Soil pollution by petroleum products, III. Kerosene stability in soil columns as affected by volatilization

The stability of kerosene in soils as affected by volatization was determined in a laboratory column experiment by following the losses in the total concentration and the change in composition of the residuals in a dune sand, a loamy sand, and a silty loam soil during a 50-day period. Seven major compounds ranging between C₉ and C₁₅ were selected from a large variety of hydrocarbons forming kerosene and their presence in the remaining petroleum product was determined. The change in composition of kerosene during the experimental period was determined by gas chromatography and related to the seven major compounds selected. The experimental conditions — air-dairy soil and no subsequent addition of water—excluded both biodegradative and leaching. losses.The losses of kerosene in air-dried soil columns during the 50-day experimental period and the changes in the composition of the remaining residues due to volatilization are reported. The volatilization of all the components determined was greater from the dune sand and loamy sand soils than from the silty loam soil. It was assumed that the reason for this behavior was that the dune sand and the loamy sand soils contain a greater proportion of large pores (>4.5 μm) than the silty loam soil, even though the total porosity of the loamy sand and the silty loam is similar. In all the soils in the experiment, the components with a high carbon number formed the main fraction of the kerosene residues after 50 days of incubation.     

Transport of silver nanoparticles (AgNPs) in soil

The effect of soil properties on the transport of silver nanoparticles (AgNPs) was studied in a set of laboratory column experiments, using different combinations of size fractions of a Mediterranean sandy clay soil. The AgNPs with average size of ∼30 nm yielded a stable suspension in water with zeta potential of −39 mV. Early breakthrough of AgNPs in soil was observed in column transport experiments. AgNPs were found to have high mobility in soil with outlet relative concentrations ranging from 30% to 70%, depending on experimental conditions. AgNP mobility through the column decreased when the fraction of smaller soil aggregates was larger. The early breakthrough pattern was not observed for AgNPs in pure quartz columns nor for bromide tracer in soil columns, suggesting that early breakthrough is related to the nature of AgNP transport in natural soils. Micro-CT and image analysis used to investigate structural features of the soil, suggest that soil aggregate size strongly affects AgNP transport in natural soil. The retention of AgNPs in the soil column was reduced when humic acid was added to the leaching solution, while a lower flow rate (Darcy velocity of 0.17 cm/min versus 0.66 cm/min) resulted in higher retention of AgNPs in the soil. When soil residual chloride was exchanged by nitrate prior to column experiments, significantly improved mobility of AgNPs was observed in the soil column. These findings point to the importance of AgNP-soil chemical interactions as a retention mechanism, and demonstrate the need to employ natural soils rather than glass beads or quartz in representative experimental investigations.     

Aldicarb and carbofuran transport in a Hapludalf influenced by differential antecedent soil water content and irrigation delay

Pesticide use in agroecosystems can adversely impact groundwater quality via chemical leaching through soils. Few studies have investigated the effects of antecedent soil water content (SWC) and timing of initial irrigation (TII) after chemical application on pesticide transport and degradation. The objectives of this study were to investigate the effects of antecedent soil water content (wet vs dry) and timing of initial irrigation (0h Delay vs 24h Delay) on aldicarb [(EZ)-2-methyl-2-(methylthio)propionaldehyde O-methylcarbamoyloxime] and carbofuran [2,3-dihydro-2,2-dimethylbenzofuran-7-yl methylcarbamate] transport and degradation parameters at a field site with Menfro silt loam (fine-silty, mixed, superactive, mesic Typic Hapludalf) soils. Aldicarb and carbofuran were applied to plots near field capacity (wet) or near permanent wilting point (dry). Half of the dry and wet plots received irrigation water immediately after chemical application and the remaining plots were irrigated after a 24h Delay. The transport and degradation parameters were estimated using the method of moments. Statistical significance determined for SWC included averages across TII levels, and significance determined for TII included averages across SWC levels. For the dry treatment, aldicarb was detected 0.10 m deeper (P<0.01) on two of the four sampling dates and carbofuran was detected at least 0.10 m deeper (P<0.05) on all of the sampling dates compared to the wet treatment. Pore water velocity was found to be higher (P<0.10) in the dry vs wet treatments on three of four dates for aldicarb and two of four dates for carbofuran. Retardation coefficients for both pesticides showed similar evidence of reduced values for the dry vs wet treatments. These results indicate deeper pesticide movement in the initially dry treatment. For aldicarb and carbofuran, estimated values of the degradation rate were approximately 40-49% lower in the initially dry plots compared to the initially wet plots, respectively. When the initial irrigation was delayed for 24h, irrespective of antecedent moisture conditions, a 30% reduction in aldicarb degradation occurred. This study illustrates the deeper transport of pesticides and their increased persistence when applied to initially dry soils.     

