The influence of metam sodium on soil respiration

Abstract

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.     

Behavior of methyl isothiocyanate in soils under field conditions in Morocco

The behavior of methyl isothiocyanate (MITC), active metabolite of metam-sodium (MS), was studied under field conditions in Morocco. MS was applied through drip irrigation in: (i) uncovered soil, (ii) soil covered with transparent polyethylene, and (iii) soil covered with virtual impermeable film. Concentrations of MITC were determined at different soil depths to determine the distribution of MITC and the concentration-time product (CTP). Six hours after MS application, in a sandy soil, MITC reaches the 20-30 cm soil layer, but remains highly concentrated in the upper 10-20 cm soil layer. In a silty clay soil, MITC was concentrated in the upper 0-10 cm soil layer. The dissipation of MITC under different conditions of application was fast and complete after seven days. However, MITC dissipation time (DT(50)) was <24 h in sandy soil treated, but 63 h in silty clay soil. Under these application conditions of MS, the plastic film reduced MITC loss to the atmosphere but the plastic film quality did not affect the behavior of MITC. The use of plastic film maintained high MITC concentrations and appropriate CTP at different soil depths.     

Emission, distribution and leaching of methyl isothiocyanate and chloropicrin under different surface containments

The environmental fate of fumigants methyl isothiocyanate (MITC) and chloropicrin (CP) is of great concern for potential air and groundwater contamination while retaining sufficient concentrations for pest control efficacy. The emission, gas phase distribution, leaching, and persistence of MITC and CP were examined in repacked columns filled with sandy soils under three surface conditions: tarp without irrigation, tarp with limited irrigation, and 5-d irrigation without tarp cover. For MITC, cumulative emission constituted 62%, 36%, and 0.3% of the amount applied under tarp without irrigation, tarp with limited irrigation, and 5-d irrigation without tarp surface conditions, respectively. The corresponding cumulative emission losses were 45%, 30%, and 5.4% for CP. During the first 24h after injection, soil air concentrations of the two fumigants were much higher in the 15-25cm depth range than other depths in the soil profile. Small amounts of leaching occurred for both fumigants, indicating potential for groundwater contamination should heavy rain fall or irrigation occurs immediately after soil fumigation. Very small amounts of residual MITC and CP (<2%) were found in the soil 24 days after the experiment. The study clearly showed that atmospheric emission and degradation were the two primary pathways of MITC and CP dissipation during soil fumigation. Emission could be effectively reduced with 5-d irrigation if small leaching is acceptable or be prevented.     

Layer of organic pine forest soil on top of chlorophenol-contaminated mineral soil enhances contaminant degradation

Chlorophenols, like many other synthetic compounds, are persistent problem in industrial areas. These compounds are easily degraded in certain natural environments where the top soil is organic. Some studies suggest that mineral soil contaminated with organic compounds is rapidly remediated if it is mixed with organic soil. We hypothesized that organic soil with a high degradation capacity even on top of the contaminated mineral soil enhances degradation of recalcitrant chlorophenols in the mineral soil below. We first compared chlorophenol degradation in different soils by spiking pristine and pentachlorophenol-contaminated soils with 2,4,6-trichlorophenol in 10-L buckets. In other experiments, we covered contaminated mineral soil with organic pine forest soil. We also monitored in situ degradation on an old sawmill site where mineral soil was either left intact or covered with organic pine forest soil. 2,4,6-Trichlorophenol was rapidly degraded in organic pine forest soil, but the degradation was slower in other soils. If a thin layer of the pine forest humus was added on top of mineral sawmill soil, the original chlorophenol concentrations (high, ca. 70 μg g^?1, or moderate, ca. 20 μg g^?1) in sawmill soil decreased by >40 % in 24 days. No degradation was noticed if the mineral soil was kept bare or if the covering humus soil layer was sterilized beforehand. Our results suggest that covering mineral soil with an organic soil layer is an efficient way to remediate recalcitrant chlorophenol contamination in mineral soils. The results of the field experiment are promising.     

