Degradation of soil fumigants as affected by initial concentration and temperature

Soil fumigation using shank injection creates high fumigant concentration gradients in soil from the injection point to the soil surface. A temperature gradient also exists along the soil profile. We studied the degradation of methyl isothiocyanate (MITC) and 1,3-dichloropropene (1,3-D) in an Arlington sandy loam (coarse-loamy, mixed, thermic Haplic Durixeralf) at four temperatures and four initial concentrations. We then tested the applicability of first-order, half-order, and second-order kinetics, and the Michaelis-Menten model for describing fumigant degradation as affected by temperature and initial concentration. Overall, none of the models adequately described the degradation of MITC and 1,3-D isomers over the range of the initial concentrations. First-order and half-order kinetics adequately described the degradation of MITC and 1,3-D isomers at each initial concentration, with the correlation coefficients greater than 0.78 (r2> 0.78). However, the derived rate constant was dependent on the initial concentration. The first-order rate constants varied between 6 and 10x for MITC for the concentration range of 3 to 140 mg kg(-1), and between 1.5 and 4x for 1,3-D isomers for the concentration range of 0.6 to 60 mg kg(-1), depending on temperature. For the same initial concentration range, the variation in the half-order rate constants was between 1.4 and 1.7x for MITC and between 3.1 and 6.1x for 1,3-D isomers, depending on temperature. Second-order kinetics and the Michaelis-Menten model did not satisfactorily describe the degradation at all initial concentrations. The degradation of MITC and 1,3-D was primarily biodegradation, which was affected by temperature between 20 and 40 degrees C, following the Arrhenius equation (r2 > 0.74).     

Theory and laboratory study of a tall passive chamber for measuring gas fluxes at soil surface

A tall passive flux chamber with a height significantly greater than its horizontal dimensions is proposed for measuring fluxes of volatile organic compounds (VOCs) at the soil surface. The main feature of this tall chamber is the presence of a vertical concentration gradient of the target gas in the chamber. The emission and transport behavior of the target gas in the soil-chamber system are analyzed using the diffusion theory. A mathematical model is developed to estimate the flux from the soil into the tall chamber, providing the target gas establishes a detectable vertical concentration gradient in the chamber. To obtain the data required for calculating flux, only two gas concentrations (C1 and C2) at two heights (h1 and h2) within the chamber need to be measured at the end of a short chamber placement time (tp). To evaluate the applicability of the tall chamber for measuring flux, several laboratory tests have been conducted, using CH2Cl2 and CH3Br as the target gases. The results indicate that the proposed tall chamber has promising potential as a method for measuring fluxes of VOCs at the soil surface.     

Effect of formulation on the behavior of 1,3-dichloropropene in soil

The fumigant 1,3-dichloropropene (1,3-D) has been identified as a partial replacement for methyl bromide (CH3Br) in soil fumigation. 1,3-Dichloropropene is formulated for soil fumigation as Telone II (Dow AgroSciences, Indianapolis, IN) for shank application and as an emulsifiable concentrate (EC) (Telone EC or InLine; Dow AgroSciences) for drip application. This study investigated the effect of formulation on the phase partitioning, transformation rate, and volatilization of 1,3-D isomers. Air-water partitioning coefficients (K(H)) were slightly higher for Telone II than for Telone EC, presumably due to the higher apparent water solubility of the EC formulation. Sorption of 1,3-D isomers in two soils was not affected by formulation. Formulation had no significant effect on the rate of 1,3-D transformation in water or soil. In general, differences in the rate of 1,3-D transformation and phase partitioning due to formulation as Telone II or Telone EC were very small. Thus, the effect of formulation on 1,3-D fate may be ignored in transformation and phase partition of 1,3-D in water and soil. Packed soil columns without plastic tarp indicated that with relatively shallow subsurface (10 cm) drip application of Telone EC, emission of 1,3-D isomers was more rapid and produced greater maximum instantaneous flux than deeper (30 cm) shank injection of Telone II. Both application methods resulted in the same cumulative emissions for both isomers, 45% for (E)-1,3-D and approximately 50% for (Z)-1,3-D. These results suggest that for drip application of fumigants to be effective in reducing emissions, the fumigant must be applied at sufficient depths to prevent rapid volatilization from the soil surface if the water application rate does not sufficiently restrict vapor diffusion.     

Herbicide sorption coefficients in relation to soil properties and terrain attributes on a cultivated prairie

The sorption of 2,4-D and glyphosate herbicides in soil was quantified for 287 surface soils (0-15 cm) collected in a 10 x 10 m grid across a heavily eroded, undulating, calcareous prairie landscape. Other variables that were determined included soil carbonate content, soil pH, soil organic carbon content (SOC), soil texture, soil loss or gain by tillage and water erosion, and selected terrain attributes and landform segments. The 2,4-D sorption coefficient (Kd) was significantly associated with soil carbonate content (-0.66; P < 0.001), soil pH (-0.63; P < 0.001), and SOC (0.47; P < 0.001). Upper slopes were strongly eroded and thus had a significantly greater soil carbonate content and less SOC compared with lower slopes that were in soil accumulation zones. The 2,4-D Kd was almost twice as small in upper slopes than in lower slopes. The 2,4-D Kd was also significantly associated with nine terrain attributes, particularly with compounded topographic index (0.59; P < 0.001), gradient (-0.48; P < 0.001), mean curvature (-0.43; P < 0.001), and plan curvature (-0.42 P < 0.001). Regression equations were generated to estimate herbicide sorption in soils. The predicted power of these equations increased for 2,4-D when selected terrain attributes were combined with soil properties. In contrast, the variation of glyphosate sorption across the field was much less dependent on our measured soil properties and calculated terrain attributes. We conclude that the integration of terrain attributes or landform segments in pesticide fate modeling is more advantageous for herbicides such as 2,4-D, whose sorption to soil is weak and influenced by subtle changes in soil properties, than for herbicides such as glyphosate that are strongly bound to soil regardless of soil properties.     