Increasing the efficiency of solute leaching: impacts of flow interruption with drainage of the “preferential flow paths”

Most soils contain preferential flow paths that can impact on solute mobility. Solutes can move rapidly down the preferential flow paths with high pore-water velocities, but can be held in the less permeable region of the soil matrix with low pore-water velocities, thereby reducing the efficiency of leaching. In this study, we conducted leaching experiments with interruption of the flow and drainage of the main flow paths to assess the efficiency of this type of leaching. We compared our experimental results to a simple analytical model, which predicts the influence of the variations in concentration gradients within a single spherical aggregate (SSA) surrounded by preferential flow paths on leaching. We used large (length: 300 mm, diameter: 216 mm) undisturbed field soil cores from two contrasting soil types. To carry out intermittent leaching experiments, the field soil cores were first saturated with tracer solution (CaBr₂), and background solution (CaCl₂) was applied to mimic a leaching event. The cores were then drained at 25- to 30-cm suction to empty the main flow paths to mimic a dry period during which solutes could redistribute within the undrained region. We also conducted continuous leaching experiments to assess the impact of the dry periods on the efficiency of leaching. The flow interruptions with drainage enhanced leaching by 10–20% for our soils, which was consistent with the model's prediction, given an optimised “equivalent aggregate radius” for each soil. This parameter quantifies the time scales that characterise diffusion within the undrained region of the soil, and allows us to calculate the duration of the leaching events and interruption periods that would lead to more efficient leaching. Application of these methodologies will aid development of strategies for improving management of chemicals in soils, needed in managing salts in soils, in improving fertiliser efficiency, and in reclaiming contaminated soils.     

Behavior of Two Phenyl Urea Herbicides in Clayey Soils and Effect of Alternating Dry-Wet Conditions on their Availability

Adsorption and mobility of linuron (3-(3,4-dichlorophenyl)-1-methoxy-1-methylurea) and diuron (3-(3,4-dichlorophenyl)-1, 1-dimethylurea) were studied in clayey soils from the Gharb area (Morocco). Soils A and B were planted with sun flower (Helianthus annuus) while soil C was planted with sugar cane (Saccharum offcinarum). Adsorption was studied for linuron in soils A and B, while mobility was studied only in soil B. Adsorption data were found to fit the Freundlich equation with correlation coefficients r² > 0.9. Freundlich coefficients (K_f, n_f) were in agreement with L and S isotherm types for soils A and B, respectively. Values of K_oc (195 and 102) indicate moderate adsorption. Desorption isotherms for linuron showed hysteresis for both soils. The pesticide would be more bound to soil A (H = 8.44) than to soil B (H = 4.01). The effect of alternating wet and dry conditions was tested for soils A and B. Results showed that retention would increase in soil subject to an additional wet and dry cycle. In the case of diuron isotherm was of type L in soil C. Desorption was noticeable at high concentrations and tended to decrease when concentrations diminished. Mobility of linuron was tested in polyvinyle chloride (PVC) columns, which received different treatments before their percolation. The pesticide was more mobile in a previously saturated column. In columns subject to a drying step after saturation with water, linuron mobility was greatly reduced.     

