Daniel J. Ashworth

Irrigation, organic matter addition, and tarping as methods of reducing emissions of methyl iodide from agricultural soil.

Methyl iodide (MeI) is increasingly being used as a highly effective alternative to the soil fumigant methyl bromide. Due to its volatile and toxic nature, MeI draws wide attention on its potential atmospheric emission following field fumigation treatment. Using soil columns that make it possible to determine emissions and gas phase distribution of soil fumigants, we studied MeI behavior in two soils differing in organic matter content. Additionally, the effectiveness of surface irrigation and tarping with virtually impermeable film (VIF) was assessed. In the lower organic matter, bare soil (control), emissions of MeI were rapid and high (83% of total). Although the peak emission flux was reduced by irrigation, the total loss was very similar to the control (82%). Tarping with VIF dramatically reduced emissions (0.04% total emissions). In the higher organic matter soil, degradation rate of MeI was increased around 4-fold, leading to a significant reduction in emissions (63% total emissions). The work suggests that surface tarping with VIF would be highly effective as an emissions reduction strategy and would also result in the maintenance of high soil gas concentrations (important for pest control). Ripping of the tarp after two weeks led to an immediate spike release of MeI, but, even so, the flux rate at this time was almost 20 times lower than the peak flux rate in the control. Even with tarp ripping, the total emission loss from the VIF treatment remained low (6%).

Emissions of 1,3-Dichloropropene and Chloropicrin after Soil Fumigation under Field Conditions

Soil fumigation is an important agronomic practice in the production of many high-value vegetable and fruit crops, but the use of chemical fumigants can lead to excessive atmospheric emissions. A large-scale (2.9 ha) field experiment was conducted to obtain volatilization and cumulative emission rates for two commonly used soil fumigants under typical agronomic practices: 1,3-dichloropropene (1,3-D) and chloropicrin. The aerodynamic method and the indirect back-calculation method using ISCST3 and CALPUFF dispersion models were used to estimate flux loss from the treated field. Over the course of the experiment, the daily peak volatilization rates ranged from 12 to 30 μg m(-2) s(-1) for 1,3-D and from 0.7 to 2.6 μg m(-2) s(-1) for chloropicrin. Depending on the method used for quantification, total emissions of 1,3-D and chloropicrin, respectively, ranged from 16 to 35% and from 0.3 to 1.3% of the applied fumigant. A soil incubation study showed that the low volatilization rates measured for chloropicrin were due to particularly high soil degradation rates observed at this field site. Understanding and quantifying fumigant emissions from agricultural soil will help in developing best management practices to reduce emission losses, reducing adverse impacts to human and ecosystem health, and providing inputs for conducting risk assessments.

Biochar Amendment to the Soil Surface Reduces Fumigant Emissions and Enhances Soil Microorganism Recovery

During soil fumigation, it is ideal to mitigate soil fumigant emissions, ensure pest control efficacy, and speed up the recovery of the soil microorganism population established postapplication. However, no current fumigant emission reduction strategy can meet all these requirements. In the present study, replicated soil columns were used to study the effect of biochar derived from rice husk (BR) and green waste (BG) applied to the soil surface on 1,3-dichloropropene (1,3-D) and chloropicrin (CP) emissions and soil gas distribution, and on microorganism population re-establishment. Relative to fumigated bare soil (no emission reduction strategy), high-density polyethylene (HDPE), and ammonium thiosulfate (ATS) treatments, BR gave dramatic emission reductions for both fumigants with no obvious emission peak, whereas BG was very effective only for 1,3-D. With BR application, the concentration of fumigant in the soil gas was higher than in the bare soil and ATS treatment. After the soil column experiment, mixing the BR with the fumigated soil resulted in higher soil respiration rates than were observed for HDPE and ATS treatments. Therefore, biochar amendment to the soil surface may be an effective strategy for fumigant emission reduction and the recovery of soil microorganism populations established postapplication.

Parent and conjugated estrogens and progestagens in surface water of the Santa Ana River: Determination, occurrence, and risk assessment.

