Formation of chloroacetic acids from soil,humic acid and phenolic moieties

The mechanism of formation of chloroacetates, which are important toxic environmental substances, has been controversial. Whereas the anthropogenic production has been well established, a natural formation has also been suggested. In this study the natural formation of chloroacetic acids from soil, as well as from humic material which is present in soil and from phenolic model substances has been investigated. It is shown that chloroacetates are formed from humic material with a linear relationship between the amount of humic acid used and chloroacetates found. More dichloroacetate (DCA) than trichloroacetate (TCA) is produced. The addition of Fe(2+), Fe(3+) and H(2)O(2) leads to an increased yield. NaCl was added as a source of chloride. We further examined the relationship between the structure and reactivity of phenolic substances, which can be considered as monomeric units of humic acids. Ethoxyphenol with built-in ethyl groups forms large amounts of DCA and TCA. The experiments with phenoxyacetic acid yielded large amounts of monochloroacetate (MCA). With other phenolic substances a ring cleavage was observed. Our investigations indicate that chloroacetates are formed abiotically from humic material and soils in addition to their known biotic mode of formation.     

Fate of Triclosan and Methyltriclosan in soil from biosolids application

This study investigates the persistence of Triclosan (TCS), and its degradation product, Methyltriclosan (MeTCS), after land application of biosolids to an experimental agricultural plot under both till and no till. Surface soil samples (n = 40) were collected several times over a three years period and sieved to remove biosolids. Concentration of TCS in the soil gradually increased with maximum levels of 63.7 ± 14.1 ng g(-1) dry wt., far below the predicted maximum concentration of 307.5 ng g(-1) dry wt. TCS disappearance corresponded with MeTCS appearance, suggesting in situ formation. Our results suggest that soil incorporation and degradation processes are taking place simultaneously and that TCS background levels are achieved within two years. TCS half-life (t(0.5)) was determined as 104 d and MeTCS t(0.5), which was more persistent than TCS, was estimated at 443 d.     

Fate and availability of glyphosate and AMPA in agricultural soil

The fate of glyphosate and its degradation product aminomethylphosphonic acid (AMPA) was studied in soil. Labeled glyphosate was used to be able to distinguish the measured quantities of glyphosate and AMPA from the background values since the soil was sampled in a field where glyphosate had been used formerly. After addition of labeled glyphosate, the disappearance of glyphosate and the formation and disappearance of AMPA were monitored. The resulting curves were fitted according to a new EU guideline. The best fit of the glyphosate degradation data was obtained using a first-order multi compartment (FOMC) model. DT(50) values of 9 days (glyphosate) and 32 days (AMPA) indicated relatively rapid degradation. After an aging period of 6 months, the leaching risk of each residue was determined by treating the soil with pure water or a phosphate solution (pH 6), to simulate rain over a non-fertilized or fertilized field, respectively. Significantly larger (p < 0.05) amounts of aged glyphosate and AMPA were extracted from the soil when phosphate solution was used as an extraction agent, compared with pure water. This indicates that the risk of leaching of aged glyphosate and AMPA residues from soil is greater in fertilized soil. The blank soil, to which 252 g glyphosate/ha was applied 21 months before this study, contained 0.81 ng glyphosate/g dry soil and 10.46 ng AMPA/g dry soil at the start of the study. Blank soil samples were used as controls without glyphosate addition. After incubation of the blank soil samples for 6 months, a significantly larger amount of AMPA was extracted from the soil treated with phosphate solution than from that treated with pure water. To determine the degree of uptake of aged glyphosate residues by crops growing in the soil, (14)C-labeled glyphosate was applied to soil 6.5 months prior to sowing rape and barley seeds. After 41 days, 0.006 +/- 0.002% and 0.005 +/- 0.001% of the applied radioactivity was measured in rape and barley, respectively.     