Effects of long-term soil amendment with sewage sludges on soil humic acid thermal and molecular properties

Sewage sludges are frequently used as soil amendments due to their high contents of organic matter and nutrients, particularly N and P. However, their effects upon the chemistry of soil humic acids, one of the main components of the soil organic matter, need to be more deeply studied in order to understand the relation between organic matter structure and beneficial soil properties. Two sewage sludges subjected to different types of pre-treatment (composted and thermally dried) with very different chemical compositions were applied for three consecutive years to an agricultural soil under long-term field study. Thermal analysis (TG–DTG–DTA) and solid-state ¹³C NMR spectroscopy were used to compare molecular and structural properties of humic acids isolated from sewage sludges, and to determine changes in amended soils. Thermally dried sewage sludge humic acids showed an important presence of alkyl and O/N-alkyl compounds (70%) while composted sludge humic acids comprised 50% aromatic and carbonyl carbon. In spite of important differences in the initial chemical and thermal properties of the two types of sewage sludges, the chemical and thermal properties of the soil humic acids were quite similar to one another after 3 years of amendment. Long-term application of both sewage sludges resulted in 80–90% enrichment in alkyl carbon and organic nitrogen contents of the soil humic acid fraction.     

Soil contamination at abandoned sawmill areas

Contamination of soil by technical chlorophenol formulation at wood preserving sites was studied. The examined soils contained 50 to 1000 mg of polychlorinated phenols (CPs), 1 to 50 mg of polychlorinated phenoxyphenols (“pre-dioxins”, PCPPs) and 0.1 to 5 mg of polychlorinated dibenzofurans (PCDFs) per kg of dry soil. CPs were found to be mobile, leaching deep into the soil, while PCPPs and PCDFs accumulated in the top soil. All three classes of contaminants were stable in soil.     

In-situ surfactant/surfactant-nutrient mix-enhanced bioremediation of NAPL (fuel)-contaminated sandy soil aquifers

SCOPE AND BACKGROUND: Contamination of soils, aquifers and groundwater by nonaqueous phase liquid (NAPL) pollutants constitutes a major environmental issue of concern, worldwide. The residual (biodegradation-resistant) hydrophobic fuel hydrocarbons entrapped in the soil porous matrix, possess a particular bioremediation challenge due to their becoming virtually immobile, nor desorbable, or water dispersible. Consequently, they are not available as substrates to the micro-organism-based biodegradation. MATERIALS AND METHODS: Our research involves the development of economically feasible, surfactant/surfactant-nutrient mix (SSNM)-enhanced bioremediation methodologies for sustainable, in situ bioremediation of fuel-contaminated aquifers. This requires, methodologically, (a) the optimization, via in vitro 'flow' (columns) lab experiments and screening processes, of an effective mixture for the intended SSNM-enhanced bioremediation; and (b) the study of the combined effect of the optimized SSNM on the solubilization/mobilization and biodegradation of NAPL (fuel) in in vitro site/aquifer-simulated bioremediation. RESULTS AND DISCUSSION: The essence of our findings: (1) kerosene's maximum enhanced mobilization - f = 3.6, compared with that of deionized water, was achieved with an SSNM having the composition of linear alkylbenzene sulfonate (LABS): coco-amphodiacetate (containing N): surfactant-nutrient X (containing both N and P) = 0.15: 0.15: 0.05 g/L, respectively; (2) 62-64% of the initial amount of kerosene in the initially saturated soil matrix, 'packed' in a column, has been eluted from it during approximately 30 days, compared with 68% of kerosene biodegradation in 'vessel' settings, in 21 days. CONCLUSIONS: (1) The indigenous microorganisms present in th vadose zones of fuel-contaminated sandy soil aquifers are potentially capable of unassisted removal of approximately 80% of the initially contained fuel (kerosene), during a period of about 42 days; (2) the major effects of the SSNM addition are (a) enhanced mobilization of the bulky NAPL; and (b) enhanced desorbtion/ solubilization/dispersion of the entrapped NAPL which, in turn, facilitate their enhanced biodegradation. RECOMMENDATIONS AND PERSPECTIVE: Our findings suggest that pre-optimized, biodegradable SSNM is essential for surfactants-based bioremediation of NAPL-contaminated aquifers, in order to make this in-situ methodology both technologically and economically feasible.     