Leaching and degradation of ethametsulfuron-methyl in soil

Leaching and degradation of the herbicide ethametsulfuron-methyl[methyl 2-[(4-ethoxy-6-methylamino-1,3,5-triazine-2-yl)carbamoylsulfamoyl]benzoate] in three soils were investigated under laboratory conditions. Ethametsulfuron-methyl was mobile on soils when tested using non-aged and aged soil columns; this mobility agreed reasonably well with Freundlich soil isotherm constants. It was found that ethametsulfuron-methyl was more mobile in alkaline sandy Vertisol soil and neutral loamy Alfisol soil than in acidic clayey Red soil. Degradation of ethametsulfuron-methyl in soils was pH-dependent; calculated half-life (t(1/2)) values ranged from 13 to 67 days. Ethametsulfuron-methyl was more persistent in neutral or weakly basic than in acidic soil. Five soil metabolites were isolated and identified by LC/MS/MS analysis. The degradation pathways included the cleavage of the sulfonylurea bridge, N- and O-dealkylation, and triazine ring opening.     

Behavior of 1,3-dichloropropene and methyl isothiocyanate in undisturbed soil columns

To develop alternatives to methyl bromide (MeBr) for soil disinfection under environmental Moroccan conditions, distribution and persistence of 1,3-dichloropropene (1,3-D) and methyl isothiocyanate (MITC) were tested in undisturbed soil columns (12 cm internal diameter, 1 m length). 1,3-D was injected at a 15 cm depth and directly followed by metam-sodium (a precursor of MITC), which was applied at the soil surface of the same column using a peristaltic pump. Concerning the distribution of these fumigants in the soil profiles, our results showed that 24 h after treatment, 1,3-D and MITC were concentrated at the 0-40 cm soil layers, and reached the deeper layers 48 h later. MITC and 1,3-D dissipation was studied and the half-life (DT50) measured were 6.5 and 8 days, respectively. Total volatilization losses reached 9% for MITC and 28% for 1,3-D. MITC and 1,3-D volatilization was found to be influence by soil water contents.The results show that by reducing volatilization, photodegradation and leaching of these fumigants a suitable alternative to MeBr use is offered.     

Effects of soil organic matter on the development of the microbial polycyclic aromatic hydrocarbons (PAHs) degradation potentials

The microbial activity in soils was a critical factor governing the degradation of organic micro-pollutants. The present study was conducted to analyze the effects of soil organic matter on the development of degradation potentials for polycyclic aromatic hydrocarbons (PAHs). Most of the degradation kinetics for PAHs by the indigenous microorganisms developed in soils can be fitted with the Logistic growth models. The microbial activities were relatively lower in the soils with the lowest and highest organic matter content, which were likely due to the nutrition limit and PAH sequestration. The microbial activities developed in humic acid (HA) were much higher than those developed in humin, which was demonstrated to be able to sequester organic pollutants stronger. The results suggested that the nutrition support and sequestration were the two major mechanisms, that soil organic matter influenced the development of microbial PAHs degradation potentials.     

Application of magnetite-activated persulfate oxidation for the degradation of PAHs in contaminated soils

In this study, feasibility of magnetite-activated persulfate oxidation (AP) was evaluated for the degradation of polycyclic aromatic hydrocarbons (PAHs) in batch slurry system. Persulfate oxidation activated with soluble Fe(II) (FP) or without activation (SP) was also tested. Kinetic oxidation of PAHs was tracked in spiked sand and in aged PAH contaminated soils at circumneutral pH. Quartz sand was spiked with: (i) single model pollutant (fluorenone) and (ii) organic extract isolated from two PAH contaminated soils (H and NM sampled from ancient coking plants) and was subjected to oxidation. Oxidation was also performed on real H and NM soils with and without an extraction pretreatment. Results indicate that oxidation of fluorenone resulted in its complete degradation by AP while abatement was very low (<20%) by SP or FP. In soil extracts spiked on sand, significant degradation of 16 PAHs was observed by AP (70-80%) in 1 week as compared to only 15% by SP or FP systems. But no PAH abatement was observed in real soils whatever the treatment used (AP, FP or SP). Then soils were subjected to an extraction pretreatment but without isolation of organic extract from soil. Oxidation of this pretreated soil showed significant abatement of PAHs by AP. On the other hand, very low degradation was achieved by FP or SP. Selective degradation of PAHs was observed by AP with lower degradation efficiency towards high molecular weight PAHs. Analyses revealed that no by-products were formed during oxidation. The results of this study demonstrate that magnetite can activate persulfate at circumneutral pH for an effective degradation of PAHs in soils. However, availability of PAHs and soil matrix were found to be the most critical factors for degradation efficiency.     

