Atmospheric volatilization of methyl bromide, 1,3-dichloropropene,and propargyl bromide through two plastic films: transfer coefficient and temperature effect

Atmospheric emission of methyl bromide (MeBr) and its potential alternative chemicals such as 1,3-dichloropropene (1,3-D) and propargyl bromide (PrBr) can contribute to air pollution and ozone depletion (for MeBr). One of the main sources of these chemicals is from agricultural soil fumigation. To understand the volatilization dynamics, emission of MeBr, 1,3-D, and PrBr through a polyethylene-based high-barrier film (HBF) and a virtually impermeable film (VIF) was measured using an air flow and sampling system that produced >90% mass balance. The experiment was conducted outdoors and was subjected to ambient daily temperature variations. The HBF film was found to be very permeable to 1,3-D and PrBr, but somewhat less permeable to MeBr. The VIF film was very impermeable to 1,3-D, PrBr, or MeBr. Measured volatilization flux, in general, exhibited strong diurnal variations which were controlled by film temperature. Unlike the HBF film, a time lag (∼12 h) was observed between high-temperatures and high-emission flux values for the VIF film. An impermeable film may be used as an effective means of controlling the atmospheric emission of MeBr and its alternative chemicals.     

Henry's law constants and mass transfer coefficients for methyl bromide and 1,3-dichloropropene applied to Florida sandy field soil

Methyl bromide, a pre-emergent soil fumigant, is scheduled to be phased out in the US by 2005, with exceptions for critical use. Comparison of some of the physical constants related to distribution and retention for methyl bromide (MBr) to other fumigants yields a useful quantification of possible alternatives. In this study, the atmospheric and subsurface dissipation of methyl bromide as well as (Z)- and (E)-1,3-dichloropropene (1,3-D) isomers in Telone II were examined. The Henry's law constants of the three chemicals at soil temperature and their mass transfer coefficients for movement through an agricultural mulch of UV-resistant, high-density polyethylene (PE) were evaluated using field data. At the soil temperature of 16.4 degrees C, calculated Henry's law constant gave a fumigant ranking of MBr (0.21)>(Z)-1,3-D (0.041)>(E)-1,3-D (0.027). Since rapid subsurface distribution of a fumigant is highly dependent on the amount in the gas phase, the greater value for Henry's law constant implies faster distribution throughout the soil. After distribution through the soil, retention of the fumigant becomes imperative. Calculation of the fumigant's mass transfer coefficients through PE from field data gave a ranking of the three chemicals: MBr (1.08 cm/h)<(E)-1,3-D (3.25 cm/h)<(Z)-1,3-D (4.13 cm/h). With mass transfer coefficients of this magnitude, it was concluded that PE film was an inadequate barrier for retaining these fumigants in an agricultural setting.     

Atmospheric flux of agricultural fumigants from raised-bed,plastic-mulch crop production systems

Atmospheric emission of methyl isothiocyanate (MITC), chloropicrin (CP), 1,3-dichloropropene (1,3-D), and dimethyl disulfide (DMDS) were measured in the field under fumigant application scenarios representative of raised bed–plastic-mulched crop production systems. For three fumigation sites located in Florida, cumulative emissions of 1,3-D, MITC and CP were less than 11%, 6% and 2%, respectively. For three fumigation sites in located in Georgia, cumulative emissions of MITC and CP were <13% and 12%, respectively while DMDS emissions varied from 37% to 95%. In the Florida sites, emission peak flux of CP occurred within the first 6 h after application. Peak emission of 1,3-D and MITC occurred between 100 and 144 h after application. In the Georgia sites where fumigated soil was covered by low density polyethylene (LDPE) plastic, emission peak flux of DMDS and MITC occurred between 12and 48 h after application. Key factors affecting atmospheric emissions were soil moisture, soil tilth and the resistance to fumigant diffusion of the plastic film used to cover soil following application. This study demonstrated reduced atmospheric emissions of agricultural fumigants under commercial production conditions when applied using good agricultural practices including soil water contents above field capacity, uniform soil tilth in the fumigation zone and the use of metalized or virtually impermeable films to further reduce fumigant emissions. The results of this study show a need for regional flux studies due to the various interactions of soil and climate with local agricultural land management practices.     

