O2 and Fe2+. The soil organic content did not vary significantly after various Fenton treatments, while the sorption of chlorophenols was 10-25% less by the oxidation. The concentration of chlorophenols in the liquid phase exhibited a "decrease and rebound" phenomenon in the batch Fenton oxidation tests. It appeared that the oxidation of SOM resulted in the release of sorbed chlorophenols which were then oxidized by the excess H2O2. An "oxidation-desorption-oxidation" scheme was proposed to describe one of the interaction mechanisms among the oxidant, SOM, and chlorophenols during oxidation.     

Aging and temperature effects on DOC and elemental release from a metal contaminated soil

The combined effect of time and temperature on elemental release and speciation from a metal contaminated soil (Master Old Site, MOS) was investigated. The soil was equilibrated at 10, 28, 45, 70 and 90 degrees C for 2 days, 2 weeks, and 2 months in the laboratory. Dissolved organic carbon (DOC), total soluble elements (by ICP), and labile metals (by DPASV) were determined in the filtered (0.22 microm) supernatants. For the samples equilibrated at 90 degrees C, DOC fractions were size fractionated by filtration and centrifugation; a subsample was only centrifuged while another was also filtered through a 0.45 microm filter. Analyses of the supernatants (ICP, DPASV, DOC) were performed on all size fraction subsamples. Dissolved organic carbon (DOC) increased both with temperature and incubation time; however, metal behavior was not as uniform. In general, total soluble metal release (ICP) paralleled the behavior of DOC, increasing with both time and temperature, and confirming the importance of soil organic matter (SOM) in metal retention. Voltammetric analysis (dpasv) of Cu and Zn showed that very little of these metals remains labile in solution due, presumably, to complexation with dissolved organic matter. Labile concentrations of Cd, on the other hand, constituted a significant portion (50%) of total soluble Cd. Copper and Al increased in solution with time (up to 2 months) and temperature up to 70 degrees C; however, at 90 degrees C the soluble concentration declined sharply. The same behavior was observed after equilibration for longer periods of time (550 days) at lower temperatures (23 and 70 degrees C). While concentrations of labile Cu and total soluble Cu and Al increased in the unfiltered samples, the trend remained the same. DPASV analysis showing shifts in labile Cu complexes with temperature and time, together with the results from the unfiltered samples, lead to the hypothesis that Cu was complexing with large polymers that could form at the elevated temperature, and thus be removed from the analyzed solution. It is possible that Cu and Al released by SOM oxidation has re-sorbed or complexed to more recalcitrant organic matter or to mineral phases. Variations in the relative molecular size fractions present within the DOC pool produced by increased time and temperature may influence the element-DOC complexes present in solution and their behavior in soil environments.     

Impact of soil organic matter on the distribution of polycyclic aromatic hydrocarbons (PAHs) in soils

The knowledge on the distribution of hydrophobic organic contaminants in soils can provide better understanding for their fate in the environment. In the present study, the n-butanol extraction and humic fractionation were applied to investigate the impact of SOM on the distribution of polycyclic aromatic hydrocarbons (PAHs). The results indicated that 80.5%-94.8% of the target PAHs could be extracted by n-butanol and 63.1%-94.6% of PAHs were associated with fulvic acid (FA). Concentrations of un-extracted PAHs increased significantly with the increasing soil organic matter (SOM), however, such an association was absent for the extractable fractions. The results suggested that the sequestration played a critical role in the accumulation of PAHs in soils. SOM also retarded the diffusion of PAHs into the humin fractions. It implied that sequestration in SOM was critical for PAH distribution in soils, while the properties of PAH compounds also had great influences.     

Sorption of naphthalene and phenanthrene by soil humic acids

Humic acids are a major fraction of soil organic matter (SOM), and sorption of hydrophobic organic chemicals by humic acids influences their behavior and fate in soil. A clear understanding of the sorption of organic chemicals by humic acids will help to determine their sorptive mechanisms in SOM and soil. In this paper, we determined the sorption of two hydrophobic organic compounds, naphthalene and phenanthrene by six pedogenetically related humic acids. These humic acids were extracted from different depths of a single soil profile and characterized by solid-state CP/MAS 13C nuclear magnetic resonance (NMR). Aromaticity of the humic acids increased with soil depth. Similarly, atomic ratios of C/H and C/O also increased with depth (from organic to mineral horizons). All isotherms were nonlinear. Freundlich exponents (N) ranged from 0.87 to 0.95 for naphthalene and from 0.86 to 0.92 for phenanthrene. The N values of phenanthrene were consistently lower than naphthalene for a given humic acid. For both compounds, N values decreased with increasing aromaticity of the humic acids, such an inverse relationship was never reported before. These results support the dual-mode sorption model where partitioning occurs in both expanded (flexible) and condensed (rigid) domains while nonlinear sorption only in condensed domains of SOM. Sorption in the condensed domains may be a cause for slow desorption, and reduced availability and toxicity with aging.     

