Field weathering of spent mushroom substrate (SMS) produces soluble compost leachate that percolates into underlying soils and may adversely impact groundwater. Laboratory experiments were conducted to investigate movement and retention of SMS leachate solutes in subsurface soil columns. Spent mushroom substrate leachate with high concentrations of dissolved organic matter (DOM) and inorganic salts was passively loaded to intact and repacked columns of Bt1 soil (fine-loamy, mixed, semiactive, mesic Typic Hapludults) and effluents were monitored for changes in chemical composition. Transport of SMS leachate in undisturbed soil cores was mainly via preferential flow, whereas matrix flow was predominant in repacked soil columns. Leachate DOM and phosphate were sorbed by soil minerals while Cl-, SO4(2-), Na+ and NH4+ were eluted. Leachate K+ displaced exchangeable native cations and was retained. Biodegradation of leachate DOM resulted in reduction and elution of soil Mn and Fe, especially in repacked columns. Persistent anoxia also inhibited nitrification. Precipitation of gypsum and CaCO3 blocked preferential flow channels, and movement of SMS leachate was subsequently reduced. The results demonstrate that SMS leachate migrates via rapid preferential flow initially, followed by matrix flow at a lower rate. Leachate solutes may transport to depth in soil profiles through preferential channels. To protect water resources, weathering of deep SMS piles should be conducted on compact surfaces or in fields with a condensed soil layer (no structural cracks) above the groundwater table, and measures controlling leachate runoff be imposed.

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.

Nitrate and other solutes resulting from field-weathering of spent mushroom substrate (SMS) percolate into underlying soils and may migrate to groundwater. A field trial was conducted to investigate the potential influences of SMS weathering on groundwater quality. Spent mushroom substrate was deposited at 90 and 150 cm pile depths over a Typic Hapludult and weathered for 2 years. Eight casing wells were installed around the SMS piles to monitor the quality changes of groundwater with a high seasonal water table of 760 cm below the surface. Although leachate solutes had moved more than 200 cm deep in soil from the surface, no significant changes of groundwater quality caused by SMS weathering were observed even one year after removal of the SMS piles (3 years total). The groundwater had pH, electrical conductivity (EC) and dissolved organic carbon (DOC) of 4.3-5.7, 0.2-0.3 dS m(-1) and 0.7-2.2 mg L(-1), respectively. The major inorganic ions were Mg(2+), Ca(2+), Na(+), Cl(-), SO(4)(2-) and NO(3)(-), with a concentration range of 2.5-68.3 mg L(-1). The results suggest that SMS leachate solutes migrated fairly slow in deep subsurface soils of the experimental field. Considering that leachate solutes may move several meters in soil through preferential flow channels, weathering of SMS in fields with a high seasonal groundwater table >or=5 m below the ground is recommended. Conservatively, SMS weathering should be conducted on compact surfaces and leachate be collected and reused as liquid fertilizers.

Metam sodium (metam) is a widely used soil fumigant. Combined application of metam and other available fumigants is intended to produce synergic pesticidal effects for a broad spectrum of pest control in soil fumigation. This study aimed to test the compatibility of metam with the halogenated fumigants 1,3-dichloropropene (1,3-D), chloropicrin, methyl bromide, methyl iodide and propargyl bromide. Halogenated fumigants and metam were spiked simultaneously into organic solvents, water and moist soils, and metam-induced degradation of these halogenated chemicals was evaluated. In all three media, the halogenated fumigants were incompatible with metam and degraded via rapid chemical reactions. The degradation rate varied with halogenated fumigant species and increased as the amount of metam present was increased. In moist soil, 15-95% of the halogenated fumigants were decomposed within 72 h by metam at a 1:1 molar ratio. Combined application of Telone C-35 (62.5% 1,3-D + 35% chloropicrin) at 265 mg kg(-1) and Vapam (42% metam) at 567 mg kg(-1) in soil resulted in complete disappearance of the applied chloropicrin and 20-38% of the 1,3-D within 8 h. The results suggest that simultaneous application of halogenated fumigants and metam at the same soil depth will not maximize pest control. In practice, sequential treatment of soil or application at different soil depths is recommended when these two types of fumigants are used in combination.

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.