Mathematical prediction of imidacloprid persistence in two Croatian soils with different texture,organic matter content and acidity under laboratory conditions

In the present laboratory study, persistence of imidacloprid (IMI) as a function of initial insecticide concentration and soil properties in two Croatian soils (Krk sandy clay and Istria clay soils) was studied and described mathematically. Upon fitting the obtained experimental data for the higher concentration level (5 mg/kg) to mathematical models, statistical parameters (R ², scaled root mean squared error and χ ² error) indicated that the single first-order kinetics model provided the best prediction of IMI degradation in the Krk sandy clay soil, while in the Istria clay soil biphasic degradation was observed. At the lower concentration level (0.5 mg/kg), the biphasic models Gustafson and Holden models as well as the first-order double exponential model fitted the best experimental data in both soils. The disappearance time (DT₅₀) values estimated by the single first-order double exponential model (from 50 to 132 days) proved that IMI can be categorized as a moderately persistent pesticide. In the Krk sandy clay soil, resulting DT₅₀ values tended to increase with an increase of initial IMI concentration, while in the Istria clay soil, IMI persistence did not depend on the concentration. Organic matter of both experimental soils provided an accelerating effect on the degradation rate. The logistic model demonstrated that the effect of microbial activity was not the most important parameter for the biodegradation of IMI in the Istria clay soil, where IMI degradation could be dominated by chemical processes, such as chemical hydrolysis. The results pointed that mathematical modeling could be considered as the most convenient tool for predicting IMI persistence and contributes to the establishment of adequate monitoring of IMI residues in contaminated soil. Furthermore, IMI usage should be strictly controlled, especially in soils with low organic matter content where the risk of soil and groundwater contamination is much higher due to its longer persistence and consequent leaching and/or moving from soil surface prior to its degradation.     

Enhanced degradation of carbazole and 2,3-dichlorodibenzo-p-dioxin in soils by Pseudomonas resinovorans strain CA10

We studied the degradation of carbazole (CAR) and 2,3-dichlorodibenzo-p-dioxin (2,3-DCDD) in soils inoculated with carbazole- and dioxin-degrader Pseudomonas resinovorans strain CA10. By using Tn5-based transposon delivery systems, this bacterium was chromosomally marked with a tandem green fluorescent protein (gfp) gene. Real-time competitive PCR and direct counting using the (gfp) marker were employed to monitor the total number of carbazole 1,9a-dioxygenase gene (carAa) and survival of CA10 cells in the soil and soil slurry microcosms. Bioaugmentation studies indicated that the survival of the marked CA10 cells in soil microcosms was strongly influenced by pH and organic matter. While the number of the marked CA10 cells decreased rapidly in pH 6 with low organic matter, a high cell density was maintained in pH 7.3 with 2.5% organic matters up to 21 days after inoculation. In pH 7.3 soil, the period needed for complete degradation of CAR (100 microg kg(-1)) was markedly shortened from 21 to 7 days by the inoculation with the CA10 cells. Single inoculation of CA10 cells into the soil slurry system of 2,3-DCDD-contaminated soil enhanced the degradation of 2,3-DCDD from 25.0% to 37.0%. In this system, the population density of CA10 cells and the total number of carAa gene were maintained up to 14 days after inoculation. By repeated inoculation (every 2 days) with CA10 cells each at a density of 10(9) CFU g(-1) of soil, almost all of the 2,3-DCDD (1 microg kg(-1)) was degraded within 14 days. Results of these experiments suggest that P. resinovorans strain CA10 may be an important resource for bioremediation of CAR and chlorinated dibenzo-p-dioxin in contaminated soils.     

