Column study of the influence of air humidity on the retention of hydrocarbons on soil

Inverse gas chromatography (IGC) is used for the analysis of the influence of air relative humidity on the retention of hexane, benzene, toluene and p-xylene in a sandy soil under experimental conditions similar to those typical of soil vapor extraction (SVE). The advantages of IGC over other techniques, are (a) an efficient use of lab resources, (b) a high sensitivity to low partitioning coefficients and (c) a closer reproduction of field conditions. In our procedure, experiments with only two samples of different mass are necessary to establish if linear isotherms can be used to describe the retention of the contaminants. This approach gives information necessary for analyzing the feasibility and design of remediation technologies with a laboratory effort significantly smaller than the adsorption/desorption cycle for isotherm determination. The retention coefficients of the contaminants decrease as humidity increases in a similar fashion for all of them, probably because the reduction in the number of the adsorption sites available for the organic compounds due to the presence of water is quite similar for all the contaminants studied. These retention coefficients may be related to those obtained for dry air conditions for all the contaminants through (R - 1)RH% = A(R - 1)dry air(B), where the parameter B is found to remain approximately constant (0.90), while the parameter A decreases linearly with the relative moisture.     

Influence of methanol on retention of hydrophobic organic chemicals in soil leaching column chromatography

The influence of methanol in methanol-water mixed eluents on the capacity factor (k'), an important parameter which could depict leaching potential of hydrophobic organic chemicals (HOCs) in soil leaching column chromatography (SLCC), was investigated. Two reference soils, GSE 17201 obtained from Bayer Landwirtschaftszentrum, Monheim, Germany and SP 14696 from LUFA, Spencer, Germany, were used as packing materials in soil columns, and isocratic elution with methanol-water mixtures at different volume fractions of methanol (phi) were tested. Short-term exposure of the column (packed with the GSE 17201 soil) to the eluents increased solute retention by a certain (23% log-unit) degree evaluated through a correlation with the retention on the same soil column but unpreconditioned by methanol-containing eluents. Long-term exposure of soil columns to the eluents did not influence the solute retention. A log-linear equation, log k' = log k'(w) - S(phi), could well and generally describe the retention of HOCs in SLCC. For the compounds of homologous series, logk'(w) had good linear relationship with S, indicating the hydrophobic partition mechanism existing in the retention process.     

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.     

Influence of soil moisture on the sequestration of organic compounds in soil

A study was conducted as a part of continuing investigation of the effect of soil moisture on the sequestration of organic compounds aged in the soil. Here, experiments focused on the effects of moisture changes within the soil before, during, and after contaminant addition. The extractability of aged (68 d) phenanthrene was greater from soil that had been subjected to wetting and drying cycles prior to solute addition as compared to soil initially maintained at constant moisture. The recovery of phenanthrene added to moist soil was increased relative to extractability from soil that was air-dried at the time of the contaminant addition. Repeated wetting and drying of soil after the addition of atrazine or phenanthrene resulted in decreased extractability of the compounds as compared to samples maintained at constant moisture. A method for rapidly sequestering contaminants is proposed and may be useful in limiting the time required for laboratory studies involving “aged” contaminants. These data build upon the findings of earlier work from our laboratory and indicate that changes in the moisture conditions of soil can affect the availability of sequestered contaminants possibly through alterations in the structure of the natural solid.     

The influence of organic matter on sorption and fate of glyphosate in soil - Comparing different soils and humic substances

Soil organic matter (SOM) is generally believed not to influence the sorption of glyphosate in soil. To get a closer look on the dynamics between glyphosate and SOM, we used three approaches: I. Sorption studies with seven purified soil humic fractions showed that these could sorb glyphosate and that the aromatic content, possibly phenolic groups, seems to aid the sorption. II. Sorption studies with six whole soils and with SOM removed showed that several soil parameters including SOM are responsible for the strong sorption of glyphosate in soils. III. After an 80 day fate experiment, ∼40% of the added glyphosate was associated with the humic and fulvic acid fractions in the sandy soils, while this was the case for only ∼10% of the added glyphosate in the clayey soils. Glyphosate sorbed to humic substances in the natural soils seemed to be easier desorbed than glyphosate sorbed to amorphous Fe/Al-oxides.     