Methyl iodide (MeI) is a promising alternative to methyl bromide in soil fumigation. The pest-control efficacy and ground water contamination risks of MeI as a fumigant are highly related to its gas-phase distribution and leaching after soil application. In this study, the distribution and leaching of MeI in soil following shank injection and subsurface drip application were investigated. Methyl iodide (200 kg ha(-1)) was directly injected or drip-applied at a 20-cm depth into Arlington sandy loam (coarse-loamy, mixed, thermic Haplic Durixeralfs) columns (12-cm i.d., 70-cm height) tarped with virtually impermeable film. Concentration profiles of MeI in the soil air were monitored for 7 d. Methyl iodide diffused rapidly after soil application, and reached a 70-cm depth within 2 h. Relative to shank injection, drip application inhibited diffusion, resulting in significantly lower concentration profiles in the soil air. Seven days after MeI application, fumigated soil was uncapped, aerated for 7 d, and leached with water. Leaching of MeI was significant from the soil columns under both application methods, with concentrations of >10 mug L(-1) in the early leachate. The leaching was greater following shank injection than drip application, with an overall potential of 33 g ha(-1) for shank injection and 19 g ha(-1) for drip application. Persistent residues of MeI remaining in soils after leaching were 50 to 240 ng kg(-1), and the contents were slightly higher following shank injection than drip application. The results suggest that fumigation with MeI may pose a risk of ground water contamination in vulnerable areas.

Methyl iodide (MeI) is considered a very promising fumigant alternative to methyl bromide (MeBr) for controlling soil-borne pests. Because atmospheric emission of highly volatile fumigants contributes to air pollution, feasible strategies to reduce emissions are urgently needed. In this study, thiourea (a nitrification inhibitor) was shown to accelerate the degradation of MeI in soil and water. In aqueous solution, the reaction between MeI and thiourea was independent of pH, although the rate of MeI hydrolysis increased in alkaline solution. Substantial increases in the rate of MeI dissipation were observed in thiourea-amended soils. Transformation of MeI by thiourea in aqueous solution was by a single chemical reaction process, while MeI degradation in thiourea-amended soil apparently involved a catalytic mechanism. The electron delocalization between the thiourea molecule and the surfaces of soil particles is energetically favorable and would increase the nucleophilic reactivity of the thiono group toward MeI, resulting in an enhancement of the dissipation rate. The soil half-life for MeI was reduced from >300 h for unamended soils to only a few hours in soil or sand amended with thiourea at a 2:1 molar ratio (thiourea:MeI). The MeI transformation rate in thiourea-amended soil increased with increasing soil temperature and decreasing soil moisture. Therefore, spraying thiourea on the soil surface to form a "reactive surface barrier" may be an effective and innovative strategy for controlling fumigant emissions to the atmosphere and for improving environmental protection.

Soil fumigants are used to control a wide variety of soil-borne pests in high-cash-value crops. Application of soil fumigants through drip irrigation systems is receiving increasing attention as a method to improve the uniformity of fumigant application. Little information is available on the emissions and soil distribution of fumigants following subsurface drip application, or the effect of plastic tarp on fumigant emissions in these systems. In these experiments, the fumigant compounds 1,3-dichloropropene (1,3-D), Vapam (a methyl isothiocyanate (MITC) precursor), and propargyl bromide (PrBr) were applied to soil beds via drip irrigation at 15 cm depth. Beds were tarped with either standard 1-mil high-density polyethylene (HDPE) or a virtually impermeable film (VIF), leaving the furrows bare. Cumulative emissions of 1,3-D, MITC, and PrBr in these tarped bedded systems was very low, amounting to <10% of the applied mass. These experiments were conducted in the winter months, with average air temperatures of 12-15 degrees C. Cumulative emissions of MITC and 1,3-D from a sandy loam field soil were decreased by > or =80% by tarping the bed with VIF rather than HDPE. A large fraction of the 1,3-D and PrBr flux was from the untarped furrows in VIF-tarped plots, indicating that inhibiting volatilization from the furrow will be important in further reducing emissions in these systems. Monitoring the fumigant distribution in soil indicated that tarping the bed with VIF resulted in a more effective containment of fumigant vapors compared to use of a HDPE tarp.