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

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

Sorption of native polyaromatic hydrocarbons (PAH) to black carbon and amended activated carbon in soil

Organic pollutants (e.g. polyaromatic hydrocarbons (PAH)) strongly sorb to carbonaceous sorbents such as black carbon and activated carbon (BC and AC, respectively). For a creosote-contaminated soil (Sigma15PAH 5500 mg kg(dry weight(dw))(-1)) and an urban soil with moderate PAH content (Sigma15PAH 38 mg kg(dw)(-1)), total organic carbon-water distribution coefficients (K(TOC)) were up to a factor of 100 above values for amorphous (humic) organic carbon obtained by a frequently used Linear-Free-Energy Relationship. This increase could be explained by inclusion of BC (urban soil) or oil (creosote-contaminated soil) into the sorption model. AC is a manufactured sorbent for organic pollutants with similar strong sorption properties as the combustion by-product BC. AC has the potential to be used for in situ remediation of contaminated soils and sediments. The addition of small amounts of powdered AC (2%) to the moderately contaminated urban soil reduced the freely dissolved aqueous concentration of native PAH in soil/water suspensions up to 99%. For granulated AC amended to the urban soil, the reduction in freely dissolved concentrations was not as strong (median 64%), especially for the heavier PAH. This is probably due to blockage of the pore system of granulated AC resulting in AC deactivation by soil components. For powdered and granulated AC amended to the heavily contaminated creosote soil, median reductions were 63% and 4%, respectively, probably due to saturation of AC sorption sites by the high PAH concentrations and/or blockage of sorption sites and pores by oil.     

Potential contributions of clay minerals and organic matter to pentachlorophenol retention in soils

Sorption of pentachlorophenol (PCP) by pure minerals and humic acids were measured to obtain additional perspective on the potential contributions of both clay minerals and soil organic matter (SOM) to contaminants retention in soils. Four types of common soil minerals and two kinds of humic acids (HAs) were tested. The sorption affinity for PCP conformed to an order of HAs > K-montmorillonite > Ca-montmorillonite > goethite > kaolinite. Such a difference in sorption capacity could be attributed to the crucial control of HAs. Clay minerals also had their contribution, especially K-montmorillonite, which played an important, if not dominant, role in the controlling process of PCP sorption. By removing 80% (on average) of the organic carbon from the soils with H(2)O(2), the sorption decreased by an average of 50%. The sorption reversibility had been greatly favored as well. Considering the uncharged mineral fractions in soil before and after H(2)O(2)-treated, the main variation in sorption behavior of the soil might thus be related to the removed organic carbon and the reduced pH. This testified rightly the interactive effect of SOM and clay minerals on PCP sorption as a function of pH.     

Effects of aquatic humic substances on a hydrophobic ultrafiltration membrane

Natural humic surface water (pH 5.9), ion exchanged samples of the same water (pH 5.5), and aqueous solutions of isolated humic substances at pH 4.5, 5.5 and 6.5, respectively, were ultrafiltered (15°C, 0.5 bar) using hydrophobic polysulfone membranes (GR51) in a cross-flow flat sheet module. The used membrane did not completely retain natural organic matter from the surface water and the addition of complexing metals did not affect the retention any further. The changes which were induced in the membranes during each filtration run were studied by simultaneous streaming potential and flux measurements in 0.01 M KCl solutions. Zeta potentials were calculated based on the streaming potentials and the results showed changes towards more negative values for all the samples due to adsorption of organic matter onto the surface of the membrane pores. Humic acid affected the membrane charges more than fulvic acid. High ionic strength and low pH enhanced flux reduction and fouling. Filtration of natural waters caused more pore plugging and flux reduction than filtration of solutions of the isolated humic substances.     

Impact of coal mine dump contaminated soils on elemental uptake by Spinacia oleracea (spinach)

The elemental uptake and the growth response of Spinacia oleracea (spinach) to the soil contaminated with the South African bituminous coal mine dump soil, viz. 0%, 5%, 15%, and 25% w/w, was investigated. The contaminated soils were analyzed for pH, cation exchange capacity (CEC), soil organic matter (SOM), and concentrations of selected heavy metals. The pH, SOM, and CEC decreased with an increase in contamination indicating the acidic nature of coal mine soil and the raise in the soil binding sites. The distribution of Fe, Mn, Ni, Cd, and Pb in the in roots and leaves of the plants was determined in two stages of plant growth. Spinach showed high accumulation of Fe and increased levels of Ni and Cd with an increase in contamination. No plant growth was recorded with 25% contamination.     