Temporal changes in kerosene content and composition in field soil as a result of leaching

A field experiment was designed to determine the combined effect of leaching and natural attenuation on the redistribution dynamics of kerosene--a volatile petroleum hydrocarbon mixture (VPHM)--and of its selected individual components in the soil subsurface. Variables included the composition of contaminant spilled, the soil water content before contamination and the leaching pattern. Temporal changes in the residual kerosene concentration and composition in the soil subsurface of the experimental field during 39 days and leaching by 500 mm of irrigation water were determined to a depth of 100 cm. The main processes controlling contaminant attenuation were volatilization and redistribution with depth. Soil hydration status was found to affect the attenuation, redistribution and composition of VPHM in the porous media. An initial relative increase of n-alkanes in the subsurface compared with the total VPHM in the first leaching period was a result of the volatilization of low vapor pressure compounds. The redistribution of individual components in the soil profile during leaching was in accordance with their physico-chemical properties.     

Residual gasoline saturation in unsaturated soil with and without organic matter

The goal of this study was to investigate the influence of one variable, natural organic matter, on residual gasoline saturation in sandy soils. Capillary pressure-saturation (P_c−S) relationships (air-gasoline) were determined for three physically-similar sandy soils, with different organic carbon contents (0.086%, 0.89% and 1.65%) and residual gasoline saturations were compared. Two initial moisture conditions, residual water saturation and air-dry, were evaluated. One soil type was packed to two different bulk densities. Visualization of the soils using cryo-scanning electron microscopy was performed to aid in better understanding the role of the organic matter in the soil. The results showed that soils with higher organic contents had higher residual gasoline saturations when starting with an initially air-dry soil. Increasing the bulk density of the same air-dried soil resulted in an increase in residual gasoline saturation. In the presence of a residual water saturation, however, residual gasoline saturations were virtually identical for the three soils and independent of bulk density; approximately 5–10 times lower than in soil that was initially air-dry. The presence of the residual water effectively coated the surface of the soil thereby reducing or eliminating gasoline/soil interactions. Some residual water may also be occupying very small pore spaces, making these locations inaccessible to the gasoline.     

Copper distribution in surface and subsurface soil horizons

The horizons of four natural soils were treated with Cu²⁺ in an acid medium to study the retention capacity of Cu. The possible mineralogical changes arising because of the treatment were also studied. The soil properties and characteristics with the greatest influence on the metal retention and its distribution among the different soil fractions were determined. Crystalline phases of each horizon were determined by X-ray diffraction (XDR). The morphology, structural distribution and particle chemical composition of soil samples were investigated using field emission scanning electron microscopy. Cu distribution in the different geochemical phases of the soil was studied using a sequential extraction. The treatment led to an increase in the amorphous phases and the formation of new crystalline phases, such as rouaite (Cu₂(NO₃)(OH)₃) and nitratine (NaNO₃). Cu was also found superficially sorbed on amorphous hydroxy compounds of Fe that interact with albite, muscovite and gibbsite, and also on spherical and curved particles of aluminium clays. The largest amount of Cu retained was in an exchangeable form, and the smallest amount associated with the crystalline Fe oxides and residual fraction. In the surface horizons, the predominant Cu retention process is complexation in organomineral associations, while in the subsurface horizons it is adsorption.     

Behavior of two phenyl urea herbicides in clayey soils and effect of alternating dry-wet conditions on their availability

Adsorption and mobility of linuron (3-(3,4-dichlorophenyl)-1-methoxy-1-methylurea) and diuron (3-(3,4-dichlorophenyl)-1, 1-dimethylurea) were studied in clayey soils from the Gharb area (Morocco). Soils A and B were planted with sun flower (Helianthus annuus) while soil C was planted with sugar cane (Saccharum offcinarum). Adsorption was studied for linuron in soils A and B, while mobility was studied only in soil B. Adsorption data were found to fit the Freundlich equation with correlation coefficients r2 > 0.9. Freundlich coefficients (Kf, nf) were in agreement with L and S isotherm types for soils A and B, respectively. Values of Koc (195 and 102) indicate moderate adsorption. Desorption isotherms for linuron showed hysteresis for both soils. The pesticide would be more bound to soil A (H = 8.44) than to soil B (H = 4.01). The effect of alternating wet and dry conditions was tested for soils A and B. Results showed that retention would increase in soil subject to an additional wet and dry cycle. In the case of diuron isotherm was of type L in soil C. Desorption was noticeable at high concentrations and tended to decrease when concentrations diminished. Mobility of linuron was tested in polyvinyle chloride (PVC) columns, which received different treatments before their percolation. The pesticide was more mobile in a previously saturated column. In columns subject to a drying step after saturation with water, linuron mobility was greatly reduced.     