Fumigants are used for control of nematodes, fungi, weeds, and insects in high-cash-value crops. Because of their high volatility, a large fraction of the applied mass may be volatilized from the soil surface following application. Emission reduction strategies are needed to prevent adverse human or environmental health impacts. Some emission-reduction strategies, such as tarping the soil surface with impermeable plastic, increase containment of fumigants in the soil. The resulting fumigant residues could cause atmospheric contamination once the tarp is disrupted, groundwater contamination if leaching is allowed, or phytotoxicity to the crop planted following fumigation. Previous research has shown that thiosulfate compounds, including ammonium thiosulfate (ATS), abiotically react with and detoxify halogenated fumigants in soil and water. In these experiments, we investigated subsurface application of ATS to reduce fumigant concentrations in the root zone, preventing off-site transport following fumigation. Results indicated that halogenated fumigants were dissipated more rapidly in soil receiving ATS application compared to those receiving water only. First-order dissipation half-lives were less than or equal to1 day for the halogenated compounds 1,3-dichloropropene and propargyl bromide. For methyl isothiocyanate, a non-halogenated fumigant that does not undergo reaction with ATS, application of ATS had no impact on the rate of dissipation in soil. These results suggest that subsurface application of ATS may be useful for the root-zone remediation of halogenated compounds.

Combined application of fumigants is a potential strategy to replace methyl bromide in the control of soil-borne pests. Unfortunately, abiotic and biotic interactions among fumigants restrict some combined application approaches. In this study, the kinetics and mechanisms of reaction between metam sodium (sodium methyldithiocarbamate) and the halogenated fumigants chloropicrin (trichloronitromethane) and 1,3-dichloropropene (1,3-D) were investigated in aqueous solution. For chloropicrin, an extremely rapid oxidation-reduction process occurred in the presence of metam sodium. The second-order rate constant for the reaction between chloropicrin and metam sodium was approximately 2 orders of magnitude greater than that for the reaction between 1,3-D isomers and metam sodium. Transformation of 1,3-D by metam sodium was associated with an aliphatic S(N)2 nucleophilic substitution process. The nucleophilic reaction of cis-1,3-D with metam sodium was significantly faster than that of the trans isomer and was correlated with a lower reaction activation energy for the cis isomer in the transition state. Combining Telone C-35 (65% 1,3-D and 35% chloropicrin) and metam sodium in solution might yield some nucleophilic sulfur species, which played an important role in the dissipation of 1,3-D. The incompatibility of chloropicrin and 1,3-D with metam sodium was also examined in soil under different application scenarios. Simultaneous application of metam sodium with chloropicrin or 1,3-D accelerated the transformation of the two halogenated fumigants, reducing their availability in soil. A sequential strategy for multiple fumigants was developed, which could be applied without the loss of active ingredient that occurs due to the reaction between fumigants. The proposed methodology may enhance pest control while maintaining environmental protection.

Propachlor and other chloroacetanilide herbicides are frequently detected contaminants of groundwater and surface water in agricultural regions. The purpose of this work was to develop a new approach to remove propachlor residues from the environment via chemical remediation by the nitrification inhibitor thiourea. The transformation processes of propachlor and thiourea mixed in aqueous solution, sand, and soil were elucidated. Analysis of transformation products and reaction kinetics indicated that an S(N)2 nucleophilic substitution reaction occurred, in which the chlorine of propachlor was replaced by thiourea, detoxifying the herbicide. It appears that propachlor undergoes a catalytic reaction in sand or soil amended with thiourea, which results in a significantly accelerated transformation rate as compared to the reaction in aqueous solution. The second-order reaction process was examined at different temperatures to investigate the role of the activation energy. The enthalpy of activation (deltaH) for the reaction of propachlor with thiourea was demonstrated to be significantly lower in sand than in aqueous solution, which provides evidence that a catalytic transformation mechanism occurs in thiourea-amended sand. The chemical reaction rate increased proportionally to the amount of thiourea added to the sand. Column experiments further suggested that the remediation strategy could be used to remove propachlor residues from sand or soil to reduce leaching and prevent contamination of surface water and groundwater.

