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1.
Pest Manag Sci ; 74(5): 1206-1212, 2018 May.
Artigo em Inglês | MEDLINE | ID: mdl-28111921

RESUMO

BACKGROUND: Biochar, a carbon-rich product of biomass pyrolysis, could limit glyphosate transport in soil and remediate contaminated water. The present study investigates the sorption/desorption behavior of glyphosate on biochars prepared from different hardwoods at temperatures ranging from 350 to 900 °C to elucidate fundamental mechanisms. RESULTS: Glyphosate (1 mg L-1 ) sorption on biochars increased with pyrolysis temperature and was highest on 900 °C biochars; however, total sorption was low on a mass basis (<0.1 mg g-1 ). Sorption varied across feedstock materials, and isotherms indicated concentration dependence. Biochars with a greater fraction of micropores exhibited lower sorption capacities, and specific surface groups were also found to be influential. Prepyrolysis treatments with iron and copper, which complex glyphosate in soils, did not alter biochar sorption capacities. Glyphosate did not desorb from biochar with CaCl2 solution; however, up to 86% of the bound glyphosate was released with a K2 HPO4 solution. CONCLUSION: Results from this study suggest a combined impact of surface chemistry and physical constraints on glyphosate sorption/desorption on biochar. Based on the observed phosphate-induced desorption of glyphosate, the addition of P-fertilizer to biochar-amended soils can remobilize the herbicide and damage non-target plants; therefore, improved understanding of this risk is necessary. © 2017 Society of Chemical Industry.


Assuntos
Carvão Vegetal/química , Glicina/análogos & derivados , Herbicidas/química , Poluentes do Solo/química , Adsorção , Cátions/química , Fenômenos Químicos , Glicina/química , Fenômenos Físicos , Temperatura , Glifosato
2.
Chemosphere ; 184: 473-481, 2017 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-28618279

RESUMO

Biochar is a solid material obtained when biomass is thermochemically converted in an oxygen-limited environment. In most previous studies, the impacts of biochar on soil properties and organic carbon (C) were investigated under controlled conditions, mainly laboratory incubation or greenhouse studies. This 2-year field study was conducted to evaluate the influence of biochar on selected soil physical and chemical properties and carbon and nitrogen fractions for two selected soil types (clay loam and a sandy loam soil) under a corn (Zea mays L.)-soybean (Glycine max L.) rotation. The three plant based biochar materials used for this study were corn stover (CS), ponderosa pine (Pinus ponderosa Lawson and C. Lawson) wood residue (PW), and switchgrass (Panicum virgatum L.) (SG). Data showed that CS and SG significantly increased the pH of acidic soil at the eroded landscape position but produced no significant change in soil pH at the depositional landscape position. The effects of biochar treatments on cold water extractable C (WSC) and nitrogen (WSN) fractions for the 0-7.5 cm depth were depended on biochar and soil type. Results suggested that alkaline biochars applied at 10 Mg ha-1 can increase the pH and WSC fraction of acidic sandy loam soil, but the 10 Mg ha-1 rate might be low to substantially improve physical properties and hot water extractable C and N fractions of soil. Application of higher rates of biochar and long-term monitoring is needed to quantify the benefits of biochar under field conditions on soils in different environmental conditions.


Assuntos
Carvão Vegetal/química , Solo/química , Agricultura/normas , Biomassa , Carbono/análise , Carvão Vegetal/farmacologia , Concentração de Íons de Hidrogênio , Nitrogênio/análise , Glycine max/química , Zea mays/química
3.
J Environ Qual ; 44(2): 594-604, 2015 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-26023978

