Emissions and distribution of methyl bromide in field beds applied at two rates and covered with two types of plastic mulches

A field experiment was conducted to compare two plastic mulches and two application rates on surface emissions and subsurface distribution of methyl bromide (MBr) in field beds in Florida. Within 30 minutes after injection of MBr to 30 cm depth, MBr had diffused upward to soil surface in all beds covered with polyethylene film (PE) or virtually impermeable film (VIF) and applied at a high rate (392 kg/ha) and a low rate (196 kg/ha). Due to the highly permeable nature of PE, within 30 minutes after injection, MBr volatilized from the bed surfaces of the two PE-covered beds into the atmosphere. The amount of volatilization was greater for the high rate-treatment bed. On the other hand, volatilization of MBr from the bed surfaces of the two VIF-covered beds were negligible. Volatilization losses occurred from the edges of all the beds covered with PE or VIF and were greater from the high rate-treatment beds. Initial vertical diffusion of MBr in the subsurface of the beds covered with PE or VIF was mainly upward, as large concentrations of MBr were detected from near bed surfaces to 20 cm depth in these beds 30 minutes after injection and little or no MBr was found at 40 cm depth. The two VIF-covered beds exhibited greater MBr concentrations and longer resident times in the root zone (0.5–40 cm depth) than corresponding PE-covered beds. Concentrations of MBr in the root zone of the high rate-treatment beds were 3.6–6.1 times larger than the low rate-treatment beds during the first days after application. In conclusion, VIF promoted retention of MBr in the root zone and, if volatilization loss from bed edges can be blocked, volatilization loss from VIF-covered beds should be negligible.     

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.     

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 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.     

Gross fluxes of methyl chloride and methyl bromide in a California oak-savanna woodland

Temperate woodland ecosystems are believed to be both a source and sink for atmospheric methyl bromide and methyl chloride. To separate the gross production and consumption fluxes in this ecosystem, we applied a stable isotope tracer technique in field and laboratory-based experiments. Flux measurements were conducted in a California oak-savanna woodland ecosystem at several intervals throughout the day during the wet and dry seasons to observe the diurnal and seasonal variability of fluxes. While gross production was small and variable, gross consumption showed a clear difference between seasons, with much larger rates during the wet season and negligible rates during the dry season. Laboratory incubations confirmed that fluxes were strongly affected by soil moisture. Consumption rates of methyl bromide, however, are less than half of the previous estimates of temperate woodland soil uptake rates during the growing season. Nevertheless, woodlands cover a significant portion of the world's land surface area and may still be an important component of the soil sink for these methyl halides.     

Calibration and testing of a dynamic flow-through chamber for field determination of methyl bromide volatilization flux

Accurate emission measurement of highly volatile chemicals such as methyl bromide (MeBr) is a crucial step in assessing their potential for environmental contamination. Use of flux chambers is a simple method for measuring emission rate under field conditions. To validate the applicability of a dynamic flow-through chamber for measuring MeBr emission, we provide a complete presentation of calibration and testing of the chamber. The calibration was made under a controlled system subject to ambient temperature changes. Two field experiments were conducted to test the chamber for measuring MeBr flux under conditions similar to commercial soil fumigation practices. In both the calibration and the two field experiments, the chamber provided accurate emission estimates. The maximum mass balance error was < 10% which is comparable to the micrometerological method. Because of its simplicity, we believe this dynamic flux chamber can be used reliably in quantifying the emission dynamics of highly volatile chemicals such as MeBr.     

Effect of soil properties on degradation and sorption of methyl bromide in soil

Methyl bromide (CH₃Br) is currently the most widely used soil fumigant, and its emission into the atmosphere after application reportedly contributes to ozone depletion in the stratosphere. Irreversible degradation and partially reversible sorption reactions affect the quantity of this furnigant reaching the soil surface and escaping into the atmosphere. Incubation studies in closed headspace vials under controlled conditions showed that degradation of CH₃Br was highly dependent on soil organic matter content, and to a lesser extent, on the moisture level in the soil. Methylation of CH₃Br on organic matter was suggested to be the major reaction that CH₃Br undergoes in the soil environment. Other soil constituents such as clay did not contribute to the degradation under moist or air-dried conditions, though enhanced degradation was observed on oven-dried montmorillonite and kaolinite clays. Within soil profiles, degradation of CH₃Br decreased with soil depth mainly due to the reduction of soil organic matter content with depth. In both Greenfield and Wasco sandy loams, the degradation rate of CH₃Br in soil layers from 0 to 270 cm could be estimated from soil organic matter content. Sorption of CH₃Br on moist soils was generally limited, and varied with soil depth. The degree of sorption could be predicted from soil moisture alone or soil moisture and organic matter content.     