Fate and availability of glyphosate and AMPA in agricultural soil

The fate of glyphosate and its degradation product aminomethylphosphonic acid (AMPA) was studied in soil. Labeled glyphosate was used to be able to distinguish the measured quantities of glyphosate and AMPA from the background values since the soil was sampled in a field where glyphosate had been used formerly. After addition of labeled glyphosate, the disappearance of glyphosate and the formation and disappearance of AMPA were monitored. The resulting curves were fitted according to a new EU guideline. The best fit of the glyphosate degradation data was obtained using a first-order multi compartment (FOMC) model. DT₅₀ values of 9 days (glyphosate) and 32 days (AMPA) indicated relatively rapid degradation. After an aging period of 6 months, the leaching risk of each residue was determined by treating the soil with pure water or a phosphate solution (pH 6), to simulate rain over a non-fertilized or fertilized field, respectively. Significantly larger (p < 0.05) amounts of aged glyphosate and AMPA were extracted from the soil when phosphate solution was used as an extraction agent, compared with pure water. This indicates that the risk of leaching of aged glyphosate and AMPA residues from soil is greater in fertilized soil. The blank soil, to which 252 g glyphosate/ha was applied 21 months before this study, contained 0.81 ng glyphosate/g dry soil and 10.46 ng AMPA/g dry soil at the start of the study. Blank soil samples were used as controls without glyphosate addition. After incubation of the blank soil samples for 6 months, a significantly larger amount of AMPA was extracted from the soil treated with phosphate solution than from that treated with pure water. To determine the degree of uptake of aged glyphosate residues by crops growing in the soil, ¹⁴C-labeled glyphosate was applied to soil 6.5 months prior to sowing rape and barley seeds. After 41 days, 0.006 ± 0.002% and 0.005 ± 0.001% of the applied radioactivity was measured in rape and barley, respectively.     

Fate of atrazine in a soil under different agronomic management practices

Agricultural management affects the movement of atrazine in soil and leaching to groundwater. The objective of this study was to determine atrazine adsorption in a soil after 20 years of atrazine application under agronomic management practices differing in tillage practice (conventional and zero tillage), residue management (with and without residue retention) and crop rotation (wheat-maize rotation and maize monoculture). Atrazine sorption was determined using batch and column experiments. In the batch experiment, the highest distribution coefficient K_d (1.1 L kg^?1) at 0–10 cm soil depth was observed under zero tillage, crop rotation and residue retention (conservation agriculture). The key factor in adsorption was soil organic matter content and type. This was confirmed in the column experiment, in which the highest K_d values were observed in treatments with residue retention, under either zero or conventional tillage (0.81 and 0.68 L kg^?1, respectively). Under zero tillage, the fact that there was no soil movement helped to increase the K_d. The increased soil organic matter content with conservation agriculture may be more important than preferential flow due to higher pore connectivity in the same system. The soil's capacity to adsorb 2-hydroxyatrazine (HA), an important atrazine metabolite, was more important than its capacity to adsorb atrazine, and was similar under all four management practices (K_d ranged from 30 to 40 L kg^?1). The HA adsorption was attributed to the type and amount of clay in the soil, which is unaffected by agronomic management. Soils under conservation agriculture had higher atrazine retention potential than soils under conventional tillage, the system that predominates in the study area.     

Fate of pyrene in contaminated soil amended with alternate electron acceptors

Creosote-contaminated soil samples from the Libby Ground Water Contamination Superfund Site in Libby, MT, were amended with the potential alternate electron acceptors (AEA) nitrate (KNO3), manganese oxide (MnO2), and amorphous iron oxyhydroxide (FeOOH) and incubated at low oxygen tensions (0-6% O2). The fate of 14C-pyrene was evaluated with respect to the different soil amendments. The fate of 14C from the radiolabeled pyrene with regard to mineralization and bound residue formation within soil humic fractions was not significantly different from controls for the iron and manganese amended soils. Nitrate amendments appeared to stimulate 14C-pyrene mineralization at a level of 170 mg NO3-N kg(-1), and inhibit mineralization at 340 mg NO3-N kg(-1). The stimulatory effect did not appear to be the result of nitrate serving as an electron acceptor. Although AEA amendments did not significantly affect the rate or extent of 14C-pyrene mineralization, results of oxygen-deprived incubations (purged with N2) indicate that AEA may be utilized by the microbial community in the unsaturated contaminated soil system.     