The influence of metam sodium on soil respiration

A laboratory experiment was performed in order to evaluate the extent to which metam sodium (MS) applied at two different recommended rates and its degradation product, methyl isothiocyanate (MITC), affect soil respiration. Results suggest that MS degradation to MITC was complete within 4 hours and that MITC decomposed quickly in a few days, except in the soil containing high organic matter where it was still present after 15 days. Following the addition of MS, a lag phase appeared in CO2-C evolution in the soil. It was longer for the higher dose of MS added and for the two soils with low organic C content. The dynamics of the process was described by the Bonde and Rosswall model and by the Gompertz RS E model for the untreated and the MS-treated soils, respectively.     

The influence of organic acids in relation to acid deposition in controlling the acidity of soil and stream waters on a seasonal basis

Much uncertainty still exists regarding the relative importance of organic acids in relation to acid deposition in controlling the acidity of soil and surface waters. This paper contributes to this debate by presenting analysis of seasonal variations in atmospheric deposition, soil solution and stream water chemistry for two UK headwater catchments with contrasting soils. Acid neutralising capacity (ANC), dissolved organic carbon (DOC) concentrations and the Na:Cl ratio of soil and stream waters displayed strong seasonal patterns with little seasonal variation observed in soil water pH. These patterns, plus the strong relationships between ANC, Cl and DOC, suggest that cation exchange and seasonal changes in the production of DOC and seasalt deposition are driving a shift in the proportion of acidity attributable to strong acid anions, from atmospheric deposition, during winter to predominantly organic acids in summer.     

Control of lead solubility in soil contaminated with lead shot: effect of soil pH

An incubation experiment was carried out to assess the rate of oxidation of Pb shot and subsequent transfer of Pb to the soil under a range of soil pH conditions. Lead shot corrosion was rapid, so that soil solution and fine earth (<1mm) Pb concentrations increased rapidly within a few months. Corrosion products, dominated by hydrocerussite (Pb(3)(CO(3))(2)(OH)(2)), developed in crusts surrounding individual Pb pellets. However, irrespective of pH, Pb(2+) activities in the soil solutions, modelled using WHAM 6, were much lower than would be the case if they were controlled by the solubility of the dominant Pb compounds present in the Pb shot crust material. In contrast, modelling of soil solid-solution phase distribution of Pb, again using WHAM 6, suggested that, at least during the 24 months of the study, soil solution Pb concentrations were more likely to be controlled by sorption of Pb by the soil solid phase.     

Influence of soil organic matter on the leaching of polycyclic aromatic hydrocarbons in soil

Polycyclic aromatic hydrocarbons (PAHs) are one of the main classes of contaminants in the terrestrial environment. Aside from total organic carbon, the ratio among the different organic matter fractions [dissolved organic matter, fulvic acid (FA), humic acid (HA) and humin] can also affect the mobility of these hydrocarbons in soils. In this study the effect of the whole organic carbon pool has been compared with that of HA and FA on the translocation of four PAHs (biphenyl, fluorene, phenanthrene and pyrene) in soil columns. Oxidized and untreated soil columns with and without HA or FA, were prepared, spilled with hydrocarbons and leached with a 0.01 M CaCl2 solution. The influence of HA and FA on PAH translocation was investigated through determinations of the PAH contents and total organic carbon (TOC) in the layers of the columns. All molecules were moved vertically by the percolating solutions, their concentrations decreasing with depths. The nonoxidized soil tended to retain more PAHs (96%) than the oxidized one (60%), confirming that organic matter plays an important role in controlling PAH leaching. The whole organic matter pool reduced the translocation of pollutants downward the profile. The addition of HA enhanced this behaviour by increasing the PAH retention in the top layers (7.55 mg and 4.00 mg in the top two layers, respectively) while FA increased their mobility (only 2.30 and 2.90 mg of PAHs were found in the top layers) and favoured leaching. In fact, in the presence of HA alone, the higher amounts of PAHs retained at the surface and the good correlation (r2=0.936) between TOC and hydrocarbon distribution can be attributed to a parallel distribution of PAHs and HA, while in the presence of FA, the higher mobility of PAHs can be attributed to the high mobility of the humic material, as expected by its extensive hydrophilic characteristics.     