Concentrations of carbon monoxide and methane at two heights above a grass field and their deposition onto the field

To investigate whether wind is a significant driving force in the diffusion of CO and CH₄ from the atmosphere into soil, we measured the concentrations of these two gases at two heights above a temperate grass field in Japan and estimated their deposition velocities using micrometeorological techniques. The concentrations were inversely correlated with wind speed, indicating that the local concentrations were influenced by ground sources. The CO and CH₄ concentrations at 0.33 m were usually lower than those at 1.3 m. Although nocturnal data are suspected to be non-stationary, by selecting several periods when the changes of the concentrations were small but larger than analytical precision, we obtained a CO velocity of 2.9 and 3.9×10⁻² cms⁻¹, agreeing with a CO deposition velocity, 3.4×10⁻² cms⁻¹, obtained by applying a method using CO₂ as a tracer. The CH₄ influx obtained by the method using CO₂ as a tracer was 13 ngm⁻² s⁻¹. The ranges of the CO deposition velocity and CH₄ influx were similar to those obtained in previous studies in grassfields and in a nearby arable field using a closed-chamber technique. This shows that light winds do not greatly accelerate CO and CH₄ uptake by soil.     

Partial solubility parameters of chlorobenzene and chlorophenol compounds at equilibrium distribution in two immiscible phases

Partial solubility parameters of chlorobenzene and chlorophenol compounds at equilibrium distribution in two immiscible phases such as soil-water system were studied. An integral distribution equilibrium equation is derived from the concept of partial solubility parameters and Flory-Hungins equation. Twelve chlorobenzenes and nineteen chlorophenols were employed in this study and their partial solubility parameters including dispersion( (δ_d),and polar van der Waals (δ_p), as well as their electron acceptor and donor solubility parameters (δ_a and δ_b) were calculated.Hildebrand's solubility parameter(δ) of the compounds was also obtained by using boiling point and formula.HPLC was performed by octadecyl-bonded phase as the stationary phase with methanol or acetonitrile as the mobile phase to determine the capacity factor k′ of all compounds for the calculation of δ_a and δ_b.     

两相均流板对弯管中气固两相运动分布特征的影响

针对燃煤电厂烟气污染物脱除系统设备入口弯管内的气固两相分布不均的问题,提出一种两相均流板,采用CFD数值模拟的方法对比分析了安装两相均流板与常规导流装置的弯道内气流速度分布、颗粒质量浓度分布以及弯管进出口压差变化特征。结果表明：在弯管内安装两相均流板较安装导流板/三角翼挡板更优,既可以使气固两相均匀分布又可以有效降低系统的压阻,克服了常规均流装置气固两相均流效果不佳、阻力大等缺点,在较低的压阻下解决燃煤电厂烟气污染物脱除系统入口气固两相混合不均匀的问题,有效提高污染物脱除效率。     

Biomonitors and the assessment of ecological impacts: distribution of herbivorous epifauna in contaminated macroalgal beds

We determined metal contents of co-occurring algae Padina crassa and Sargassum sp. in Port Jackson (Australia), and relationships between metal levels and the abundance of epifaunal amphipods. Copper, lead and zinc concentrations were amongst the highest yet recorded in these algae. Copper, manganese and lead concentrations were far greater in P. crassa than Sargassum sp., possibly due to the low growth of P. crassa in proximity to contaminated sediments. However, in manipulative experiments the proximity of algae to sediments did not explain these differences. The abundance of herbivorous amphipods correlated negatively with the copper content of P. crassa, but not with the lower concentrations in Sargassum sp. The greater contamination of P. crassa led to patchy distributions of metals in algal beds and recolonisation experiments showed Sargassum sp. acts as a refuge from contaminants for epifauna. The contamination of macroalgae may pose threats to epifauna in harbours around the world.     