RESUMO

Open surface inlets that connect to subsurface tile drainage systems provide a direct pathway for movement of sediment, nutrients, and agrochemicals to surface waters. This study was conducted to determine the reduction in drainage effluent total suspended sediment (TSS) and phosphorus (P) concentrations and loads when open surface inlets were replaced with blind (in gravel capped with 30 cm of soil) or gravel (in very coarse sand/fine gravel) inlets. In Indiana, a pair of closed depressions in adjacent fields was fitted with open inlet tile risers and blind inlets in 2005 and monitored for flow and water chemistry. Paired comparisons on a storm event basis during the growing season for years 2006 to 2013 showed that TSS loads were 40.4 and 14.4 kg ha event for tile risers and blind inlets, respectively. Total P (TP) and soluble reactive P (SRP) loads were 66 and 50% less for the blind inlets, respectively. In Minnesota, TSS and SRP concentrations were monitored for 3 yr before and after modification of 24 open inlets to gravel inlets in an unreplicated large-field on-farm study. Median TSS concentrations were 97 and 8.3 mg L and median SRP concentrations were 0.099 and 0.064 mg L for the open inlet and gravel inlet periods, respectively. Median TSS and SRP concentrations were elevated for snowmelt vs. non-snowmelt seasons for open and gravel inlets. Both replacement designs reduced suspended sediment and P concentrations and loads. The Indiana study suggests blind inlets will be effective beyond a 10-yr service life.

4.
J Hazard Mater ; 279: 244-56, 2014 Aug 30.
Artigo em Inglês | MEDLINE | ID: mdl-25064262

RESUMO

The tentative connection between the biochar surface chemical properties and their influence on microbially mediated mineralization of C, N, and S with the help of enzymes is not well established. This study was designed to investigate the effect of different biomass conversion processes (microwave pyrolysis, carbon optimized gasification, and fast pyrolysis using electricity) on the composition and surface chemistry of biochar materials produced from corn stover (Zea mays L.), switchgrass (Panicum virgatum L.), and Ponderosa pine wood residue (Pinus ponderosa Lawson and C. Lawson) and determine the effect of biochars on mineralization of C, N, and S and associated soil enzymatic activities including esterase (fluorescein diacetate hydrolase, FDA), dehydrogenase (DHA), ß-glucosidase (GLU), protease (PROT), and aryl sulfatase (ARSUL) in two different soils collected from footslope (Brookings) and crest (Maddock) positions of a landscape. Chemical properties of biochar materials produced from different batches of gasification process were fairly consistent. Biochar materials were found to be highly hydrophobic (low H/C values) with high aromaticity, irrespective of biomass feedstock and pyrolytic process. The short term incubation study showed that biochar had negative effects on microbial activity (FDA and DHA) and some enzymes including ß-glucosidase and protease.


Assuntos
Carvão Vegetal/química , Microbiologia do Solo , Biomassa , Carbono/química , Enzimas/análise , Microscopia Eletrônica de Varredura , Nitrogênio/química , Panicum/química , Pinus/química , Enxofre/química , Zea mays/química
5.
J Environ Sci Health B ; 48(12): 1049-57, 2013.
Artigo em Inglês | MEDLINE | ID: mdl-24007482

RESUMO

Sorption and desorption of aminocyclopyrachlor (6-amino-5-chloro-2-cyclopropylpyrimidine-4-carboxylic acid) were compared to that of the structurally similar herbicide picloram (4-amino-3,5,6-trichloro-2-pyridinecarboxylic acid) in three soils of differing origin and composition to determine if picloram data is representative of aminocyclopyrachlor behavior in soil. Aminocyclopyrachlor and picloram batch sorption data fit the Freundlich equation and was independent of concentration for aminocyclopyrachlor (1/n = 1), but not for picloram (1/n = 0.80-0.90). Freundlich sorption coefficients (K f) for aminocyclopyrachlor were lowest in the eroded and depositional Minnesota soils (0.04 and 0.12 µmol ((1-1/n)) L(1/n) kg(-1)) and the highest in Molokai soil (0.31 µmol ((1-1/n)) L(1/n) kg(-1)). For picloram, K f was lower in the eroded (0.28 µmol ((1-1/n)) L(1/n) kg(-1)) as compared to the depositional Minnesota soil (0.75 µmol ((1-1/n)) L(1/n) kg(-1)). Comparing soil to soil, K f for picloram was consistently higher than those found for aminocyclopyrachlor. Desorption of aminocyclopyrachlor and picloram was hysteretic on all three soils. With regard to the theoretical leaching potential based on groundwater ubiquity score (GUS), leaching potential of both herbicides was considered to be similar. Aminocyclopyrachlor would be ranked as leacher in all three soils if t1/2 was > 12.7 days. To be ranked as non-leacher in all three soils, aminocyclopyrachlor t1/2 would have to be <3.3 days. Calculated half-life that would rank picloram as leacher was calculated to be ∼15.6 d. Using the current information for aminocycloprachlor, or using picloram data as representative of aminocycloprachlor behavior, scientists can now more accurately predict the potential for offsite transport of aminocycloprachlor.