The influence of soil contamination on the concentrations of PCBs in milk in Siberia

Although atmospheric deposition is generally the dominant pathway of PCBs into agricultural food chains, soil ingestion by livestock can be important in some cases. The relationship between PCB levels in cow's milk and in pasture soil was studied in the Irkutsk region in Siberia where an historical atmospheric source(s) of PCBs has led to widespread contamination of soil. Milk samples were collected in spring and again in autumn from 18 different farms and analyzed for PCBs. Pasture soil samples were also collected and analyzed. The PCB concentrations in both milk and soil ranged over more than an order of magnitude between the farms. A good correlation was obtained between PCB levels in autumn milk and in soil. This together with a range of other evidence suggested that ingestion of pasture soil was the dominant source of the PCB contamination in the milk. The average soil ingestion rate was estimated to be 1700 g/d, which is at the upper end of values reported in the literature. This may be due to the arid summer climate or the animal husbandry practices in Siberia.     

Linear solvation energy relationships regarding sorption and retention properties of hydrophobic organic compounds in soil leaching column chromatography

The capacity factors of a series of hydrophobic organic compounds (HOCs) were measured in soil leaching column chromatography (SLCC) on a soil column, and in reversed-phase liquid chromatography on a C18 column with different volumetric fractions (phi) of methanol in methanol-water mixtures. A general equation of linear solvation energy relationships, log(XYZ) XYZ0 + mV(I)/100 + spi + bbetam + aalpham, was applied to analyze capacity factors (k'), soil organic partition coefficients (Koc) and octanol-water partition coefficients (P). The analyses exhibited high accuracy. The chief solute factors that control logKoc, log P, and logk' (on soil and on C18) are the solute size (V(I)/100) and hydrogen-bond basicity (betam). Less important solute factors are the dipolarity/polarizability (pi*) and hydrogen-bond acidity (alpham). Log k' on soil and log Koc have similar signs in four fitting coefficients (m, s, b and a) and similar ratios (m:s:b:a), while log k' on C18 and logP have similar signs in coefficients (m, s, b and a) and similar ratios (m:s:b:a). Consequently, logk' values on C18 have good correlations with logP (r > 0.97), while logk' values on soil have good correlations with logKoc (r > 0.98). Two Koc estimation methods were developed, one through solute solvatochromic parameters, and the other through correlations with k' on soil. For HOCs, a linear relationship between logarithmic capacity factor and methanol composition in methanol-water mixtures could also be derived in SLCC.     

The influence of humic acids on the phytoextraction of cadmium from soil

Cadmium poses a major environmental and human health threat because of its constant release through anthropogenic activities. A need, therefore, exists for cost-effective remediation procedures. Phytoremediation, the use of plants to extract contaminants from soils and groundwater, has revealed great potential. However, it is limited by the fact that plants need time, nutrient supply and, moreover, have a limited metal uptake capacity. Synthetic chelators have shown positive effects in enhancing heavy metal extraction through phytoremediation, but they have also revealed a vast number of negative side-effects. The objective of this research was to investigate the use of humic acids as an alternative to synthetic chelators. Humic acids were applied to a cadmium-contaminated soil at various dosages, and the uptake of cadmium into Nicotiana tabacum SR-1 was determined in relation to the amounts of total and bioavailable cadmium in the soil. It was found that the theoretical bioavailability of cadmium, as determined by diethylenetriaminepentaacetic acid (DTPA) extraction, did not change, but its plant uptake was enhanced significantly, in some cases up to 65%. Humic acids added at a rate of 2 g kg(-1) soil increased the cadmium concentration in the shoots from 30.9 to 39.9 mg kg(-1). A possible reason for this enhancement is the decrease in pH, resulting in higher cadmium availability. Another possibility taken into account is that plants may take up cadmium complexes with humic acid fragments, which result from microbiological degradation or, self-dissociation.     

The effect of soil organic matter on fate of polycyclic aromatic hydrocarbons in soil: A microcosm study

A microcosm study was conducted to address the influences of air-soil partition and sequestration on the fate of polycyclic aromatic hydrocarbons (PAHs) in soil. Sterilized and unsterilized soils with soil organic carbon (SOC) content ranging from 0.23 to 7.06% were incubated in a chamber with six PAHs supplied through air. After 100 d of incubation when the system approached pseudo-steady state, the PAHs concentrations in the unsterilized soils still correlated with SOC significantly, while the association did not exist for those sterilized. The lower degradation rate in the soil with higher SOC was likely the major reason for the association between SOC and PAHs concentrations, while the decreased surface porosity likely suppressed such correlation for the sterilized samples. The results indicated that the sequestration was likely the major mechanism for the accumulation of PAHs in soils, while both of the soil porosity and PAHs properties had observed influences.     