Sorption and degradation of neonicotinoid insecticides in tropical soils

ABSTRACT

Neonicotinoids are the most widely applied class of insecticides in cocoa farming in Ghana. Despite the intensive application of these insecticides, knowledge of their fate in the Ghanaian and sub-Saharan African environment remains low. This study examined the behavior of neonicotinoids in soils from cocoa plantations in Ghana by estimating their sorption and degradation using established kinetic models and isotherms. Studies of sorption were conducted using the batch equilibrium method on imidacloprid, thiamethoxam, clothianidin, acetamiprid and thiacloprid, while degradation of imidacloprid, thiamethoxam and their respective deuterated counterparts was studied using models proposed by the European forum for coordination of pesticide fate and their use (FOCUS). Analytes were extracted using the quick, easy, cheap, effective, rugged and safe (QuEChERS) procedure and quantified by liquid chromatography-tandem mass spectrometry (LC–MS/MS). Average recoveries were high (≥ 85%) for all analytes. The findings from the study suggest that neonicotinoid insecticides may be persistent in the soils studied based on estimated half-lives > 150 days. The study also revealed generally low-sorption coefficients for neonicotinoids in soils, largely influenced by soil organic carbon.     

The aerobic soil degradation of spinosad ‐ a novel natural insect control agent

Abstract

Spinosad is a natural product with biological activity against a range of insects including lepidoptera. It is comprised of two major components namely spinosyns A and D. The degradation of spinosad in soil under aerobic conditions was investigated using two U.S. soils (a silt loam and a sandy loam) which were treated with either ¹⁴C‐spinosyn A or ‐spinosyn D at a 2X use rate of 0.4mg/kg soil for spinosyn A and 0.1mg/kg for spinosyn D. Further samples of soil were pre‐sterilised prior to treatment in order to establish whether spinosyns A and D degrade abiotically. Flasks of treated soil were incubated in the dark at 25°C for up to one year after treatment.

HPLC and LC‐MS of soil extracts confirmed that the major degradation product of spinosyn A was spinosyn B, resulting from demethylation on the forosamine sugar. Other dégradâtes were hydroxylation products of spinosyns A and B, with hydroxylation probably taking place on the aglycone portion of the molecule. Half lives were similar for both spinosyns and were in the range 9–17 days, with longer half lives in the pre‐sterilised soils (128–240 days) suggesting that degradation was largely microbial.     

Factors influencing 2,4-D sorption and mineralization in soil

This study quantified 2,4-D [(2,4-dichlorophenoxy)acetic acid] sorption and mineralization rates in five soils as influenced by soil characteristics and nutrient contents. Results indicated that 2.4-D was weakly sorbed by soil, with Freundlich distribution coefficients ranging from 0.81 to 2.89 microg(1 - 1/n) g(-1) mL(1/n). First-order mineralization rate constants varied from 0.03 to 0.26, corresponding to calculated mineralization half-lives of 3 and 22 days, respectively. Herbicide sorption generally increased with increasing soil organic carbon content, but the extent of 2,4-D sorption per unit organic carbon varied among the soils due to differences in soil pH, clay content and/or organic matter quality. Herbicide mineralization rates were greater in soils that sorbed more 2,4-D per unit organic carbon, and that had greater soil nitrogen contents. We conclude that the effect of sorption on herbicide degradation cannot be generalized without a better understanding of the effects of soil characteristics and nutrient content on herbicide behavior in soil.     

Limitations on the role of incorporated organic matter in reducing pesticide leaching.

The use of organic amendments has been suggested as a method of controlling pesticide leaching through soils. The enarenados soils of the intensive horticulture of the Almeria province of southern Spain contain buried organic matter horizons above a soil layer amended with clay. This region is ideal for understanding the potential for and limitations of organic amendments in preventing pesticide pollution. This study measured the sorption and degradation potential of carbofuran in this soil system and the hydrological behaviour of the soil horizons. The sorption of carbofuran was controlled by the organic carbon content, the degradation was strongly pH-dependent and the acidic organic layer protected the sorbed carbofuran against degradation. Hydrologically, the soil system is dominated by ponding above an amended clay layer and by the presence of macropores that can transport water through this clay. A simple model is proposed on this basis and shows that although high levels of dissolved organic carbon can be released by buried organic horizons, the major control on re-release of sorbed pesticide is the potential for sorption hysteresis in this organic layer. A comparison of sorption and degradation data for carbamate insecticides used in the region with groundwater observations for these compounds shows that no amount of incorporated organic would protect against pollution from highly water-soluble compounds.     