The present study investigated the occurrence of 13 parent and conjugated estrogens and progestagens in surface water of the Santa Ana River. With the exception of the synthetic hormones 17α-ethynylestradiol and mestranol, other compounds were detected at least twice at 10 representative sites, with the ubiquitous estrone (E1) and 17β-estradiol-3-sulfate as the dominant compounds quantified (0.24-6.37 ng/L and 0.49-9.25 ng/L, respectively). Sites near dairy farms exhibited high levels of conjugates, whereas those close to a sewage treatment plant (STP) effluent outlet displayed relatively high concentrations of E1. Principle component analysis coupled with multiple linear regression revealed dairy farms and the STP as the 2 significant contamination sources, accounting for 69.9% and 31.1% of the total hormone burden, respectively. Risk assessment results suggested E1 and 17β-estradiol (E2) as the 2 hormones with the largest risks to aquatic organisms, and which combined, contributed >90% of the total estrogenicity. Most of the sites investigated showed that E1 and E2 posed a medium risk (0.1 < risk quotient < 1), whereas each induced a high risk (risk quotient >1) at sites severely impacted by the STP and dairy farms. These results suggest that river health would benefit from effective treatment of waste at the STP and dairy farms prior to discharge. Environ Toxicol Chem 2016;35:2657-2664.

Transport and Fate of Methyl Iodide and Its Pest Control in Soils

For fumigants, information on transport and fate as well as pest control is needed to develop management practices with the fewest negative environmental effects while offering sufficient pest control efficacy. For this purpose, a 2-D soil chamber with a surface-mounted flux chamber was designed to determine volatilization, real-time soil gas-phase concentration, degradation, and organism survivability after methyl iodide (MeI) fumigation. Three types of pests were used to give a broad spectrum of pest control information. An infected sandy loam soil with a volumetric water content of 10.6% was packed carefully into the 2-D chamber to a bulk density of 1.34 g cm(-3). After MeI fumigation at a rate of 56.4 kg ha(-1) for 24 h, about 28.9% of MeI was emitted into air, 6.8% remained in the soil, and 43.6% degraded in the soil (based on the residual iodide concentration). The uncertainty in the measured MeI degradation using iodide concentration was thought to mainly contribute to the unrecovered MeI (about 20%). The citrus nematodes [Tylenchulus semipenetrans] were effectively eliminated even at low concentration-time (CT) values (<30 microg h mL(-1)), but all Fusarium oxysporum survived. The response of barnyardgrass seeds [Echinochloa crus-galli] spatially varied with the CT values in the chamber. To fully control barnyardgrass seeds, CT of greater than 300 microg h mL(-1) was required. Using this experimental approach, different fumigant emission reduction strategies can be tested, and mathematical models can be verified to determine which strategies produce the least emission to the atmosphere while maintaining sufficient pest control efficacy.

Effect of co-formulation of 1,3-dichloropropene and chloropicrin on evaporative emissions from soil.

Co-formulations of 1,3-dichloropropene (1,3-D) and chloropicrin (CP) are commonly used for preplant fumigation in the production of high-value crops. Various ratios of 1,3-D to CP are available in these co-formulations. Collation of previous field data suggested that when the two fumigants were co-applied, the emissions of CP were significantly lower than when CP was applied singly. However, none of these previous studies had a control treatment with CP applied alone, alongside a treatment where CP was co-applied with 1,3-D under the same climatic and edaphic conditions. This work aimed to address this issue by measuring emission fluxes from soil columns maintained under controlled conditions in which 1,3-D and CP were applied alone and as four commercial co-formulations with various 1,3-D:CP ratios. A strong positive relationship between CP emissions and CP percentage in the formulation was observed. Furthermore, strong positive relationships between CP degradation half-life and CP percentage in the formulation and between CP degradation half-life and total column emissions suggested that the lower emissions were due to faster CP degradation when the CP percentage (and hence initial application mass) in the formulation was low. The presence of 1,3-D did not significantly affect the degradation rate of CP, and, therefore, it is hypothesized that co-application was, in itself, not a significant factor in emission losses from the columns. The findings have implications for the accurate modeling of CP because the effect of initial mass applied on CP degradation rate is not usually considered.

Transfers of Iodine in the Soil–Plant–Air System: Solid–Liquid Partitioning, Migration, Plant Uptake and Volatilization

This chapter discusses the soil–plant–air system processes controlling the behavior of iodine. The vast majority of soil iodine is most likely adsorbed to the soil solid phase, although appreciable amounts may be released into the liquid and gaseous phases, particularly under anoxic soil conditions. From the liquid phase, iodine can be transported to surface- and groundwaters, plant roots and, consequently, the human diet. From the gaseous phase, iodine can be transported to the atmosphere where human exposure may occur due to inhalation. Iodine partitioning between all three-soil phases (solid, liquid, gas) leads to potential transfers away from the soil body, e.g., by leaching, plant uptake, and volatilization. However, partitioning into the liquid and gaseous phases clearly does occur, primarily under anoxic conditions due to the presence of poorly sorbed iodine species. Mobility of iodine under anoxic soil conditions is markedly greater than under oxic conditions. Accumulations of iodine at the boundary between anoxic and oxic soil regions are likely to occur. Volatilization of iodine, primarily as methyl iodide, occurs from both soil and plants. Again, the presence of anoxic soil conditions is likely to enhance this process. Plants with roots able to tolerate anoxic conditions (e.g., rice) tend to take up greater quantities of iodine from the soil. Although the majority of soil iodine remains adsorbed to the soil solid phase, its release into the liquid and gaseous phases does occur, enabling potential transfer pathways that are likely to increase human exposure to iodine.