Assuntos
Herbicidas/química , Picloram/química , Pirimidinas/química , Poluentes do Solo/química , Adsorção , Água Subterrânea/análise , Meia-Vida , Solo/química , Poluentes Químicos da Água/química
6.
J Agric Food Chem ; 60(44): 10936-41, 2012 Nov 07.
Artigo em Inglês | MEDLINE | ID: mdl-23030723

RESUMO

Saflufenacil partitioning and dissipation were evaluated in soils from an eroded prairie landscape to provide information on its expected environmental fate. Saflufenacil K(d) values followed trends in soil organic carbon content. In surface soils, K(d) values ranged from 0.05 to 0.2 L kg(-1) in the depositional lower slope and from 0.02 to 0.06 L kg(-1) in the eroded upper slope. In subsurface soils, K(d) values were an order of magnitude higher in the lower slope (mean 0.1 L kg(-1)) than in the upper slope (mean 0.01 L kg(-1)). Sorption was slightly higher in samples aged 1-8 weeks compared to freshly spiked soils. Mean dissipation half-lives (DT(50)) were 13 d in surface soils and 32 d in subsurface soils. The observed low sorption and relatively rapid dissipation of saflufenacil suggest that this herbicide will be readily available for degradation or plant uptake in the root zone.


Assuntos
Ecossistema , Herbicidas/química , Pirimidinonas/química , Poluentes do Solo/química , Sulfonamidas/química , Cromatografia Líquida de Alta Pressão , Meia-Vida , Espectrometria de Massas em Tandem
7.
Pest Manag Sci ; 68(9): 1272-7, 2012 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-22517778

RESUMO

BACKGROUND: Sorption and dissipation of aged metolachlor were characterized in rehabilitated and eroded prairie soils using sequential batch slurry (conventional) and accelerated solvent extraction (ASE). RESULTS: In spite of an almost twofold difference in soil organic carbon (OC) content, S-metolachlor sorption coefficients (K(d)) and dissipation rates (DT(50)) were the same in soils from different landscape positions within an eroded landform. Soil was moved within the landform to increase productivity. In areas receiving topsoil addition, S-metolachlor K(d) was higher and DT(50) was longer than in eroded areas. The efficiency of extraction was higher for ASE than for conventional extractions. No consistent aging effect on K(d) was observed. Mineralization in 8 weeks accounted for < 10% of the applied metolachlor. CONCLUSION: The results of this laboratory study support a field dissipation study. Both showed that S-metolachlor has the same retention and dissipation rate throughout an eroded landform, which was not expected owing to the large variability in soil properties, including OC concentrations. Altering soil properties by adding topsoil increased metolachlor sorption and persistence. The method of extraction (conventional versus ASE) affected calculated sorption coefficients and dissipation rates. In all cases, groundwater ubiquity scores (GUSs) categorized metolachlor as having intermediate mobility.