Effects of phosphate additions to soil on lead and phosphate concentrations of Holcus lanatus grown on lead amended soil

Holcus lanatus was grown in soil artificially amended with lead and phosphate. Shoot lead concentrations in the second harvest were lower where 50 mg kg⁻¹ phosphate was added to soil compared with unfertilized soil. Greater levels of fertilization did not decrease shoot lead concentrations further. The most likely mechanism was considered to be one of growth dilution and not chemical precipitation of an insoluble lead-phosphate compound in soil, as has been speculated in the past.     

PAHs in background soils from Western Europe: influence of atmospheric deposition and soil organic matter

The levels and distribution of polynuclear aromatic hydrocarbons (PAHs) were determined in soil samples from background locations in the UK and Norway, to investigate their spatial distribution and the controlling environmental factors. Concentrations ranged between 42 and 11200 microg kg(-1) (geometric mean 640 microg kg(-1)) and 8.6 and 1050 microg kg(-1) (150 microg kg(-1)) dry weight in the UK and Norwegian soil, respectively. Proximity to sources and locations susceptible to high atmospheric depositional inputs resulted in higher concentrations. Statistically significant relationships were observed between PAH and total organic carbon (TOC) in the Norwegian samples. High molecular weight PAHs correlated with black carbon (BC) in UK-woodland soil. These observations support the hypothesis that TOC plays an important role in the retention of PAHs in soil and that PAHs are often combined with BC during combustion emissions. PAHs with 4 and more rings comprised approximately 90% of total PAHs in the UK soil, but only 50% in the Norwegian soil. The mixture of PAHs implied that fractionation occurred during long-range atmospheric transport and deposition. The lighter PAHs with lower K(ow) values more readily reached the most remote sites. The heavier PAHs with higher K(ow) values remained in closer proximity to sources.     

The role of organic ligands in ferrous-induced photochemical degradation of 2,4-dichlorophenoxyacetic acid

Recent studies have shown that hydrogen peroxide is generated in a ferrioxalate-induced photoreductive reaction, but information about the effect of organic ligands on the photochemical behaviour of ferrous species is limited. The degradation of the herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) by a ferrous-catalyzed oxidation in the presence of various ligands such as formate, citrate, malelate, oxalate, and ethylenediaminetetra-acetic acid (EDTA) was studied. The experiments were conducted under either dark or irradiated (350n m) conditions. Forty-two percent and 34% of 2,4-D were removed by the Fe(2+)/oxalate/UV and Fe(2+)/citrate/UV processes, respectively, after 30 min of reaction and oxidative intermediates were obtained in both cases. The presence of hydroxylated intermediates suggests that 2,4-D may be attacked by hydroxyl radicals, which are the products of the photo-Fenton-like reaction. As such, hydrogen peroxide was produced by the photolysis of ferrous oxalate or ferrous citrate, referred to hereafter as photogenerated H(2)O(2). As expected, the total removal percentage of 2,4-D jumped to 97% when 1mM of hydrogen peroxide (so-called spiked H(2)O(2)) was externally added to the reaction vessel to initiate the Fe(2+)/oxalate/UV process. Therefore, the treatment of 2,4-D by the Fe(2+)/oxalate/H(2)O(2)/UV system can be operated in two steps: the photolysis of ferrous oxalate first, followed by adding the spiked H(2)O(2) sometime after the commencement of the reaction. A two-phase model has been developed to describe this tandem ferrous-catalyzed photooxidation, which would help to achieve the mineralization of 2,4-D.     