Weathering of piled material in the field is a popular method to treat spent mushroom substrate (SMS) before reuse. During the weathering process, rainfall and snowmelt pass through SMS piles and a large amount of solutes is released in the leachate. To investigate solute release patterns, the field weathering process was simulated under controlled conditions in the laboratory. Fresh SMS was packed in an acrylic column (20 cm i.d.) to 150 cm height and leached intermittently with a cumulative total of 230 cm of deionized water over 180 days. Leachate was collected and analyzed for dissolved organic carbon (DOC), dissolved organic nitrogen (DON), electrical conductivity (EC), and inorganic salts. Solute release patterns were described using first order models, and total released solutes were calculated. The SMS leachate had DOC, DON and EC values ranging from 450 to 15,500 mg L−1, 50 to 1,700 mg L−1, and 3 to 50 dS m−1, respectively. The major inorganic cations were K+, Na+, Ca2+, Mg2+ and NH4+, and anions were Cl− and SO42−. Release of DOC, DON, and bivalent cations Ca2+ and Mg2+ were described by a first order Exponential Rise to Maximum model, while releases of monovalent ions Cl−, K+, Na+ and NH4+ were described as a first order Sigmoidal Logistic process, and SO42− release was best modeled by a Sigmoidal Chapman equation. Following six months and 230 cm applied water, 3.1 kg of DOC, 0.58 kg of dissolved N, and 8.6 kg of inorganic salts were leached per cubic meter of bulk SMS (220 kg oven dry mass). Weathering of SMS involves a significant removal of nutrients from the composted material, which can contribute to pollution of soil and groundwater.

Hydrolysis is the major pathway for fumigant 1,3-dichloropropene (1,3-D) degradation in water and soil, yet the process is not well understood. Experiments were conducted to investigate the effect of various environmental factors on the rate of 1,3-D hydrolysis. Cis-, trans-1,3-D and their isomeric mixture were spiked into water and Arlington soil (coarse-loamy, mixed, thermic Haplic Durixeralfs) and incubated under different conditions. The rate of 1,3-D hydrolysis in water and soil were evaluated based on its residual amount and Cl- release, respectively. 1,3-D hydrolyzed rapidly in deionized water, with a half-life of 9.8 d at 20 degrees C. The hydrolysis was pH dependent, with low pH inhibiting and high pH favoring the reaction. Other factors such as isomeric differences, photo irradiation, suspended particles, and small amounts of co-solutes had little effect on the reaction. In soil, 1,3-D hydrolyzed following pseudo first-order kinetics. The hydrolysis rate constant increased with soil moisture content and decreased with the initial 1,3-D concentration. At 20 degrees C, > 60% of the 1,3-D applied at < 0.61 g kg(-1) in 10% moisturized soil hydrolyzed within 30 d. The soil particle size and mineralogy had little effect on the reaction rate. Organic matter promoted 1,3-D degradation via direct substitution reactions, and the trans-isomer showed preference over the cis- to react with certain organic molecules. Microbial contributions were initially insignificant, and became important as soil microorganisms adapted to the fumigant. The results suggest that to accelerate 1,3-D degradation, pH, soil moisture, and organic amendment should be considered.

The mixture of 1,3-dichloropropene (1,3-D) and chloropicrin (CP) is used as a preplant soil fumigant. In comparison with individual fumigants, application of a mixture may affect the environmental dissipation and fate of each chemical, such as emission and degradation. We investigated the degradation of CP, 1,3-D, and their mixture in fresh soils and sterile soils, and evaluated the competitive characteristic of fumigants in the mixture. The degradation of low concentrations of CP in fresh soil was accelerated at early times in the presence of 1,3-D, whereas the addition of CP reduced the degradation rate of trans-1,3-D, possibly by inhibiting the activity of trans-1,3-D degrading microorganisms. The potential of applying amendments to the soil to increase the rate of CP and 1,3-D degradation was also illustrated. The degradation of both fumigants was significantly enhanced in soils amended with ammonium thiosulfate (ATS) and sodium diethyldithiocarbamate (Na-DEDTC) compared with unamended soil. Competitive degradation was observed for CP in amended soils in the presence of 1,3-D. The degradation of cis-1,3-D in amended soils spiked as a mixture of 1,3-D and CP was repressed compared with the rate of degradation in samples spiked with 1,3-D only. This implied that in abiotic degradation, CP and cis-1,3-D competed for a limited number of reaction sites in amended soil, resulting in decreased degradation rates. No significant influence of fumigant mixtures was observed for trans-1,3-D in amended soil.