SBAR内不同有机负荷下2种好氧颗粒污泥形成及除磷性能

在SBAR中首先采用低有机负荷继而提高负荷的方法成功培养出2种不同类型的好氧颗粒污泥。在长期培养过程中,对SBAR系统中的微生物特征包括污泥浓度、SVI沉降指数等指标及系统对废水中COD和氮磷去除性能进行评估。在稳定阶段,通过在不同浓度NaCl溶液中测试和对比SBAR内2种颗粒污泥的沉降性能。结果表明,系统经过89 d的低有机负荷(0.75 kg COD/(m3·d))运行,小颗粒污泥缓慢形成,表面光滑,外观规则为近似球形;大幅度提高有机负荷(1.6 kg COD/(m3·d))促使大颗粒污泥的快速形成,多数为椭球形,并且颗粒边缘清晰透明;经过93 d稳定运行,成熟的小颗粒和大颗粒的平均直径分别为0.35 mm 和1.35 mm;随着大颗粒污泥的增多,系统除磷效果明显增强;在不同盐浓度(0%~15%)条件下大颗粒污泥比小颗粒污泥沉降速度更高;小颗粒污泥在大于2%的NaCl溶液出现悬浮现象而大颗粒仅在15%的NaCl溶液出现悬浮现象,进一步说明大颗粒污泥密度相对较大。     

Temperature-dependent rate coefficients for the reactions of Cl atoms with methyl methacrylate,methyl acrylate and butyl methacrylate at atmospheric pressure

Rate coefficients for the gas-phase reactions of Cl atoms with a series of unsaturated esters CH₂C(CH₃)C(O)OCH₃ (MMA), CH₂CHC(O)OCH₃ (MAC) and CH₂C(CH₃)C(O)O(CH₂)₃CH₃ (BMA) have been measured as a function of temperature by the relative technique in an environmental chamber with in situ FTIR detection of reactants. The rate coefficients obtained at 298 K in one atmosphere of nitrogen or synthetic air using propene, isobutene and 1,3-butadiene as reference hydrocarbons were (in units of 10^?10 cm³ molecule^?1 s^?1) as follows: k_(Cl+MMA) = 2.82 ± 0.93, k_(Cl+MAC) = 2.04 ± 0.54 and k_(Cl+BMA) = 3.60 ± 0.87. The kinetic data obtained over the temperature range 287–313 K were used to derive the following Arrhenius expressions (in units of cm³ molecule^?1 s^?1): k_(Cl+MMA) = (13.9 ± 7.8) × 10^?15 exp[(2904 ± 420)/T], k_(Cl+MAC) = (0.4 ± 0.2) × 10^?15 exp[(3884 ± 879)/T], k_(Cl+BMA) = (0.98 ± 0.42) × 10^?15 exp[(3779 ± 850)/T]. All the rate coefficients display a slight negative temperature dependence which points to the importance of the reversibility of the addition mechanism for these reactions. This work constitutes the first kinetic and temperature dependence study of the reactions cited above.An analysis of the available rates of addition of Cl atoms and OH radicals to the double bond of alkenes and unsaturated and oxygenated volatile organic compounds (VOCs) at 298 K has shown that they can be related by the expression: log k_OH = 1.09 log k_Cl ? 0.10. In addition, a correlation between the reactivity of unsaturated VOCs toward OH radicals and Cl atoms and the HOMO of the unsaturated VOC is presented. Tropospheric implications of the results are also discussed.     

A comparison of extinction and size distribution data measured at two urban sites in the U.S. and Europe

Extinction coefficients and mass size distributions were measured at St. Louis, MO. and at Vienna, Austria with the same instrumentation (an 11-wavelength automated telephotometer and an 8-stage low pressure cascade impactor, both designed at the University of Vienna). A comparison between the sites gave lower extinction coefficients, mean aerodynamic diameters, standard deviations and mass concentrations of the accumulation mode at the St. Louis site and a similar dependence of extinction on relative humidity.     