Degradation kinetics of forchlorfenuron in typical grapevine soils of India and its influence on specific soil enzyme activities

The rate of degradation of forchlorfenuron, a cytokinin-based plant growth regulator (PGR) was explored in typical grapevine soils of India with simultaneous evaluation of its effect on biochemical attributes of the test soils in terms of the activities of specific soil microbial enzymes. In all the test soils, namely clay, sandy-loam and silty-clay, the dissipation rate was faster at the beginning, which slowed down with time, indicating a non-linear pattern of degradation. Degradation in soils could best be explained by two-compartment 1st + 1st order kinetics with half-life ranging between 4–10 days. The results suggest that organic matter might be playing a major role in influencing the rate of degradation of forchlorfenuron in soil. The rate of degradation in sandy-loam soil was fastest followed by clay and silty-clay soils, respectively. Comparison of the rate of degradation in natural against sterilized soils suggests that microbial degradation might be the major pathway of residue dissipation. Changes in soil enzyme activities as a consequence of forchlorfenuron treatment were studied for extra-cellular enzymes namely acid phosphatase, alkaline phosphatase and β -glucosidase and intracellular enzyme-dehydrogenase. Although small changes in enzyme activities were observed, forchlorfenuron did not have any significant deleterious effect on the enzymatic activity of the test soils. Simple correlation studies between degradation percentage and individual enzyme activities did not establish any significant relationships. The pattern and change of enzyme activity was primarily the effect of the incubation period rather than the effect of forchlorfenuron itself.     

Biodegradation and speciation of residual SS-ethylenediaminedisuccinic acid (EDDS) in soil solution left after soil washing

This paper aims to investigate the degradation and speciation of EDDS-complexes (SS-ethylenediaminedisuccinic acid) in soil following soil washing. The changes in soil solution metal and EDDS concentrations were investigated for three polluted soils. EDDS was degraded after a lag phase of 7-11 days with a half-life of 4.18-5.60 days. No influence of EDDS-speciation on the reaction was observed. The decrease in EDDS resulted in a corresponding decrease in solubilized metals. Changes in EDDS speciation can be related to (1) initial composition of the soil, (2) temporarily anoxic conditions in the soil slurry after soil washing, (3) exchange of EDDS complexes with Cu even in soils without elevated Cu and (4) formation of NiEDDS. Dissolved organic matter is important for metal speciation at low EDDS concentrations. Our results show that even in polluted soils EDDS is degraded from a level of several hundred micromoles to below 1 microM within 50 days.     

Effect of sludge-amendment or nutrient addition on the biodegradation of the herbicide isoproturon in soil

Adding sludge to agricultural soil results in added organic matter, nutrients and metallic and/or organic pollutants. These components may modify the behaviour of pesticides in the soil. We monitored possible changes in the degradation of the herbicide isoproturon (production of CO2 and degradation products) in soil amended with sludge, heavy metals or nitrogen and phosphorus. The treated and control soils were incubated under controlled conditions for 60 days. The nitrogen and phosphorus had the greatest effect on isoproturon degradation, independent of the presence of pollutants. Mineralisation of the herbicide to CO2 was slow and seemed to be linked to a fast degradation and to the accumulation of a complex degradation product that was neither catabolized nor adsorbed, 4,4'-diisopropylazobenzene. This degradation pathway also produced smaller amounts of non-extractable residues. Sewage sludge had no significant effect on isoproturon degradation, despite a large increase of organic matter mineralisation (factor 2).     