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.     

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.     

Adsorption and catalytic decomposition of methyl bromide and methyl iodide on activated carbons

Methyl bromide (MeBr) is commonly used for fumigating structures and commodities. Emission of MeBr during such treatments is environmentally detrimental because of the reaction of MeBr with stratospheric ozone. In this study we evaluated adsorption of MeBr and methyl iodide (MeI) – a potential MeBr replacement, on five commercial activated carbons, and studied water-initiated catalytic decomposition of adsorbed fumigants. All carbon samples showed great adsorption affinity to MeBr and MeI, with the adsorption capacity for MeI several times greater than that for MeBr on the same carbon. For the same fumigant, adsorption was affected by the type of carbon and the concentration of fumigant. Water initiated decomposition of both fumigants, liberating Br⁻ or I⁻ as a transformation product. The rate of decomposition increased with increasing temperature, and was also influenced by the carbon type. The half-life of MeBr or MeI on Centaur, a catalytically modified carbon, was <2 h at 80°C. The rapid decomposition of MeBr and MeI on wet carbons at elevated temperatures may be used to detoxify these fumigants after adsorption on activated carbons.     

Effects of soil fumigants on methanotrophic activity

Negative impacts on methane (CH₄) oxidation capacity have already been observed for a variety of agronomic practices, but the effect of soil fumigation on CH₄ oxidation has not been investigated. Fumigation is a common practice in agricultural crop and nursery seedling protection. Soils from various agricultural experiment stations, forest nurseries, and a landfill were evaluated for effects of 1,3-dichloropropene (1,3-D), methyl isothiocyanate (MITC), and chloropicrin (CP) on CH₄ oxidation capacities. All three fumigants significantly reduced CH₄ oxidation rates in historically non-fumigated soils (>50%). 1,3-D enhanced CH₄ oxidation in 3 out of 5 previously fumigated soils and MITC increased CH₄ oxidation rates in all historically MITC-fumigated soils compared to controls. CP universally decreased oxidation capacity regardless of fumigation history. These results support the conclusion that CH₄ oxidation effects are fumigant specific and that prior fumigation history plays a vital role in determining the impact on CH₄ oxidizer community functionality, which may have implications on the global CH₄ cycle.     

Relative effect of soil moisture on emissions and distribution of 1,3-dichloro-propene and chloropicrin in soil columns

Emissions of soil fumigants are regulated to protect air quality in California. Irrigation prior to fumigation can reduce fumigant emissions at relatively low costs; however, the optimum range of soil water content that reduces emissions without reducing efficacy is not clearly defined. The objective of this study was to determine the effects of soil water content [at 30, 45, 60, 75, 90 and 100% field capacity (FC)] on the emission and distribution of fumigants 1,3-dichloropropene (1,3-D) and chloropicrin (CP) in columns packed with a sandy loam soil. After injecting equal amounts of cis-1,3-D, trans-1,3-D, and CP, fumigant emissions and distribution in soil were monitored for 14 days. Emissions of all three compounds showed similar response to soil water content except that CP emissions were lower than both isomers of 1,3-D. The emission peak flux was highest and occurred earliest in the driest soil while it was reduced and delayed as soil water content increased. After the peak, emission flux decreased rapidly in the driest soil but more slowly in higher water content treatments. Initially, higher soil water content resulted in substantially lower cumulative emissions among the treatments, but as time progressed, the differences in cumulative emissions decreased or even disappeared. These trends were likely due to the effect of the closed-bottom short soil columns which allowed fumigants to only move upward and contribute to emission. Higher fumigant concentrations in the soil–gas phase were observed in high soil water content treatments, due to less emission loss and more fumigant retained in the soil.     