Assuntos
Acetamidas/química , Herbicidas/química , Poluentes do Solo/química , Solo/química , Adsorção , Resíduos de Drogas/química , Cinética
8.
J Environ Qual ; 40(5): 1375-82, 2011.
Artigo em Inglês | MEDLINE | ID: mdl-21869499

RESUMO

Minimizing atmospheric emissions of soil fumigants is critical for protecting human and environmental health. Covering the soil surface with a plastic tarp is a common approach to restrict fumigant emissions. The mass transfer of the fumigant vapors through the tarp is often the rate-limiting factor in fumigant emissions. An approach for standardizing measurements of film permeability is proposed that is based on determining the resistance (R) of films to diffusion of fumigants. Using this approach, values were determined for more than 200 film-chemical combinations under a range of temperature, relative humidity, and film handling conditions. Resistance to diffusion was specific for each fumigant/film combination, with the largest range of values observed for the fumigant chloropicrin. For each fumigant, decreased with increasing temperature. Changes in film permeability due to increases in temperature or field installation were generally less than a factor of five. For one film, values determined under conditions of very high relative humidity (approximately 100%) were at least 100 times lower than when humidity was very low (approximately 2%). This approach simplifies the selection of appropriate films for soil fumigation by providing rapid, reproducible, and precise measurements of their permeability to specific fumigants and application conditions.


Assuntos
Praguicidas , Plásticos , Poluentes do Solo , Meio Ambiente , Permeabilidade
9.
Int J Microbiol ; 20112011.
Artigo em Inglês | MEDLINE | ID: mdl-20871863

RESUMO

Persistence of Escherichia coli (E. coli) O157:H7 in the environment is a major concern to vegetable and fruit growers where farms and livestock production are in close proximity. The objectives were to determine the effects of preplant fumigation treatment on the survival of E. coli O157:H7 in two soils and the effects of indigenous bacterial populations on the survival of this pathogen. Real-time PCR and plate counts were used to quantify the survival of E. coli O157:H7 in two contrasting soils after fumigation with methyl bromide (MeBr) and methyl iodide (MeI). Ten days after fumigation, E. coli O157:H7 counts were significantly lower (P = .0001) in fumigated soils than in the non-fumigated. Direct comparison between MeBr and MeI within each soil indicated that these two fumigants showed similar impacts on E. coli O157:H7 survival. Microbial species diversity as determined by DGGE was significantly higher in clay soil than sandy soil and this resulted in higher initial decline in population in clay soil than in sandy soil. This study shows that if soil is contaminated with E. coli O157:H7, fumigation alone may not eliminate the pathogen, but may cause decrease in microbial diversity which may enhance the survival of the pathogen.

10.
J Agric Food Chem ; 57(16): 7427-33, 2009 Aug 26.
Artigo em Inglês | MEDLINE | ID: mdl-19653694

RESUMO

Information regarding solute and water transport as affected by soil properties, topography, and climatic conditions is required to improve and validate transport models. This study evaluated the dissipation of bromide applied to the soil surface in the fall and spring to undisturbed (eroded) and rehabilitated landforms, in which topsoil was moved from depositional areas to the eroded upper slope. Despite large changes in soil properties, the amount and center of mass of bromide remaining in the top 1 m of soil was the same in undisturbed and rehabilitated plots. Approximately 60% of the fall-applied bromide was lost during the winter and early spring, presumably due to leaching and runoff. The center of mass of spring-applied bromide remained at depths of <30 cm. At the end of the experiment, 33% of the spring-applied bromide was detected in soil and 56% in corn plants. These results suggest that little bromide was leached out of the root zone in the spring and that plant uptake was a major route of bromide dissipation during the growing season.