Effect of Films on 1,3-Dichloropropene and Chloropicrin Emission, Soil Concentration, and Root-Knot Nematode Control in a Raised Bed

Soil fumigation is an important component of U.S. agriculture, but excessive emissions can be problematic. The objective of this study was to determine the effects of agricultural films (e.g., tarps) on soil fumigant atmospheric emissions and spatiotemporal distributions in soil, soil temperature, and plant pathogen control in the field using plastic films with various permeabilities and thermal properties. A reduced rate of 70% InLine (60.8% 1,3-dichloropropene (1,3-D) and 33.3% chloropicrin (CP)) was applied via drip line to raised soil beds covered with standard high-density polyethylene film (HDPE), thermic film (Thermic), or virtually impermeable film (VIF). 1,3-D and CP emission rates were determined using dynamic flux chambers, and the concentrations in soil were measured using a gas sampler. The pest control efficacy for the three treatments was determined using bioassay muslin bags containing soil infested with citrus nematodes (Tylenchulus semipenetrans). The results show that the Thermic treatment had the highest emission rates, followed by the HDPE and VIF treatments, and the soil concentrations followed the reverse order. In terms of pest control, covering the beds with thermic film led to sufficient and improved efficacy against citrus nematodes compared to standard HDPE film. Under HDPE, >20% of nematodes survived in the soil at 30 cm depth at day 12. The VIF treatment substantially reduced the emission loss from the bed (2% of the Thermic and 6% of the HDPE treatments) and eliminated plant parasitic nematodes because of its superior ability to entrap fumigant and heat within soils. The findings imply that not only the film permeability but also the synergistic ability to entrap heat should be considered in the development of new improved films for fumigation.

Mitigating 1,3-dichloropropene, chloropicrin, and methyl iodide emissions from fumigated soil with reactive film.

Implicated as a stratospheric ozone-depleting compound, methyl bromide (MeBr) is being phased out despite being considered to be the most effective soil fumigant. Its alternatives, i.e., 1,3-dichloropropene (1,3-D, which includes cis and trans isomers), chloropicrin (CP), and methyl iodide (MeI), have been widely used. High emissions of MeI from fumigated soil likely put farm workers and other bystanders at risk of adverse health effects. In this study, two types of constructed reactive film were tested for their ability to mitigate emissions of 1,3-D, CP, and MeI using laboratory permeability cells. Before activation, these films act as a physical barrier to trap fumigants leaving soil. After activation of the reactive layer containing ammonium thiosulfate solution, the films also act as a sink for the fumigants. Over 97% of trans-1,3-D and 99% of the cis-1,3-D, CP and MeI were depleted when they passed into the reactive film. Half-lives (t(1/2)) of cis-, trans-1,3-D, CP and MeI under activated reactive film were 1.2, 1.4, 1.6, and 2.0 h respectively at 40 °C.

1,3-Dichloropropene and Chloropicrin Emissions Following Simulated Drip Irrigation to Raised Beds under Plastic Films

Using laboratory soil chambers a nonscaled representation of an agricultural raised bed was constructed. For a sandy loam soil, 1,3-dichloropropene (1,3-D) and chloropicrin (CP) were applied at 5 cm depth with an excess of water (simulated drip irrigation). Application was made under both high density polyethylene (HDPE) and virtually impermeable film (VIF) covering the soil bed (the furrow was left uncovered). Soil gas distribution of the fumigants, together with emissions into the headspace above the bed, sidewall and furrow were determined over time. Total emissions from the HDPE treatment were cis 1,3-D 28%, trans 1,3-D 24%, and CP 8%. Due to its lower permeability, the values for VIF were 13%, 7%, and 1.5%, respectively. With HDPE, the majority (86-93%) of the emissions occurred from the bed, while for VIF the majority (92-99%) of the emissions was from the furrow. Compared to a range of literature values for shank injection, the use of drip application appears to offer a benefit in reducing 1,3-D and CP emissions. However, the most meaningful comparison is with our previous data for simulated shank injection where the same soil was covered (completely) with the same plastic films (1). In this comparison, only 1,3-D emissions under HDPE were lower with drip application; 1,3-D emissions under VIF and CP emissions under both films were greater with the drip application.