Atmospheric volatilization and distribution of (Z)- and (E)-1,3-dichloropropene in field beds with and without plastic covers

The fumigant 1,3-dichloropropene (1,3-D) is considered to be a potential replacement for methyl bromide when methyl bromide is phased out in 2005. This study on surface emissions and subsurface diffusion of 1,3-D in a Florida sandy soil was conducted in field beds with or without plastic covers. After injection of the commercial fumigant Telone II by conventional chisels to field beds at 30cm depth which were covered with polyethylene film (PE), virtually impermeable film, or no cover (bare), (Z)- and (E)-1,3-D rapidly diffused upward. Twenty hours after injection, majority of (Z)- and (E)-1,3-D had moved upward from 30 cm depth to the layer of 5-20 cm depth. Downward movement of the two isomers in the beds with or without a plastic cover was not significant. (Z)-1,3-D diffused more rapidly than (E)-1,3-D. Virtually impermeable films (VIF) had a good capacity to retain (Z)- and (E)-1,3-D in soil pore air space. Vapor concentrations of the two isomers in the shallow subsurface of the field bed covered with VIF were greater than that in the two beds covered with polyethylene film (PE) or no cover (bare). In addition, VIF cover provided more uniform distribution of (Z)- and (E)-1,3-D in shallow subsurface than PE cover or no cover. Virtually impermeable film also had a better capability to retard surface emissions of the two isomers from soil in field beds than PE cover or no cover.     

Persistence, distribution, and emission of Telone C35 injected into a Florida sandy soil as affected by moisture, organic matter, and plastic film cover

With the phase-out of methyl bromide scheduled for 2005, alternative fumigants are being sought. This study of Telone C35, a mixture of (Z)- and (E)-1,3-dichloropropene (1,3-D) with chloropicirin (CP), focuses on its emissions, distribution, and persistence in Florida sandy soil in microplots with different soil-water and organic matter carbon (C) content with and without two different plastic film mulches. The addition of CP did not affect the physical behavior of the isomers of 1,3-D. Slower subsurface dispersion and longer residence time of the mixed fumigant occurred at higher water content. An increase in the percent organic carbon in the soil led to a more rapid decrease for chloropicirin than for 1,3-dichloropene isomers. The use of a virtually impermeable film (VIF) for soil cover provided a more even distribution and longer persistence under all the conditions studied in comparison to polyethylene (PE) film cover or no cover. The conditions of near field capacity water content, low organic matter, and a virtually impermeable film cover yielded optimum conditions for the distribution, emission control, and persistence of Telone C35 in a Florida sandy soil.     

Persistence,Distribution, and Emission of Telone C35 Injected into a Florida Sandy Soil as Affected by Moisture,Organic Matter,and Plastic Film Cover

Abstract

With the phase-out of methyl bromide scheduled for 2005, alternative fumigants are being sought. This study of Telone C35, a mixture of (Z)- and (E)-1,3-dichloropropene (1,3-D) with chloropicirin (CP), focuses on its emissions, distribution, and persistence in Florida sandy soil in microplots with different soil–water and organic matter carbon (C) content with and without two different plastic film mulches. The addition of CP did not affect the physical behavior of the isomers of 1,3-D. Slower subsurface dispersion and longer residence time of the mixed fumigant occurred at higher water content. An increase in the percent organic carbon in the soil led to a more rapid decrease for chloropicirin than for 1,3-dichloropene isomers. The use of a virtually impermeable film (VIF) for soil cover provided a more even distribution and longer persistence under all the conditions studied in comparison to polyethylene (PE) film cover or no cover. The conditions of near field capacity water content, low organic matter, and a virtually impermeable film cover yielded optimum conditions for the distribution, emission control, and persistence of Telone C35 in a Florida sandy soil.     