Assuntos
Brometos/análise , Solo/análise , Brometos/metabolismo , Plantas/metabolismo , Estações do Ano , Movimentos da Água
11.
J Agric Food Chem ; 57(16): 7434-9, 2009 Aug 26.
Artigo em Inglês | MEDLINE | ID: mdl-19653695

RESUMO

The impact of varying soil, landscape, and climate conditions on the off-site transport of pesticides must be determined to develop improved pesticide management practices. This study quantified the rate of S-metolachlor dissipation after fall and spring application in eroded and rehabilitated landforms in which topsoil was moved from the lower slope to the upper slope. Fall-applied metolachlor provided no control of annual grasses because approximately 80% was removed from the root zone during the winter and early spring, presumably by leaching and runoff. S-Metolachlor dissipated in the spring with a DT(50) of 24-29 days. These results suggest that fall-applied metolachlor may not provide economic weed control and presents an increased risk of water contamination. Although landscape position and bulk soil movement within the landform had a large impact on soil properties, no significant differences in metolachlor dissipation between different landscape positions and between eroded and rehabilitated landforms were observed.


Assuntos
Acetamidas/análise , Praguicidas/análise , Poluentes do Solo/análise , Solo/análise , Estações do Ano , Movimentos da Água
12.
J Agric Food Chem ; 57(5): 1975-81, 2009 Mar 11.
Artigo em Inglês | MEDLINE | ID: mdl-19199601

RESUMO

Information regarding pesticide mobility is critical for the evaluation of pesticide management practices. Lysimeters have been used worldwide to assess the transport and plant uptake of solutes under relevant moisture regimes and crop production practices. We used repacked field lysimeters to evaluate the leaching and plant uptake of the herbicides pendimethalin, clopyralid, mecoprop (MCPP), and dicamba following fall and spring application to soil cropped to winter rye (Secale cereale L.). In most fall and spring trials, mass loss of herbicide through leaching was <3% of the amount applied. On the basis of this 6 year experiment, it appears that clopyralid is the most mobile of the tested herbicides in this soil, followed by dicamba, mecoprop, and pendimethalin. None of the herbicides was present in rye grain or straw at concentrations that exceed current E.U. or U.S. tolerances.


Assuntos
Agricultura/instrumentação , Herbicidas/química , Herbicidas/metabolismo , Secale/metabolismo , Cinética , Estações do Ano , Secale/química , Solo/análise
13.
J Agric Food Chem ; 56(16): 7367-72, 2008 Aug 27.
Artigo em Inglês | MEDLINE | ID: mdl-18651743

RESUMO

Pyrazosulfuron ethyl (PE) and halosulfuron methyl (HM) are two new highly active sulfonylurea herbicides that have been widely used for weed control in a variety of vegetables and other crops. These two herbicides have similar molecular structures, differing only in the substitutions on the pyrazole ring. Chemical hydrolysis is a primary process affecting the environmental fate of sulfonylurea pesticides. The hydrolytic transformation kinetics of PE and HM were investigated as a function of pH and temperature. For both herbicides, the hydrolysis rate was pH-dependent and increased with increasing temperature. The hydrolysis of both sulfonylureas was much faster in acidic or basic media than under neutral conditions. Identification of hydrolytic products by liquid chromatography-mass spectrometry (LC-MS) suggested that both PE and HM were subject to cleavage and contraction of the sulfonylurea bridge. The hydrolysis rate of HM was significantly higher than that of PE in alkaline solutions, despite their structural similarity. A chlorine substitution on HM's pyrazole ring makes HM more susceptible to bridge contraction than PE under basic conditions. The hydrolysis of HM and PE was relatively unaffected by the presence of cyclic oligosaccharides (cyclodextrins), indicating that natural OH-containing organic compounds occurring in aquatic environments may have little impact on the transformation of these sulfonylurea herbicides.