The fumigant methyl iodide (MeI, iodomethane) is considered a promising alternative to methyl bromide (MeBr) for soil-borne pest control in high-cash-value crops. However, the high vapor pressure of MeI results in emissions of a significant proportion of the applied mass into the ambient air, and this may lead to pollution of the environment. Integrating the application of certain agrochemicals with soil fumigation provides a novel approach to reduce excessive fumigant emissions. This study investigated the potential for several agrochemicals that are commonly used in farming operations, including fertilizers and nitrification inhibitors, to transform MeI in aqueous solution. The pseudo-first-order hydrolysis half-life (t(1/2)) of MeI was approximately 108 d, while the transformation of MeI in aqueous solutions containing selected agrochemicals was more rapid, with t(1/2) < 100 d (t(1/2) < 0.5 d in some solutions containing nitrification inhibitors). The influence of these agrochemicals on the rate of MeI degradation in soil was also determined. Adsorption to soil apparently reduced the availability of some nitrification inhibitors in the soil aqueous phase and lowered the degradation rate in soil. In contrast, addition of the nitrification inhibitors thiourea and allylthiourea to soil significantly accelerated the degradation of MeI, possibly due to soil surface catalysis. The t(1/2) of MeI was <20 h in thiourea- and allylthiourea-amended soil, considerably less than that in unamended soil (t(1/2) > 300 h).

Dissolved organic matter (DOM) is a heterogeneous mixture of organic compounds that plays an important role in the movement of DOM-associated pollutants. In this study, transport and fractionation of DOM in soils was investigated in flow-through soil columns. Dissolved organic matter derived from spent mushroom substrate weathering was pumped through packed columns (2.5 cm X 10 cm) comprising a coarse-loamy subsoil (mixed, semiactive, mesic Typic Hapludult), and effluents were monitored for changes in the composition of DOM. Effluent DOM was characterized for LTV absorbance, molecular weight, acidity, and hydrophilicity. Transport through the columns resulted in preferential retention of specific DOM constituents as indicated by comparison with a Br- tracer. During the transport process, effluent DOM exhibited decreasing values of E-2/E-3 (from 10.3 to 6.2), acidity (from 20.8 to 13.1 mmol(c) g(-1) C), and hydrophilicity (39.0 to 28.4%), and increasing values of molar absorptivity (from 164 to 310 L mol(-1) C cm(-1)) and number and weight-averaged molecular weight (from 1770 to 3150 and 2450 to 4180 Da, respectively). These results indicate that DOM fractions with higher molecular weight, higher molar absorptivity, lower E-2/E-3 ratio, lower acidity, and lower hydrophilicity were adsorbed preferentially by soil minerals, whereas the inverse fractions were transported preferentially. The adsorbed DOM could not be completely desorbed by DOM-free background solution, indicating a strongly bound fraction. Sorptive fractionation of DOM during transport likely affects the transport behavior of DOM-complexed constituents.

Fumigants are commonly thought to be short-lived in soil, but residues have been found in soils years following application. In this study, formation and extraction of persistent soil fumigant residues were investigated. Fumigants 1,3-dichloropropene (1,3-D), chloropicrin (CP), and methyl isothiocyanate (MITC) were spiked into Arlington, Glenelg, and Hagerstown soils and incubated for 30 d under controlled conditions. The incubated soils were evaporated for 20 h prior to extraction with a variety of organic solvents at different temperatures. Extraction with acetonitrile in sealed vials at 80 degrees C for 24 h was the most efficient method to recover persistent soil fumigant residues. At application rates of 1000-1700 mg (kg of soil)(-1), persistent residues of 1,3-D, CP, and MITC in the three soils ranged from 5 to 67 mg kg(-1). The residue content increased with application rate, correlated positively with soil silt content, decreased dramatically as indigenous organic matter (OM) was removed, and changed little with external OM addition. Adsorption to clay surfaces was not important in fumigant retention, while pulverization of soil aggregates significantly decreased persistent fumigant residues. The results suggest that persistent fumigant residues are retained in soil intra-aggregate micropores resulting from binding clay flocs and silt particles by humic substances.