Effect of different soil types on the enchytraeids Enchytraeus albidus and Enchytraeus luxuriosus using the herbicide Phenmedipham

Soil ecotoxicology studies are usually performed in standard soils, such as the OECD (Organization for Economic Cooperation and Development) artificial soil or the LUFA St. 2.2, a natural soil. When assessing the toxic effects in the environment, soil properties are often different from those in standard soils, which might lead to a different exposure situation for the test species and, therefore, to a different evaluation of the risk of the test substance. Selected to cover a broad range of properties and based on the Euro-Soils concept, 18 different soils were studied regarding their suitability to two test species: Enchytraeus albidus and Enchytraeus luxuriosus (Enchytraeidae). In reproduction tests, the test species reacted differently to the tested soils, but both enchytraeids did not survive in acid soils (i.e. pH相似文献   

The effect of municipal sludge compost on the mobility and bioavailability of Cd in a sierozem-wheat system in an arid region northwest of China

The effect of sewage sludge on the mobility and the bioavailability of trace metals in plant-soil systems have aroused wide interested and been widely explored. Based on a wheat-cultivating experiment, the effect of municipal sludge compost (MSC) on the mobility and bioavailability of Cd in a soil-wheat system was studied. With the application of MSC, soil organic matter (SOM), total nitrogen (TN), and total phosphorus (TP) in the soil increased significantly, while concentrations of trace metals (Cu, Zn, Ni, Pb, Cd) were below the China’s minimum thresholds. The application of MSC could improve wheat growth. The application of MSC at the rate of 0.5 % had no significant effect on the chemical fraction distribution of Cd in soil. In two soil treatments, Cd mainly existed in the labile chemical fractions (exchangeable chemical fraction (EXCF) and carbonate chemical fraction (CABF)). However, the application of MSC could reduce accumulation of Cd by wheat. Cd contents in each part of the MSC-applied wheat were significantly less than that of non-MSC-applied wheat. In the tested soils, the extractable concentrations decreased in the order: EDTA > MgCl₂ ≈ NH₄OAc > DTPA. There were no significant differences between soil treatments in the amounts of extractable Cd when the extraction was done under neutral conditions, although significant differences were observed when the extraction was done under alkaline conditions. In this study, the DTPA extraction procedure provided a good indication of Cd bioavailability. Our results suggest that, in the short term at least, amending soils with MSC may benefit crop dry matter production while not increasing the risk of human exposure to Cd through consumption of wheat grown on MSC-amended soils.     

Evaluation of the toxicity of two soils from Jales Mine (Portugal) using aquatic bioassays

Soil contamination can be one path for streams and groundwater contamination. As a complement of chemical analysis and total contaminants determination, bioassays can provide information on the bioavailable fraction of chemical compounds, focusing on the retention and habitat function of soils. In this study the evaluation of the toxicity of two soils from the abandoned Jales Mine (Portugal) regarded both functions. The buffer capacity of soils was tested with bioassays carried out using the cladoceran Daphnia magna and the marine bacteria Vibrio fischeri. The habitat function of soils was evaluated with the reproduction bioassay with the collembolan Folsomia candida. The Microtox solid-phase test was performed with V. fischeri using soil as test medium, and soil elutriates were extracted to perform the Microtox basic test, and an immobilization and reproduction bioassay with D. magna. The marine bacteria showed high sensitivity to the soil with low heavy metal content (JNC soil) and to JNC soil elutriates, while the soil with highest heavy metal content (JC soil) or soil elutriates exposure did not cause any toxic effect. In the bioassays with D. magna, organisms showed sensitivity to JNC and also to JC soil elutriates. Both mobilization and reproduction features were inhibited. The bioassay with F. candida did not reflect any influence of the contaminants on their reproduction. Although JNC soil presented lower heavy metal contents, elutriates showed different patterns of contamination when compared to JC soil and elutriates, which indicates different retention and buffer capacities between soils. Results obtained in this study underlined the sensitivity and importance of soil elutriate bioassays with aquatic organisms in the evaluation strategy in soil ERA processes.     

Behavior of triadimefon in two Lebanese soils.