Assuntos
Herbicidas/química , Pirazóis/química , Pirimidinas/química , Compostos de Sulfonilureia/química , Água/química , Ciclodextrinas/farmacologia , Concentração de Íons de Hidrogênio , Hidrólise , Cinética , Soluções , Temperatura
14.
Environ Sci Technol ; 41(18): 6454-9, 2007 Sep 15.
Artigo em Inglês | MEDLINE | ID: mdl-17948793

RESUMO

The prevalent use of soil fumigants has resulted in air pollution in some agricultural regions. Our previous research showed that application of thiosulfate fertilizers at the soil surface may offer an effective and economical approach to reduce the emission of halogenated fumigants via a chemical remediation process. In this fumigant emission-reduction strategy, volatile 1,3-dichloropropene (1,3-D) reacts with thiosulfate to generate a nonvolatile Bunte salt (thiosulfate derivative of 1,3-D). However, the decomposition of the Bunte salt may be associated with the production of perceptible odors. This study investigated the stability of this reaction product in different environmental media. Hydrolysis experiments demonstrated that the thiosulfate derivative was relatively stable in neutral and moderately acidic aqueous solutions. In contrast, the thiosulfate derivative was readily converted to a dialkyl disulfide via a base hydrolysis process in pH 10 buffer solution. In a strongly acidic solution, a mercaptan and a dialkyl disulfide compound were detected as two primary hydrolysis products. In soil, this initial reaction product underwent a series of biotic conversions to generate several volatile or semivolatile organic sulfur compounds. The formation and distribution of four volatile/semivolatile products in the air and soil were detected in different soils treated with the thiosulfate derivative of 1,3-D. This study indicated that odors occurring in soil treated with halogenated fumigants and thiosulfate fertilizers might arise from the generation and release of these and other volatile/semivolatile organic sulfur products. The environmental fate and effects of such volatile/semivolatile sulfur compounds should be considered in the application of sulfur-containing fertilizers in fumigated fields.


Assuntos
Compostos Alílicos/química , Tiossulfatos/química , Hidrocarbonetos Clorados , Inseticidas/química , Modelos Químicos , Estrutura Molecular , Solo/análise , Poluentes do Solo/química , Volatilização
15.
J Agric Food Chem ; 55(21): 8630-9, 2007 Oct 17.
Artigo em Inglês | MEDLINE | ID: mdl-17880161

RESUMO

Two-year field dissipation studies were conducted in three soil types in Minnesota to examine the processes affecting the dissipation of the herbicide isoxaflutole and its phytotoxic diketonitrile metabolite (DKN) under relatively cool, wet soil conditions. Plots of cuphea were treated with isoxaflutole and potassium bromide, a nonsorbed, nondegraded tracer. Replicate soil cores were collected six times during the growing season to a depth of 1 m, and the bromide or herbicide concentration was measured in each of five depth increments. The dissipation half-life (DT50) of isoxaflutole + DKN was 8-18 days in each soil. Bromide and herbicide concentrations were low at depths >40 cm throughout the study, and herbicide concentrations in soil 100 days after application were usually undetectable. Simulation modeling using Hydrus-1D for the loam soil suggested that plant uptake was an important mechanism of dissipation.


Assuntos
Herbicidas/química , Isoxazóis/química , Nitrilas/química , Solo/análise , Sulfonas/química , Brometos/análise , Clima , Meia-Vida , Herbicidas/análise , Isoxazóis/análise , Isoxazóis/metabolismo , Nitrilas/análise , Sulfonas/análise
16.
J Environ Sci Health B ; 42(6): 641-7, 2007 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-17701699

RESUMO

This study was undertaken to determine sorption coefficients of eight herbicides (alachlor, amitrole, atrazine, simazine, dicamba, imazamox, imazethapyr, and pendimethalin) to seven agricultural soils from sites throughout Lithuania. The measured sorption coefficients were used to predict the susceptibility of these herbicides to leach to groundwater. Soil-water partitioning coefficients were measured in batch equilibrium studies using radiolabeled herbicides. In most soils, sorption followed the general trend pendimethalin > alachlor > atrazine approximately amitrole approximately simazine > imazethapyr > imazamox > dicamba, consistent with the trends in hydrophobicity (log K(ow)) except in the case of amitrole. For several herbicides, sorption coefficients and calculated retardation factors were lowest (predicted to be most susceptible to leaching) in a soil of intermediate organic carbon content and sand content. Calculated herbicide retardation factors were high for soils with high organic carbon contents. Estimated leaching times under saturated conditions, assuming no herbicide degradation and no preferential water flow, were more strongly affected by soil textural effects on predicted water flow than by herbicide sorption effects. All herbicides were predicted to be slowest to leach in soils with high clay and low sand contents, and fastest to leach in soils with high sand content and low organic matter content. Herbicide management is important to the continued increase in agricultural production and profitability in the Baltic region, and these results will be useful in identifying critical areas requiring improved management practices to reduce water contamination by pesticides.