Degradation kinetics of forchlorfenuron in typical grapevine soils of India and its influence on specific soil enzyme activities

The rate of degradation of forchlorfenuron, a cytokinin-based plant growth regulator (PGR) was explored in typical grapevine soils of India with simultaneous evaluation of its effect on biochemical attributes of the test soils in terms of the activities of specific soil microbial enzymes. In all the test soils, namely clay, sandy-loam and silty-clay, the dissipation rate was faster at the beginning, which slowed down with time, indicating a non-linear pattern of degradation. Degradation in soils could best be explained by two-compartment 1st+1st order kinetics with half-life ranging between 4-10 days. The results suggest that organic matter might be playing a major role in influencing the rate of degradation of forchlorfenuron in soil. The rate of degradation in sandy-loam soil was fastest followed by clay and silty-clay soils, respectively. Comparison of the rate of degradation in natural against sterilized soils suggests that microbial degradation might be the major pathway of residue dissipation. Changes in soil enzyme activities as a consequence of forchlorfenuron treatment were studied for extra-cellular enzymes namely acid phosphatase, alkaline phosphatase and beta -glucosidase and intracellular enzyme-dehydrogenase. Although small changes in enzyme activities were observed, forchlorfenuron did not have any significant deleterious effect on the enzymatic activity of the test soils. Simple correlation studies between degradation percentage and individual enzyme activities did not establish any significant relationships. The pattern and change of enzyme activity was primarily the effect of the incubation period rather than the effect of forchlorfenuron itself.     

Fugacity modelling to predict the distribution of organic contaminants in the soil:oil matrix of constructed biopiles

Level I and II fugacity approaches were used to model the environmental distribution of benzene, anthracene, phenanthrene, 1-methylphenanthrene and benzo[a]pyrene in a four phase biopile system, accounting for air, water, mineral soil and non-aqueous phase liquid (oil) phase. The non-aqueous phase liquid (NAPL) and soil phases were the dominant partition media for the contaminants in each biopile and the contaminants differed markedly in their individual fugacities. Comparison of three soils with different percentage of organic carbon (% org C) showed that the % org C influenced contaminant partitioning behaviour. While benzene showed an aqueous concentration worthy of note for leachate control during biopiling, other organic chemicals showed that insignificant amount of chemicals leached into the water, greatly reducing the potential extent of groundwater contamination. Level II fugacity model showed that degradation was the dominant removal process except for benzene. In all three biopile systems, the rate of degradation of benzo(a)pyrene was low, requiring more than 12 years for soil concentrations from a spill of about 25 kg (100 mol) to be reduced to a concentration of 0.001 microgg(-1). The removal time of 1-methylphenanthrene and either anthracene or phenanthrene was about 1 and 3 years, respectively. In contrast, benzene showed the highest degradation rate and was removed after 136 days in all biopile systems. Overall, this study confirms the association of risk critical contaminants with the residual saturation in treated soils and reinforces the importance of accounting for the partitioning behaviour of both NAPL and soil phases during the risk assessment of oil-contaminated sites.     

Comparative abiotic or biotic degradation of carboxin by two Entisols with different surface properties or Pseudomonas aeruginosa strain: A toxicity study using the crustacean Thamnocephalus platyurus

The microcrustacean Thamnocephalus platyurus was used to detect the toxicity reduction of carboxin in abiotic degradation compared to biotic degradation. The abiotic degradation was obtained using two sterilized Entisols with different surface properties while the biotic degradation by Pseudomonas aeruginosa was obtained using the fungicide as the only C source. The results showed that the highest toxicity reduction rates for the abiotic degradation were achieved in 20 days with 49.2% for the coarser soil, 60.7% for the soil with a finer texture, whereas for the biotic degradation, 60.6%. Analysis (¹H NMR) showed that the soils transformed carboxin to produce sulfoxide and enol in different concentrations depending on the soil properties, while P. aeruginosa metabolized the fungicide to produce inorganic compounds such as ammonium and nitrite, minor degradation pathways were oxidized to sulfoxide and hydrolytic ring-opening to 2-[(2-hydroxyethyl)thio]acetoacetanilide enol. These results indicated that the degradation of carboxin occurred via abiotic catalytic processes as well as via biotic transformation leading to less toxic derivatives and such phenomena are caused by exchange/surface features of soils, rather than by the mere content of clay or organic matter fractions.