The retention and fate of triadimefon fungicide were studied under two environmental conditions. Field studies were conducted on two soils, a sandy loam soil (Fanar) and a clay soil (Raouda). Fanar is a wet coastal area while Raouda is a dry agricultural area of the Bekaa plain located at an elevation of 870 m above sea level. Triadimefon was applied with a jet sprayer at 267 g a.i.ha(-1) and 200 g a.i.ha(-1) at Fanar and Raouda, respectively. Reconstituted soil columns (600 x 30 mm) glasses, were used to study the fungicide movement and metabolism in the two soils. Analyses of triadimefon and its metabolites were carried out using gas chromatography (GC) and high performance liquid chromatography (HPLC). The results indicated a weak reversibility of the adsorbed fraction in the clay soil. Clay is considered an important factor in triadimefon adsorption. Triadimefon mobility in the sandy-loam soil was relatively high in comparison with behavior in the clay soil where about half of the applied fungicide was detected in the upper 25 cm of soil, six days after treatment. Rapid degradation of triadimefon to triadimenol was observed in the two soils. The observed half-life was 8 days in sandy-loam and 13 days in clay soils.     

Adsorption studies of the herbicide simazine in agricultural soils of the Aconcagua valley, central Chile

Simazine is a s-triazine herbicide that has been applied worldwide for agriculture. This herbicide is the second most commonly detected pesticide in surface and groundwater in the United States, Europe and Australia. In this study, simazine adsorption behaviour was studied in two agricultural soils of the Aconcagua valley, central Chile. The two studied soils were soil A (loam, 8.5% organic matter content) and soil B (clay-loam, 3.5% organic matter content). Three times higher simazine adsorption capacity was observed in soil A (68.03 mg kg⁻¹) compared to soil B (22.03 mg kg⁻¹). The simazine adsorption distribution coefficients (K_d) were 9.32 L kg⁻¹ for soil A and 7.74 L kg⁻¹ for soil B. The simazine adsorption enthalpy in soil A was −21.0 kJ mol⁻¹ while in soil B the adsorption enthalpy value was −11.5 kJ mol⁻¹. These results indicate that simazine adsorption process in these soils is exothermic, governing H bonds the adsorption process of simazine in both the loam and clay-loam soils. These results and the potentiometric profiles of both soils, suggest that simazine adsorption in soil A is mainly governed by simazine–organic matter interactions and in soil B by simazine–clay interactions. The understanding of simazine sorption–desorption processes is essential to determine the pesticide fate and availability in soil for pest control, biodegradation, runoff and leaching.     

Nitric oxide and nitrous oxide emission from Hungarian forest soils; linked with atmospheric N-deposition

Studies of forest nitrogen (N) budgets generally measure inputs from the atmosphere in wet and dry deposition and outputs via hydrologic export. Although denitrification has been shown to be important in many wetland ecosystems, emission of N oxides from forest soils is an important, and often overlooked, component of an ecosystem N budget. During 1 year (2002–03), emissions of nitric oxide (NO) and nitrous oxide (N₂O) were measured from Sessile oak and Norway spruce forest soils in northeast Hungary. Accumulation in small static chambers followed by gas chromatography-mass spectrometry detection was used for the estimation of N₂O emission flux. Because there are rapid chemical reactions of NO and ozone, small dynamic chambers were used for in situ NO flux measurements. Average soil emissions of NO were 1.2 and 2.1 μg N m⁻² h⁻¹, and for N₂O were 15 and 20 μg N m⁻² h⁻¹, for spruce and oak soils, respectively. Due to the relatively high soil water content, and low C/N ratio in soil, denitrification processes dominate, resulting in an order of magnitude greater N₂O emission rate compared to NO. The previously determined N balance between the atmosphere and the forest ecosystem was re-calculated using these soil emission figures. The total (dry+wet) atmospheric N-deposition to the soil was 1.42 and 1.59 g N m⁻² yr⁻¹ for spruce and oak, respectively, while the soil emissions are 0.14 and 0.20 g N m⁻² yr⁻¹. Thus, about 10–13% of N compounds deposited to the soil, mostly as and , were transformed in the soil and emitted back to the atmosphere, mostly as greenhouse gas (N₂O).