Gas-phase sorption-desorption of propargyl bromide and 1,3-dichloropropene on plastic materials

The goal of this research was to provide information for choosing appropriate materials for studying gas-phase concentrations of propargyl bromide (3BP) and 1,3-dichloropropene (1,3-D) in laboratory experiments. Several materials were tested and found to sorb both gas-phase chemicals in the following order: stainless steel (SS) < Teflon polytetrafluoroethylene (PTFE-FEP) approximately flexible polyvinyl chloride (PVC) approximately acrylic < low-density polyethylene (PE) < vinyl approximately silicone < polyurethane foam (PUF). Sorption of SS was insignificant and PUF sorbed all the fumigant that was applied. For the other materials, linear sorption coefficients (Kd) for 3BP ranged from 3.0 cm3 g(-1) for PVC to 215 cm3 g(-1) for silicone. Freundlich sorption coefficients for 1,3-D ranged from 11.5 to 371 cm3 g(-1). First-order desorption rate constants in an open system ranged from 0.05 to 1.38 h(-1) for 3BP and from 0.07 to 1.73 h(-1) for 1,3-D. In a closed system, less than 2% of sorbed fumigant desorbed from vinyl while up to 99% desorbed from PVC within 24 h when equilibrated at the highest headspace concentration. Sorption of both fumigants was linearly related to the square root of time except for vinyl and silicone. This may indicate non-fickian diffusion of fumigant into the polymer matrix. Vinyl, silicone, PE, and PUF should be avoided for quantitative study of organic gases, except possibly as a trapping medium. Use of PTFE, PVC, and acrylic may require correction for sorption-desorption and diffusion.     

Simulation study of the Lower Cretaceous geothermal reservoir for aquifer thermal energy storage

Environmental Geochemistry and Health - The aquifer thermal energy storage (ATES) has gained attention in several countries as an installation for increasing the energy efficiency of geothermal...     

Competitive degradation between the fumigants chloropicrin and 1,3-dichloropropene in unamended and amended soils

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.     

Use of composted animal manures to reduce 1,3-dichloropropene emissions

Atmospheric emission of the soil fumigant 1,3-dichloropropene (1,3-D) has been associated with the deterioration of air quality in certain fumigation areas. To minimize the environmental impacts of 1,3-D, feasible and cost-effective control strategies are in need of investigation. One approach to reduce emissions is to enhance the surface layer of a soil to degrade 1,3-D. A field study was conducted to determine the effectiveness of composted steer manure (SM) and composted chicken manure (CKM) to reduce 1,3-D emissions. SM or CKM were applied to the top 5-cm soil layer at a rate of 3.3 or 6.5 kg m(-2). An emulsified formulation of 1,3-D was applied through drip tape at 130.6 kg ha(-1) into raised beds. The drip tape was placed in the center of each bed (102 cm wide) and 15 cm below the surface. Passive flux chambers were used to measure the loss of 1,3-D for 170 h after fumigant application. Results indicated that the cumulative loss of 1,3-D was about 48% and 28% lower in SM- and CKM-amended beds, respectively, than in the unamended beds. Overall, both isomers of 1,3-D behaved similarly in all treatments. The cumulative loss of 1,3-D, however, was not significantly different between the two manure application rates for either SM or CKM. The results of this study demonstrate the feasibility of using composted animal manures to control 1,3-D emissions.     

Effects of environmental factors on 1,3-dichloropropene hydrolysis in water and soil

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.     

Managing agricultural emissions to the atmosphere: state of the science, fate and mitigation, and identifying research gaps

The impact of agriculture on regional air quality creates significant challenges to sustainability of food supplies and to the quality of national resources. Agricultural emissions to the atmosphere can lead to many nuisances, such as smog, haze, or offensive odors. They can also create more serious effects on human or environmental health, such as those posed by pesticides and other toxic industrial pollutants. It is recognized that deterioration of the atmosphere is undesirable, but the short- and long-term impacts of specific agricultural activities on air quality are not well known or understood. These concerns led to the organization of the 2009 American Chemical Society Symposium titled . An outcome of this symposium is this special collection of 14 research papers focusing on various issues associated with production agriculture and its effect on air quality. Topics included emissions from animal feeding operations, odors, volatile organic compounds, pesticides, mitigation, modeling, and risk assessment. These papers provide new research insights, identify gaps in current knowledge, and recommend important future research directions. As the scientific community gains a better understanding of the relationships between anthropogenic activities and their effects on environmental systems, technological advances should enable a reduction in adverse consequences on the environment.