Fate of parathion in soil under sub‐tropical field conditions

Abstract

Persistence, metabolism and binding of ¹⁴C‐parathion in alkaline sandy loam soil under sub‐tropical conditions of Delhi were studied for 545 days. After 3 days of treatment, ¹⁴C‐residues declined to 41% of the amount applied. The dissipation curve was biphasic; an initial rapid phase (up to 7 days) followed by slow dissipation. The half life of dissipation was only 3.36 days for the first phase and 84 days for the slow phase. The overall half life was 64.5 days. The total residues at zero‐time were 10.65 μg/g dry soil and were almost totally extractable. The extracts consisted of parathion, 4‐aminophenol, 4‐nitrophenol and paraoxon. The bound residues gradually increased and accounted for the total residue at the end of one year (0.7 μg/g).     

Fate of pharmaceutical compounds and steroid hormones in soil: study of transfer and degradation in soil columns

Numerous chemical products are dispersed into the environment, and the consequences can be sometimes harmful to humans and ecosystems. Pharmaceutical compounds and hormone steroids are among these substances that concern the scientific community. Currently, little data are available on the presence and fate of these compounds in the environment and, in particular, for solid matrices. Therefore, the aim of this work was to perform soil column experiments to evaluate the accumulation, transfer and degradation of these substances in soil. The analyses were based on efficient sample preparation followed by sensitive and selective liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS). For this purpose, 23 compounds were chosen including both pharmaceutical compounds as well as steroid hormones. In addition, this experiment was performed on two soils with different properties (% clay, pH, etc.). To the best of our knowledge, no soil column experiments have been performed previously on a large number of pharmaceutical compounds and steroid hormones. Significant transfer was observed only for sulphonamides that can be justified by their polarity (log K _ow ?相似文献   

Fate and degradation of triasulfuron in soil and water under laboratory conditions

The behavior and fate of triasulfuron (TRS) in water and soil systems were examined in laboratory studies. The degradation of TRS in both buffer solution and soil was highly pH-sensitive. The rate of degradation could be described with a pseudo first-order kinetic and was much faster at pH 4 than at pH 7 and 9. Aqueous hydrolysis occurred by cleavage of the sulfonylurea bridge to form 2-(2-chloroethoxy) benzenesulfonamide (CBSA) and [(4-methoxy-6-methyl-1,3,5-triazin-2-yl)amino] (AMMT). AMMT was unstable in aqueous solutions in any pH condition but it degraded more quickly at pH 4 and 9. CBSA did not degrade in aqueous solutions or in enriched cultures but it underwent a quick degradation in the soil. The rates of TRS degradation in sterile and non-sterile soils were similar, suggesting that microorganisms played a minimal role in the breakdown process. This hypothesis is supported by the results of studies on the degradation of TRS by enriched cultures during which the molecule underwent a prevalently chemical degradation.     

Fate and degradation of triasulfuron in soil and water under laboratory conditions

The behavior and fate of triasulfuron (TRS) in water and soil systems were examined in laboratory studies. The degradation of TRS in both buffer solution and soil was highly pH-sensitive. The rate of degradation could be described with a pseudo first-order kinetic and was much faster at pH 4 than at pH 7 and 9. Aqueous hydrolysis occurred by cleavage of the sulfonylurea bridge to form 2-(2-chloroethoxy) benzenesulfonamide (CBSA) and [(4-methoxy-6-methyl-1,3,5-triazin-2-yl)amino] (AMMT). AMMT was unstable in aqueous solutions in any pH condition but it degraded more quickly at pH 4 and 9. CBSA did not degrade in aqueous solutions or in enriched cultures but it underwent a quick degradation in the soil. The rates of TRS degradation in sterile and non-sterile soils were similar, suggesting that microorganisms played a minimal role in the breakdown process. This hypothesis is supported by the results of studies on the degradation of TRS by enriched cultures during which the molecule underwent a prevalently chemical degradation.     

Fate of imidacloprid in soil and plant after application to cotton seeds

This study aimed to investigate the persistence of imidacloprid in soil after application to cotton seeds and to obtain a complete picture on the mass balance of this compound in soil and cotton plants. The study was carried out as a pot culture experiment under laboratory conditions using a Gaucho formulation containing ¹⁴C-labeled imidacloprid. Three treatments of cotton seeds were made in sandy loamy soil: live seeds grown in autoclaved soil, dead seeds put in live soil and live seeds grown in live soil. Results showed that total ¹⁴C recoveries decreased by time ranging 93.8–96.2, 77.1–88.4 and 53.5–62.4% of the applied radioactivity at 7, 14, and 21 d after application, respectively. The reduction in the extracted ¹⁴C from soil coincided with the increase of non-extracted ones. Levels of bound ¹⁴C was always less in autoclaved soil than in live ones. Results revealed also that only 1.8–6.8% of the applied ¹⁴C was taken up by the plants and fluctuated within the test period. ¹⁴C levels were higher in plants grown in autoclaved soil than those in live ones and the radioactivity tended to accumulate on the edges of cotton leaves. Most of the radioactivity in the soil extracts was identified as unchanged ¹⁴C-imidacloprid.     