Assuntos
Herbicidas/química , Medição de Risco , Poluentes do Solo/análise , Poluentes Químicos da Água/análise , Abastecimento de Água/normas , Adsorção , Agricultura , Monitoramento Ambiental/métodos , Herbicidas/análise , Lituânia , Modelos Químicos , Poluentes do Solo/química , Solubilidade , Fatores de Tempo , Movimentos da Água , Poluentes Químicos da Água/química
17.
J Agric Food Chem ; 54(21): 8163-70, 2006 Oct 18.
Artigo em Inglês | MEDLINE | ID: mdl-17032024

RESUMO

Sorption-desorption is one of the most important processes affecting the leaching of pesticides through soil because it controls the amount of pesticide available for transport. Subsurface soil properties can significantly affect pesticide transport and the potential for groundwater contamination. This research characterized the sorption-desorption of imidacloprid (1-[(6-chloro-3-pyridinyl)-methyl]-N-nitro-2-imidazolidinimine) and three of its metabolites, 1-[(6-chloro-3-pyridinyl)methyl]-2-imidazolidinone (imidacloprid-urea), 1-[(6-chloro-3-pyridinyl)methyl]-4,5-dihydro-1H-imidazol-2-amine (imidacloprid-guanidine), and 1-[(6-chloro-3-pyridinyl)methyl]-1H-imidazol-2-amine (imidacloprid-guanidine-olefin), as a function of changing soil properties with depth in two profiles extending from the surface to a depth of 1.8 or 8 m. Sorption of each compound was highly variable and hysteretic in all cases. Normalizing the sorption coefficients (K(f)) to the organic carbon or the clay content of the soil did not reduce the variability in sorption coefficients for any compound. These results illustrate the importance of evaluation of the sorption data used to predict potential mobility. Understanding the variability of soil properties and processes as a function of depth is necessary for accurate prediction of pesticide dissipation.


Assuntos
Imidazóis/química , Imidazóis/metabolismo , Inseticidas/química , Inseticidas/metabolismo , Solo/análise , Adsorção , Neonicotinoides , Nitrocompostos , Poluição da Água
18.
Environ Sci Technol ; 40(7): 2402-7, 2006 Apr 01.
Artigo em Inglês | MEDLINE | ID: mdl-16646481

RESUMO

Soil fumigants are becoming an important source of volatile organic compounds (VOCs) in air, especially in some agricultural areas. In this study, we used thiourea to construct a reactive surface barrier (RSB) at the soil surface for reducing 1,3-dichloropropene (1,3-D) volatilization. The agrochemical thiourea could rapidly transform volatile 1,3-D to nonvolatile products via an SN2 nucleophilic substitution reaction. A catalytic mechanism in thiourea-amended soil facilitated the conversion process. A packed soil column system was employed to investigate the emissions and distribution of 1,3-D and optimize the original fumigant emission-reduction strategy. Volatilization of 1,3-D from the soil surface was significantly reduced in columns amended with a thiourea RSB compared with that of bare soil. Volatilization flux and cumulative emissions decreased with increasing thiourea application rate and increasing fumigation depth in packed soil columns. Surface amendment with the RSB did not affect the subsurface distribution of 1,3-D in the soil profile. Combined application of a thiourea RSB and plastic tarps had a synergetic effect in emission control and could eliminate the relatively high fumigant flux that occurs upon tarp disruption. Therefore, this reduced-risk practice was very effective in reducing atmospheric emissions of VOCs from soil treatment with halogenated fumigants.