Atmospheric Volatilization and Distribution of (Z)- and (E)-1,3-Dichloropropene in Field Beds with and without Plastic Covers

Abstract

The fumigant 1,3-dichloropropene (1,3-D) is considered to be a potential replacement for methyl bromide when methyl bromide is phased out in 2005. This study on surface emissions and subsurface diffusion of 1,3-D in a Florida sandy soil was conducted in field beds with or without plastic covers. After injection of the commercial fumigant Telone II by conventional chisels to field beds at 30 cm depth which were covered with polyethylene film (PE), virtually impermeable film, or no cover (bare), (Z)- and (E)-1,3-D rapidly diffused upward. Twenty hours after injection, majority of (Z)- and (E)-1,3-D had moved upward from 30 cm depth to the layer of 5–20 cm depth. Downward movement of the two isomers in the beds with or without a plastic cover was not significant. (Z)-1,3-D diffused more rapidly than (E)-1,3-D. Virtually impermeable films (VIF) had a good capacity to retain (Z)- and (E)-1,3-D in soil pore air space. Vapor concentrations of the two isomers in the shallow subsurface of the field bed covered with VIF were greater than that in the two beds covered with polyethylene film (PE) or no cover (bare). In addition, VIF cover provided more uniform distribution of (Z)- and (E)-1,3-D in shallow subsurface than PE cover or no cover. Virtually impermeable film also had a better capability to retard surface emissions of the two isomers from soil in field beds than PE cover or no cover.     

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.     

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.     

Comparison of surface emissions and subsurface distribution of cis- and trans-1,3-dichloropropene and chloropicrin in sandy field beds covered with four different plastic films

The purpose of this study was to conduct a field study at a Florida field site on surface emissions and subsurface distribution of cis-and trans-1,3-dichloropropene (1,3-D) and chloropicrin (CP) in raised beds injected with Telone C35 with four replications. A total of 16 beds were applied with Telone C35 by chisel injection and covered with four different plastic films, 4 beds for each film. Each bed was installed with five 20-cm long soil pore air probes and a surface air collection pan at arbitrarily locations along the length of each bed for sampling soil pore air and surface air, respectively, for analysis of the three biologically active compounds, cis- and trans-1,3-D and CP. We found that average concentrations of the three compounds at 20-cm depth among the beds covered with four different plastic films generally were not statistically different. Among the four beds covered with the same plastic film, average concentrations of the three compounds were statistically different only in the four metallic PE covered beds at 5 and 24 hours after injection. Volatilization rates of the three compounds among the beds covered with four different plastic films, with the exception of CP at 48 hours after injection, were not statistically different. It appeared that initial upward diffusion and volatilization flux were influenced by solar radiation. Initial subsurface concentrations of the three compounds and volatilization flux, especially cis-1,3-D, were greater in the beds on the east side of the field than that in the beds on the west side of the field. Whether or not difference in initial subsurface concentrations of the compounds between east side beds and west side beds may influence fumigant efficacy remains to be determined.     

Comparison of surface emissions and subsurface distribution of cis- and trans-1,3-dichloropropne and chloropicrin in sandy field beds covered with four different plastic films

The purpose of this study was to conduct a field study at a Florida field site on surface emissions and subsurface distribution of cis-and trans-1,3-dichloropropene (1,3-D) and chloropicrin (CP) in raised beds injected with Telone C35 with four replications. A total of 16 beds were applied with Telone C35 by chisel injection and covered with four different plastic films, 4 beds for each film. Each bed was installed with five 20-cm long soil pore air probes and a surface air collection pan at arbitrarily locations along the length of each bed for sampling soil pore air and surface air, respectively, for analysis of the three biologically active compounds, cis- and trans-1,3-D and CP. We found that average concentrations of the three compounds at 20-cm depth among the beds covered with four different plastic films generally were not statistically different. Among the four beds covered with the same plastic film, average concentrations of the three compounds were statistically different only in the four metallic PE covered beds at 5 and 24 hours after injection. Volatilization rates of the three compounds among the beds covered with four different plastic films, with the exception of CP at 48 hours after injection, were not statistically different. It appeared that initial upward diffusion and volatilization flux were influenced by solar radiation. Initial subsurface concentrations of the three compounds and volatilization flux, especially cis-1,3-D, were greater in the beds on the east side of the field than that in the beds on the west side of the field. Whether or not difference in initial subsurface concentrations of the compounds between east side beds and west side beds may influence fumigant efficacy remains to be determined.     