Fate of metolachlor under subirrigation in a sandy soil: a lysimeter study

A three-year field lysimeter study was conducted to investigate the role of subirrigation systems in reducing the risk of water pollution from metolachlor (2-chloro-N-(2-ethyl-6-methlphenyl)-N-(2-methoxy-1-methylethyl)ace tamide). Nine large PVC lysimeters, 1 m long x 0.45 m diameter, were packed with a sandy soil. Three water table management treatments, i.e. two subirrigation treatments with constant water table depths of 0.4 and 0.8 m, respectively, and a free drainage treatment in a completely randomized design with three replicates were used. Corn (Zea mays L.) was grown in each lysimeter, and at the beginning of summer of each year metolachlor was applied, at the locally recommended rate of 2.75 kg a.i./ha. Soil and water samples were collected at different time intervals after each natural or simulated rainfall event. Metolachlor was extracted from these samples and analyzed using Gas Chromatography. Results obtained in this three year study, (1993-1995), lead to the conclusion that metolachlor is quite mobile since it leached to a depth of 0.85 m below the soil surface quite early in the growing season. Metolachlor concentrations decreased with depth as well as with time. The shallower water table in the 0.4 m subirrigation treatment showed less residues in the soil solution than that of other treatments. However, a mass balance study, supported by an independent laboratory investigation, shows that water table management, statistically, has no significant effect on the reduction of metolachlor residues in sandy soils.     

Fate of metolachlor under subirrigation in a sandy soil: A lysimeter study

Abstract

A three‐year field lysimeter study was conducted to investigate the role of subirrigation systems in reducing the risk of water pollution from metolachlor (2‐chloro‐N‐(2‐ethyl‐6‐methlphenyl)‐N‐(2‐methoxy‐l‐methylethyl)acetamide). Nine large PVC lysimeters, 1 m long x 0.45 m diameter, were packed with a sandy soil. Three water table management treatments, i.e. two subirrigation treatments with constant water table depths of 0.4 and 0.8 m, respectively, and a free drainage treatment in a completely randomized design with three replicates were used. Corn (Zea mays L.) was grown in each lysimeter, and at the beginning of summer of each year metolachlor was applied, at the locally recommended rate of 2.75 kg a.i./ha. Soil and water samples were collected at different time intervals after each natural or simulated rainfall event. Metolachlor was extracted from these samples and analyzed using Gas Chromatography.

Results obtained in this three year study, (1993–1995), lead to the conclusion that metolachlor is quite mobile since it leached to a depth of 0.85 m below the soil surface quite early in the growing season. Metolachlor concentrations decreased with depth as well as with time. The shallower water table in the 0.4 m subirrigation treatment showed less residues in the soil solution than that of other treatments. However, a mass balance study, supported by an independent laboratory investigation, shows that water table management, statistically, has no significant effect on the reduction of metolachlor residues in sandy soils.     

毒死蜱在不同土壤腐殖酸上的吸附/解吸特征

通过平衡振荡法研究毒死蜱在不同来源土壤腐殖酸(Has)上的吸附/解吸行为.结果表明,毒死蜱在Has上的等温吸附行为用Freundlich模型描述相对更合理;它们的吸附等温线在实验范围内基本呈直线,且吸附能力很强,顺序为:紫色潮土Has＞黄壤Has＞中性紫色土Has＞酸性紫色土Has＞腐殖土Has;但毒死蜱的解吸率较小,其值均小于26.70%,有明显的滞后现象,尤其是腐殖土Has和紫色潮土Has,固定能力顺序为:紫色潮土Has＞腐殖土Has＞中性紫色土Has＞酸性紫色土Has＞黄壤Has.由于不同来源土壤中Has的组成结构差异明显,它们对毒死蜱的吸附/解吸规律表现出不同的特征.土壤Has对毒死蜱的吸附/解吸行为的影响是多种因素综合作用的结果,具体作用机理尚待进一步研究.     