Effects of thermal desorption on the composition of two coking plant soils: impact on solvent extractable organic compounds and metal bioavailability

To evaluate the efficiency and the influence of thermal desorption on the soil organic compartment, contaminated soils from coking plant sites (NM and H) were compared to their counterparts treated with thermodesorption. The extractable organic matter, and the metal content and distribution with soil compartments were studied.In both thermodesorbed soils, PAH (polycyclic aromatic hydrocarbon) degradation exceeded 90%. However, the thermal desorption led not only to a volatilization of the organic compounds but also to the condensation of extractable organic matter.The treatments only affected the Fe and Zn distribution within the more stable fractions, whereas the organic compound degradation did not affect their mobility and availability.     

Effect of coal mine soil contamination on the elemental uptake and distribution in two edible Amaranthus species, A. dubius and A. hybridus

The impact of coal mine dump contaminated soil on the elemental uptake by two edible plants, namely, Amaranthus dubius (red herbs) and Amaranthus hybridus (green herbs), was studied by investigating their response and ability to tolerate and accumulate varying levels of elements in their roots and shoots. The vegetation was grown on varying amounts of contaminated soil, viz. 0%, 5%, 15%, 25% w/w using coal mine dump soil. The soil was analyzed for soil pH, cation exchange capacity (CEC), soil organic matter (SOM), moisture content, and selected heavy metals. The distribution of six metals, namely, Pb, Cd, Hg, Ni, Mn, and Fe, in roots, stem, and leaves of the plants was determined in two stages of growth after 5 weeks and 10 weeks. All soil and plant samples were microwave digested and subjected to heavy metal analysis using the ICP-OES, GFAAS, and CVAAS. The pH of the coal mine dump contaminated soil decreased with an increase in contamination. Both the SOM and CEC values decreased, which increases the availability of elements, by providing more binding sites in the soil. Relatively, the red herbs had higher elemental concentrations than the green herbs. Both plants recorded high manganese accumulation. No mercury was detected in the soils or plants.     

Speciation of zinc in contaminated soils

The chemical speciation of zinc in soil solutions is critical to the understanding of its bioavailability and potential toxic effects. We studied the speciation of Zn in soil solution extracts from 66 contaminated soils representative of a wide range of field conditions in both North America and Europe. Within this dataset, we evaluated the links among the dissolved concentrations of zinc and the speciation of Zn(2+), soil solution pH, total soil Zn, dissolved organic matter (DOM), soil organic matter (SOM) and the concentrations of different inorganic anions. The solid-liquid partitioning coefficient (K(d)) for Zn ranged from 17 to 13,100Lkg(-1) soil. The fraction of dissolved Zn bound to DOM varied from 60% to 98% and the soil solution free Zn(2+) varied from 40% to 60% of the labile Zn. Multiple regression equations to predict free Zn(2+), dissolved Zn and the solid-liquid partitioning of Zn are given for potential use in environmental fate modeling and risk assessment. The multiple regressions also highlight some of the most important soil properties controlling the solubility and chemical speciation of zinc in contaminated soils.     

Potential availability of heavy metals to phytoextraction from contaminated soils induced by exogenous humic substances

Effective phytoremediation of soils contaminated by heavy metals depends on their availability to plant uptake that, in turn, may be influenced by either the existing soil humus or an exogenous humic matter. We amended an organic and a mineral soil with an exogenous humic acid (HA) in order to enhance the soil organic carbon (SOC) content by 1% and 2%. The treated soils were further enriched with heavy metals (Cu, Pb, Cd, Zn, Ni) to a concentration of 0, 10, 20, and 40 microg/g for each metal and allowed to age at room temperature for 1 and 2 months. After each period, they were extracted for readily soluble and exchangeable (2.5% acetic acid), plant-available (DTPA, Diethylentriaminepentaacetic acid), and occluded (1 N HNO(3)) metal species. Addition of HA generally reduced the extractability of the soluble and exchangeable forms of metals. This effect was directly related to the amount of added HA and increased with ageing time. Conversely, the potentially plant-available metals extracted with DTPA were generally larger with increasing additions of exogenous HA solutions. This was attributed to the formation of metal-humic complexes, which ensured a temporary bioavailability of metals and prevented their rapid transformation into insoluble species. Extractions with 1 N HNO(3) further indicated that the added metals were present in complexes with HA. The observed effects appeared to also depend on the amount of native SOC and its structural changes with ageing. The results suggest that soil amendments with exogenous humic matter may accelerate the phytoremediation of heavy metals from contaminated soil, while concomitantly prevent their environmental mobility.     