The influence of metam sodium on soil respiration

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.     

Emissions from soil fumigation in two raised bed production systems tarped with low permeability films

Raised beds are used to produce some high-value annual fruit and vegetable crops such as strawberry in California (CA) and tomato in Florida (FL), USA. Pre-plant soil fumigation is an important tool to control soil-borne pests in the raised beds. However, fumigant emissions have detrimental environmental consequences. Field trials were conducted to evaluate emissions of 1,3-dichloropropene (1,3-D) and chloropicrin (CP) in two different production systems with raised beds covered by different tarps. In the CA trial, InLine (60.8% 1,3-D and 33.3% CP) was drip-applied at 340 kg ha⁻¹ to 5 cm deep in the beds (30 cm high and 107 cm wide) tarped with polyethylene (PE) or virtually impermeable film (VIF). In the FL trial, carbonated Telone C35 (63.4% 1,3-D and 34.7% CP) was shank-applied at 151 kg ha⁻¹ to 20 cm deep in the beds (22 cm high and 76 cm wide) tarped with totally impermeable film (TIF). Emissions from tarped beds relative to furrows were contrary between the two trials. For the CA trial, the emission was 47% of applied 1,3-D and 27% of applied CP from PE tarped beds and 31% of applied 1,3-D and 15% of applied CP from VIF tarped beds, while that from uncovered furrows was <0.4% for both chemicals in both fields. In the FL trial, only 0.1% 1,3-D was emitted from the TIF tarped beds, but 27% was measured from the uncovered furrows. Factors contributing to the differences in emissions were chiefly raised-bed configuration, tarp permeability, fumigant application method, soil properties, soil water content, and fumigant carbonation. The results indicate that strategies for emission reduction must consider the differences in agronomic production systems. Modifying raised bed configuration and fumigant application technique in coarse textured soils with TIF tarping can maximize fumigation efficiency and emission reduction.     

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.     

Sorption of the fumigant 1,3-dichloropropene on soil

The fumigant 1,3-dichloropropene (1,3-D) is considered a major replacement to methyl bromide, which is to be phased out of use in the United States by 2005. The main purpose of this study was to evaluate soil-water partitioning of 1,3-D in two California agricultural soils (Salinas clay loam and Arlington sandy loam). The partition coefficients (Kd and Kf) were determined by directly measuring the concentration of 1,3-D in the solid phase (Cs) and aqueous phase (Cw) after batch equilibration. In the Salinas clay loam, the Kf of cis-1,3-D in adsorption and desorption isotherms was 0.47 and 0.54, respectively, with respective values of 0.39 and 0.49 for trans-1,3-D. This slight hysteric effect suggests that a different range of forces are involved in the adsorption and desorption process. Since n was near unity in the Freundlich equation, the Freundlich isotherms can also be approximated using the liner isotherm. At 25 degrees C, the Kd of the 1,3-D isomers in both soils ranged from 0.46 to 0.56, and the Koc (organic matter partition coefficient) ranged from 58 to 70. The relatively low Kd values and a Koc that falls within the range of 50-150, suggests that 1,3-D is weakly sorbed and highly mobile in these soils. Understanding the sorption behavior of 1,3-D in soil is important when developing fumigation practices to reduce the movement of 1,3-D to the air and groundwater.