Assuntos
Compostos Alílicos/química , Solo/análise , Tioureia/química , Catálise , Hidrocarbonetos Clorados
19.
J Agric Food Chem ; 54(6): 2280-7, 2006 Mar 22.
Artigo em Inglês | MEDLINE | ID: mdl-16536608

RESUMO

The chlorinated fumigants chloropicrin (trichloronitromethane) and 1,3-dichloropropene (1,3-D) are extensively used in agricultural production for the control of soilborne pests. The reaction of these two fumigants with hydrogen sulfide species (H2S and HS-) was examined in well-defined anoxic aqueous solutions. Chloropicrin underwent an extremely rapid redox reaction in the hydrogen sulfide solution. Transformation products indicated reductive dechlorination of chloropicrin by hydrogen sulfide species to produce dichloro- and chloronitromethane. The transformation of chloropicrin in hydrogen sulfide solution significantly increased with increasing pH, indicating that H2S is less reactive toward chloropicrin than HS- is. For both 1,3-D isomers, kinetics and transformation products analysis revealed that the reaction between 1,3-D and hydrogen sulfide species is an S(N)2 nucleophilic substitution process, in which the chlorine at C3 of 1,3-D is substituted by the sulfur nucleophile to form corresponding mercaptans. The 50% disappearance time (DT50) of 1,3-D decreased with increasing hydrogen sulfide species concentration at a constant pH. Transformation of 1,3-D was more rapid at high pH, suggesting that the reactivity of hydrogen sulfide species in the experimental system stems primarily from HS-. Because of the relatively low smell threshold values and potential environmental persistence of organic sulfur products yielded by the reaction of 1,3-D and HS-, the effects of reduced sulfide species should be considered in the development of alternative fumigation practices, especially in the integrated application of sulfur-containing fertilizers.


Assuntos
Compostos Alílicos/química , Cloro/química , Hidrocarbonetos Clorados/química , Sulfeto de Hidrogênio/química , Inseticidas/química , Fenômenos Químicos , Físico-Química , Fumigação , Concentração de Íons de Hidrogênio , Oxirredução
20.
Environ Toxicol Chem ; 24(8): 1867-74, 2005 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-16152955

RESUMO

Halogenated fumigants have been used extensively in production agriculture to control soilborne pests. These types of pesticides are highly volatile and are prone to affect air quality and imperil public health. In the present study, a chemical tarp approach, termed a reactive surface barrier (RSB), was developed to reduce the emission of fumigant 1,3-dichloropropene (1,3-D) from the soil surface. The agrochemicals thiourea and allylthiourea were tested as active reagents for the construction of a RSB, where these soil amendments react with 1,3-D to form nonvolatile isothiuronium ions at the soil surface and, thereby, impede fumigant emission into the atmosphere. The feasibility of the method largely depends on the reactivity of 1,3-D and the RSB agrochemicals in soil as well as on the mobility, persistence, and toxicity of the transformation products. Therefore, the reaction kinetics and transformation mechanism of 1,3-D by thiourea and allylthiourea were studied comprehensively in aqueous solution and soil. A catalytic process occurring at the surface of soil colloids facilitated the reaction between 1,3-D and thiourea in amended soils. The rate of 1,3-D transformation in thiourea-amended soil increased with decreasing soil moisture or increasing thiourea amendment level. In a field trial, a thiourea RSB reduced cumulative 1,3-D emissions by more than 80% relative to that in bare soil surface. The present results clearly indicate that this chemical remediation technology has great potential to control the emissions of volatile halogenated organic contaminants and to mitigate atmospheric pollution.


Assuntos
Compostos Alílicos/química , Inseticidas/química , Solo , Cromatografia Gasosa , Cromatografia Gasosa-Espectrometria de Massas , Hidrocarbonetos Clorados , Propriedades de Superfície , Tioureia/análogos & derivados , Tioureia/química
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