Fate of the 14C-labeled herbicide prosulfocarb in a soil and in a sediment-water system

The fate of ¹⁴C-labeled herbicide prosulfocarb was studied in an agricultural soil and in a sediment-water system, the sediment part of which was derived from Yangtze Three Gorges Reservoir, China. Time-course studies were performed for 28 d and 49 d, respectively. Main transformation routes of ¹⁴C-prosulfocarb were mineralization to ¹⁴CO₂ and formation of nonextractable residues amounting to 12.13% and 10.43%, respectively, after 28 days (soil), and 9.40% and 11.98%, respectively, after 49 d (sediment-water system). Traces of prosulfocarbsulfoxide were detected by means of TLC, HPLC, and LC-MS; other transformation products were not found. Initial extraction of soil assays using 0.01 M CaCl₂ solution showed that the bioavailability of the herbicide was considerably low; immediately after application (0.1 d of incubation), only 4.78% of applied radioactivity were detected in this aqueous fraction. DT₅₀ values of ¹⁴C-prosulfocarb estimated from radio-TLC and -HPLC analyses were above 28 d in soil and ranged between 29 d and 49 d in the sediment-water system. Partitioning of ¹⁴C from water to sediment phase occurred with DT₅₀ slightly above 2 d. With regard to the sediment-water system, adsorption occurred with log K_oc = 1.38 (calculated from 2 day assays) and 2.35 (49 d assays). As similarly estimated from portions of ¹⁴C found in CaCl₂ extracts of the 0.1 d assays, ¹⁴C-prosulfocarb's log K_oc in soil was 2.96. With both experiments, similar portions of nonextractable radioactivity were associated with all soil organic matter fractions, i.e. nonhumics, fulvic acids, humic acids, and humin/minerals. Throughout all sample preparation, the experiments were severely impaired by losses of radioactivity especially with concentration of samples containing water in vacuo. All findings pointed to volatility of parent prosulfocarb in presence of water rather than volatility of transformation products. According to literature data, this behavior of prosulfocarb was not expected, though volatility was demonstrated under field conditions.     

Fate of hexachlorobenzene-14C in wheat plants and soil under outdoor conditions

Residues of hexachlorobenzene-¹⁴C were found in all parts of wheat plants grown from treated seeds or in contaminated soil. Besides the parent compound and bound residues in plants and soil, very small amounts of soluble acidic metabolites were present in plants, which were characterized and determined quantitatively.     

Fate of tetrabromobisphenol A and hexabromocyclododecane brominated flame retardants in soil and uptake by plants

The fate of tetrabromobisphenol A (TBBPA) and hexabromocyclododecane diastereomers (α-, β-, and γ-HBCD) and uptake by plants (cabbage and radish) was investigated. In a short-term (8 weeks) experiment, sorption to soil matrix resulted in 90% decline in recovery of these compounds in the experimental soil. However, nearly 50% of initial HBCDs recovered in mixed cabbage-radish treatments, which suggested that interspecific plant interactions might enhance the bioavailability of HBCDs. Although both plant species could uptake TBBPA and HBCDs, cabbage showed greater accumulating ability. Up to 3.5-10.0-fold higher HBCD concentrations were observed than TBBPA concentrations in all plant tissues, and the distribution of HBCDs in plant tissues was diastereomer-specific. The predominance of α-HBCD in shoot tissues for both species might be attributed to diastereomer-specific translocation of HBCDs, shift in diastereomer pattern and/or selective metabolization of γ-HBCD within plants. The results showed that strong sorption to soil particles reduced the potential of human exposure to BFRs in the soil. However, plants increased the exposure risk by uptaking these compounds and by enhancing their bioavailability. The results also provide insight into transport mechanisms of TBBPA and HBCD diastereomers in soil-plant systems.     