Evaluation of weather conditions for methyl bromide ambient air monitoring in Monterey, Santa Cruz, and Kern Counties in the year 2000

Weather condition is one of the most important factors affecting spatial and temporal distributions of air pollutants, especially for short-term air dispersion. Abnormal weather conditions might lead to higher or lower ambient air concentrations than they would be under normal weather conditions. Therefore, testing for normality of weather conditions during the air monitoring period is an essential step for evaluating ambient air monitoring results. In this paper, a distance method was used to select a most representative weather station from the available candidates. An array of meteorological elements were identified that affect air dispersion and transportation. A statistical method was used to determine whether the weather conditions during the air monitoring period were significantly different from that of previous years. Using methyl bromide ambient air monitoring as a case study, this paper documents the methods, procedures, and results of weather analysis for Monterey, Santa Cruz, and Kern Counties during ambient air monitoring periods for methyl bromide in the year 2000. With a few exceptions, the meteorological elements and atmospheric stability factors, such as wind speeds, wind directions, and stability classes, during the monitoring period were in the normal range. Although there were higher frequencies of stable atmospheric conditions in Monterey/Santa Cruz Counties than in Kern County, weather conditions during the monitoring period were not significantly different from normal local weather conditions of previous years. Consequently, the subchronic air concentrations observed during the ambient air monitoring periods for methyl bromide in the year 2000 was taken under typical weather conditions of those areas at that time of the year.     

Persistence of Bacillus thuringiensis deposits in a hardwood forest,after aerial application of a commercial formulation at two dosage rates

Abstract

A commercial formulation of Bacillus thuringiensis Berliner var. kurstaki (BTK), Foray® 48B, was sprayed aerially over four blocks B13, B14, B15A and B15B in an oak forest in Wayne County, Pennsylvania during May 1990. B13 and B14 were sprayed at 75 billion international units (BIU) in 5.91 litres/ha and the other two at 50 BIU in 3.94 litres/ha. Oak foliage was collected at different intervals of time after treatment. Three types of bioassays were conducted against fourth instar gypsy moth larvae, viz., direct feeding of sprayed foliage, feeding on diet containing homogenized foliage, and force‐feeding of foliar extracts. Larval mortalities were converted into international units of BTK activity per unit area (IU/cm²) of foliage. Foliar extracts were also subjected to enzyme‐linked immunosorbent assay (ELISA) to determine the concentration of delta‐endotoxin protein. Regardless of the type of bioassay used, bioactivity of BTK persisted in foliage for about a week in all the blocks. The half‐life of inactivation, DT₅₀, ranged from ca 12 to 22 h. The immunoassay data indicated a shorter duration of persistence (i.e., about 2 d) of the delta‐endotoxin protein, with DT₅₀ values ranging from 10 to 15 h. Formulation ingredients present in Foray 48B played a role in the toxicity of BTK to gypsy moth larvae.     

Droplet size spectra and deposits of Bacillus thuringiensis aerial sprays,following application at two volume rates over an oak forest

Abstract

Dipel® 8AF, a commercial formulation of Bacillus thuringiensis (B.t.) was sprayed undiluted at 30 BIU in 1.8L/ha over a block B1, and sprayed after dilution with water at 30 BIU in 6.2 L/ha over another block B2 in an oak forest infested with the gypsy moth (Lymantria dispar L.) in southeastern Ontario, Canada. Spray was applied in May 1987 using a Cessna 188 Agtruck aircraft equipped with four Hicronair^® AU4000 atomizers. Droplet sizes were measured at mid‐canopy level of oak trees and at ground level using cylindrical Kromekote® cards. Deposit per unit area was assessed on aluminum oak leaves.

At the lower volume rate of 1.8 L/ha, spray droplets were smaller and droplets/cm² were lower on the cylindrical Kromekote cards in B1 than those obtained in B2 which received the higher volume rate of 6.2 L/ha. The average deposit per unit area of the aluminum oak leaves, expressed in nL of the spray volume per cm² surface area, was also correspondingly lower in B1 than in B2. This was attributed to the higher volume rate of spray application used in B2 than in B1, which resulted in larger droplets and a greater volume deposit/cm² in B2.