The effect of pH, ion strength and reactant content on the complexation of Cu2+ by various natural organic ligands from water and soil in Hong Kong

The complexation constants for copper associated with different natural organic ligands, including dissolved organic carbon (DOC) extracted from water, water soluble organic carbon (WSOC), fulvic acid (FA) and humic acid (HA) from soil, were determined and then compared based on discrete single site model. Both ion-selective electrode (ISE) and anodic stripping voltammetry were used to determine the content of free copper ions, while the relative number of complexation sites was estimated using a fluorescence quenching (FQ) at the same time. ISE proved to be the most applicable technique when the concentration of copper was above 10(-7) moll(-1). The logk values for two WSOC sample sites (Song Ziyuan and Xin Niangtan) were 4.64 and 4.66; higher than both the DOC and HA values yet lower than the FA values, which were unusually high due to unavoidable pollution from the cation exchange resin used during the purification process. Binding affinities between the copper ions and the organic ligands obtained from streams in Yong Wei (DOC) and Song Ziyuan (WSOC) were influenced by pH, ion strength, and reactant concentration. Values for logk increased with increases in pH (ion strength of 0.1 N). At pH 4, the logk values decreased with increases in the supporting electrolyte concentration and total copper ion additions.     

The organic contamination level based on the total soil mass is not a proper index of the soil contamination intensity

Concentrations of organic contaminants in common productive soils based on the total soil mass give a misleading account of actual contamination effects. This is attributed to the fact that productive soils are essentially water-saturated, with the result that the soil uptake of organic compounds occurs principally by partition into the soil organic matter (SOM). This report illustrates that the soil contamination intensity of a compound is governed by the concentration in the SOM (C_om) rather than by the concentration in whole soil (C_s). Supporting data consist of the measured levels and toxicities of many pesticides in soils of widely differing SOM contents and the related levels in in-situ crops that defy explanation by the C_s values. This SOM-based index is timely needed for evaluating the contamination effects of food crops grown in different soils and for establishing a dependable priority ranking for intended remediation of numerous contamination sites.     

Influence of organic acids on the transport of heavy metals in soil

Vegetation historically has been an important part of reclamation of sites contaminated with metals, whether the objective was to stabilize the metals or remove them through phytoremediation. Understanding the impact of organic acids typically found in the rhizosphere would contribute to our knowledge of the impact of plants in contaminated environments. Heavy metal transport in soils in the presence of simple organic acids was assessed in two laboratory studies. In the first study, thin layer chromatography (TLC) was used to investigate Zn, Cd, and Pb movement in a sandy loam soil as affected by soluble organic acids in the rhizosphere. Many of these organic acids enhanced heavy metal movement. For organic acid concentrations of 10mM, citric acid had the highest R(f) values (frontal distance moved by metal divided by frontal distance moved by the solution) for Zn, followed by malic, tartaric, fumaric, and glutaric acids. Citric acid also has the highest R(f) value for Cd movement followed by fumaric acid. Citric acid and tartaric acid enhanced Pb transport to the greatest degree. For most organic acids studied, R(f) values followed the trend Zn>Cd>Pb. Citric acid (10mM) increased R(f) values of Zn and Cd by approximately three times relative to water. In the second study, small soil columns were used to test the impact of simple organic acids on Zn, Cd, and Pb leaching in soils. Citric acid greatly enhanced Zn and Cd movement in soils but had little influence on Pb movement. The Zn and Cd in the effluents from columns treated with 10mM citric acid attained influent metal concentrations by the end of the experiment, but effluent metal concentrations were much less than influent concentrations for citrate <10mM. Exchangeable Zn in the soil columns was about 40% of total Zn, and approximately 80% total Cd was in exchangeable form. Nearly all of the Pb retained by the soil columns was exchangeable.     

The influence of paddy soil drying on Tc insolubilization by bacteria

Tc insolubilization in four soils samples was compared by pre-incubating them in both dry and wet states, then measuring Tc concentrations in solution when the samples were saturated with an excess of water spiked with 99Tc. Soils pre-incubated in a dry state showed higher Tc insolubilization than soils incubated in a wet state. To clarify the difference in Tc insolubilization, Eh, bacterial abundances, and bacterial species compositions in the dry and wet ponding water samples were determined. For the wet ponding water samples, Eh values were forced to decrease, but no increase in Tc insolubilization was observed. The dry and wet ponding water samples had similar numbers of bacteria. However, denaturing gradient gel electrophoresis analysis revealed that they had different bacterial species compositions. These results suggested the difference in bacterial species compositions would account for the difference in Tc insolubilization.