Fate and transport of carbamazepine in soil aquifer treatment (SAT) infiltration basin soils

The transport and fate of the pharmaceutical carbamazepine (CBZ) were investigated in the Dan Region Reclamation Project (SHAFDAN), Tel-Aviv, Israel. Soil samples were taken from seven subsections of soil profiles (150 cm) in infiltration basins of a soil aquifer treatment (SAT) system. The transport characteristics were studied from the release dynamics of soil-resident CBZ and, subsequently, from applying a pulse input of wastewater containing CBZ. In addition, a monitoring study was performed to evaluate the fate of CBZ after the SAT. Results of this study indicate adsorption, and consequently retardation, in CBZ transport through the top soil layer (0-5 cm) and to a lesser extent in the second layer (5-25 cm), but not in deeper soil layers (25-150 cm). The soluble and adsorbed fractions of CBZ obtained from the two upper soil layers comprised 45% of the total CBZ content in the entire soil profile. This behavior correlated to the higher organic matter content observed in the upper soil layers (0-25 cm). It is therefore deduced that when accounting for the full flow path of CBZ through the vadose zone to the groundwater region, the overall transport of CBZ in the SAT system is essentially conservative. The monitoring study revealed that the average concentration of CBZ decreased from 1094 ± 166 ng L⁻¹ in the recharged wastewater to 560 ± 175 ng L⁻¹ after the SAT. This reduction is explained by dilution of the recharged wastewater with resident groundwater, which may occur as it flows to active reclamation wells.     

Intrinsic degradation of volatile fatty acids in laboratory-compacted clayey soil

Volatile fatty acids (VFAs) represent the major organic constituent of landfill leachate and provide the greatest potential for leachate induced organic contamination of groundwater (e.g. as represented by an increase in the concentration of dissolved organic carbon and chemical oxygen demand). Long-term diffusion tests were performed for laboratory-compacted clayey soil plugs exposed to continuous supply of synthetic leachate containing VFAs. Significant microbial activity developed upon exposure of the soil's indigenous microorganisms to these degradable contaminants. The growth of heterotrophic aerobic bacteria (HAB, which include facultative anaerobes), sulfate reducing bacteria (SRB) and methanogenic bacteria carrying out fermentation and mineralization of the VFAs became evident after 30-50 days of testing. The maximum microbial counts of (2-8) x 10(8) and (0.1-1) x 10(8) cfu/g for HAB and SRB were localized in the soil layer at the interface with the source of organic and inorganic nutrients. Regardless of this rapid growth in microbial population, the VFA consumption was small and measurable only after a lag of 140-180 days. It is considered that this lag of otherwise readily degradable organic compounds (such as VFAs) persisted due to a combination of the effects of a high initial concentration of these acids (2.4 g/l as dissolved organic carbon, DOC) applied to carbon starved soil microorganisms and the small pore size of the compacted clay. Once the significant amounts of gas were generated from fermentation, conditions developed for improved mass transport and exchange of the nutrients and bacteria and the outcome of the intrinsic degradation was more apparent. The breakdown of VFAs that followed after the lag was localized near the top of the soil and was characterized by a short half-life of 0.75-5 days for DOC (total VFAs as dissolved organic carbon).     

Equilibrium sorption of phenanthrene by soil humic acids

This study investigated the effect of chemical heterogeneity of humic acids (HAs) on the equilibrium sorption of phenanthrene by HA extracts. Six HA samples were extracted from three different soils with 0.5 M NaOH and 0.1 M Na₄P₂O₇ and were characterized with elemental analysis, infrared spectrometry, and solid-state ¹³C nuclear magnetic resonance (NMR) spectrometry. The equilibrium sorption measurements were carried out with a batch technique and using the six HA solids as the sorbents and phenanthrene as the sorbate. The measured sorption isotherm data were fitted to the Freundlich equation. The results showed that, for the same soil, (i) the total HA mass extracted with Na₄P₂O₇ was 13.7–22.6% less than that extracted with NaOH, (ii) the Na₄P₂O₇-extracted HA had higher O/C atomic ratio, greater content of polar organic carbons (POC), and lower aliphatic carbon content than the NaOH-extracted HA, and (iii) the Na₄P₂O₇-extracted HA exhibited greater sorption isotherm linearity and but not dramatic difference in sorption capacities than the NaOH extracted HA. The differences in the HA properties resulting from the two different extraction methods may be because NaOH can hydrolyze insoluble HA fractions such as fatty acid like macromolecules bound on soils whereas Na₄P₂O₇ could not. As a result, the HAs extracted with the two different methods had different polarity and functionality which affected their sorption property for phenanthrene.