Metal extractability patterns to evaluate (potentially) mobile fractions in periurban calcareous agricultural soils in the Mediterranean area—analytical and mineralogical approaches

A set of periurban calcareous agricultural Mediterranean soils was spiked with a mixture of Cd, Cu, Pb and Zn at two levels within the limit values proposed by current European legislation, incubated for up to 12 months, and subjected to various one-step extraction procedures to estimate mobile (neutral salts) and potentially mobile metal fractions (complexing and acidic extraction methods). The results obtained were used to study metal extractability patterns according to the soil characteristics. The analytical data were coupled with mineralogical investigations and speciation modelling using the Visual Minteq model. The formation of soluble metal-complexes in the complexing extracts (predicted by the Visual Minteq calculations) led to the highest extraction efficiency with complexing extractants. Metal extractability patterns were related to both content and composition of carbonate, organic matter, Fe oxide and clay fractions. Potentially mobile metal fractions were mainly affected by the finest soil fractions (recalcitrant organic matter, active lime and clay minerals). In the case of Pb, scarce correlations between extractable Pb and soil constituents were obtained which was attributed to high Pb retention due to the formation of 4PbCO₃·3PbO (corroborated by X-ray diffraction). In summary, the high metal proportion extracted with complexing agents highlighted the high but finite capacity to store potentially mobilizable metals and the possible vulnerability of these soils against environmental impact from metal accumulation.     

Study of the trace metal ion influence on the turnover of soil organic matter in cultivated contaminated soils

The role of metals in the behaviour of soil organic matter (SOM) is not well documented. Therefore, we investigated the influence of metals (Pb, Zn, Cu and Cd) on the dynamic of SOM in contaminated soils where maize (C4 plant) replaced C3 cultures. Three pseudogley brown leached soil profiles under maize with a decreasing gradient in metals concentrations were sampled. On size fractions, stable carbon isotopic ratio (delta13C), metals, organic carbon and nitrogen concentrations were measured in function of depth. The determined sequence for the amount of C4 organic matter in the bulk fractions: M3 (0.9)>M2 (0.4)>M1 (0.3) is in agreement with a significant influence of metals on the SOM turnover. New C4 SOM, mainly present in the labile coarser fractions and less contaminated by metals than the stabilised C3 SOM of the clay fraction, is more easily degraded by microorganisms.     

Transport of anthracene and benz(a)anthracene through iron-quartz and three aquifer materials in laboratory columns

In groundwater systems, dissolved natural organic matter (NOM) can influence the mobility of organic contaminants by altering the contaminant behavior in water and solid phases. The transport of anthracene and benz(a)anthracene (B(a)A) was studied in the presence and absence of NOM and/or soil organic matter (SOM) in column experiments. The results show that sorption are related to the properties of polycyclic aromatic hydrocarbons (PAHs), NOM and SOM. In the Fe-quartz media, the amount of NOM (20 mg/l) in solution had a little effect on increasing the apparent solubility of anthracene and countering increased anthracene sorption. In the natural (Bemidji) soil, Suwannee river fulvic acid (SRFA, 20 mg/l) and Suwannee river humic acid (SRHA) in water did not compete with SOM for anthracene, indicating that SOM has higher partition efficiency for anthracene. It was also observed that slow diffusion through an organic phase apparently caused most of the observed tailing in column breakthrough curves (BTCs). Even though the fOC of washed Bemidji sediment was very low, the transport of B(a)A was retarded significantly, however, and the transport of B(a)A was shown to be facilitated by dissolved NOM.     

The solid-solution partitioning of heavy metals (Cu,Zn, Cd,Pb) in upland soils of England and Wales

Ninety-eight surface soils were sampled from the uplands of England and Wales, and analysed for loss-on-ignition (LOI), and total and dissolved base cations, Al, Fe, and trace heavy metals (Cu, Zn, Cd, Pb). The samples covered wide ranges of pH (3.4-8.3) and LOI (9-98%). Soil metal contents measured by extraction with 0.43 mol l-1 HNO3 and 0.1 mol l-1 EDTA were very similar, and generally lower than values obtained by extraction with a mixture of concentrated nitric and perchloric acids. Total heavy metal concentrations in soil solution depend positively upon soil metal content and [DOC], and negatively upon pH and LOI, values of r2 ranging from 0.39 (Cu) to 0.81 (Pb). Stronger correlations (r2=0.76-0.95) were obtained by multiple regression analysis involving free metal ion (Cu2+, Zn2+, Cd2+, Pb2+) concentrations calculated with the equilibrium speciation model WHAM/Model VI. The free metal ion concentrations depend positively upon MHNO3 and negatively upon pH and LOI. The data were also analysed by using WHAM/Model VI to describe solid-solution interactions as well as solution speciation; this involved calibrating each soil sample by adjusting the content of "active" humic matter to match the observed soil pH. The calibrated model provided fair predictions of total heavy metal concentrations in soil solution, and predicted free metal ion concentrations were in reasonable agreement with the values obtained from solution-only speciation calculations.