Development of a methyl bromide collection system for fumigated farmland

Recent research has indicated that up to 73% of the methyl bromide (MeBr) applied to agricultural farmland is ultimately emitted to the atmosphere despite the practice of complete coverage of the fields with polyethylene (PE) tarp. To reduce the emission of MeBr, several techniques have been investigated. An alternative that has received little consideration is the collection and recycle or treatment of MeBr emissions. We investigated the potential of using a two-layer tarp system for collecting the MeBr. Laboratory experiments with a small two-layer diffusion reactor were conducted to determine the mass transfer coefficient (K) of MeBr through tarps and to validate a model of the collection system. For PE tarps K was 1.15 x 10(-6) m s-1 at 20 degrees C and 5.2 x 10(-6) m s-1 at 60 degrees C. K for so-called virtually impermeable films ranged from 4.6 x 10(-10) m s-1 to 1.3 x 10(-8) m s-1. The mathematical model was then used to simulate a full scale fumigant field application. Results indicate excellent agreement between the model, laboratory experiments, and previous field studies. Total emission from the field was a function of the air exchange rate through the swept volume between the two layers, the length of time the field is covered by the collection system, and the mass transfer coefficient of MeBr though the tarps. The results indicate that the proposed two-layer system can be very effective in collecting MeBr emissions from fumigated farmland.     

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.     

Interaction of methyl bromide with soil

Because methyl bromide (CH3Br) is a widely used agricultural fumigant for soil disinfection, it is important to know the chemical behavior and fate of CH3Br as a result of its use for soil treatment. A solid-state 13C NMR study of 13CH3Br-treated soil and soil-component samples shows that methylation of soil organic matter may be the major pathway for degradation of CH3Br in soils. Adsorption of CH3Br on a dried clay like Ca-montmorillonite or kaolinite does not contribute directly to the degradation of CH3Br. The results are interpreted in terms of the chemical structures of separated soil fractions and the nature of the separation procedure.     

Depleting methyl bromide residues in soil by reaction with bases

Despite generally being considered the most effective soil fumigant, methyl bromide (MeBr) use is being phased out because its emissions from soil can lead to stratospheric ozone depletion. However, a large amount is still currently used due to Critical Use Exemptions. As strategies for reducing the postfumigation emissions of MeBr from soil, Ca(OH)(2), K(2)CO(3), and NH(3) were assessed as means of promoting MeBr degradation. Ammonia aqueous solution (NH(4)OH) was the most effective, because MeBr can be degraded by both hydrolysis and ammonolysis. At 20 °C, the half-lives (t(1/2)) of MeBr were 18.0, 2.5, and 1.3 h in 0.1, 1.0, and 2.0 M NH(4)OH, respectively. In 1.0 M NH(4)OH, increasing the solution temperature to 40 °C reduced the half-life of MeBr to 0.23 h. Ammonia amendment to moist soil also promoted MeBr transformation, and the MeBr degradation rate increased with increasing soil temperature. NH(4)OH (30%, 16 M) very effectively reacted with MeBr that was contained under plastic film. Under Hytibar (a virtually impermeable film, VIF), over 99.5% of the MeBr could be destroyed by 30% NH(4)OH in 8 h at 20 °C. On the basis of these results, good management practices (i.e., VIF plus NH(4)OH) could be developed for continued use of MeBr as a soil fumigant under Critical Use Exemptions, without significant emissions.     

Bioreactors for removing methyl bromide following contained fumigations

Use of methyl bromide (MeBr) as a quarantine, commodity, or structural fumigant is under scrutiny because its release to the atmosphere contributes to the depletion of stratospheric ozone. A closed-system bioreactor consisting of 0.5 L of a growing culture of a previously described bacterium, strain IMB-1, removed MeBr (> 110 micromol L(-1)) from recirculating air. Strain IMB-1 grew slowly to high cell densities in the bioreactor using MeBr as its sole carbon and energy source. Bacterial oxidation of MeBr produced CO2 and hydrobromic acid (HBr), which required continuous neutralization with NaOH for the system to operate effectively. Strain IMB-1 was capable of sustained oxidation of large amounts of MeBr (170 mmol in 46 d). In an open-system bioreactor (10-L fermenter), strain IMB-1 oxidized a continuous supply of MeBr (220 /micromol L(-1) in air). Growth was continuous, and 0.5 mol of MeBr was removed from the air supply in 14 d. The specific rate of MeBr oxidation was 7 x 10(-16) mol cell(-1) h(-1). Bioreactors such as these can therefore be used to remove large quantities of contaminant MeBr, which opens the possibility of biodegradation as a practical means for its disposal.     

Reducing 1,3-dichloropropene emissions from soil columns amended with thiourea

Soil fumigants are becoming an important source of volatile organic compounds (VOCs) in air, especially in some agricultural areas. In this study, we used thiourea to construct a reactive surface barrier (RSB) at the soil surface for reducing 1,3-dichloropropene (1,3-D) volatilization. The agrochemical thiourea could rapidly transform volatile 1,3-D to nonvolatile products via an SN2 nucleophilic substitution reaction. A catalytic mechanism in thiourea-amended soil facilitated the conversion process. A packed soil column system was employed to investigate the emissions and distribution of 1,3-D and optimize the original fumigant emission-reduction strategy. Volatilization of 1,3-D from the soil surface was significantly reduced in columns amended with a thiourea RSB compared with that of bare soil. Volatilization flux and cumulative emissions decreased with increasing thiourea application rate and increasing fumigation depth in packed soil columns. Surface amendment with the RSB did not affect the subsurface distribution of 1,3-D in the soil profile. Combined application of a thiourea RSB and plastic tarps had a synergetic effect in emission control and could eliminate the relatively high fumigant flux that occurs upon tarp disruption. Therefore, this reduced-risk practice was very effective in reducing atmospheric emissions of VOCs from soil treatment with halogenated fumigants.     

Abiotic methyl bromide formation from vegetation, and its strong dependence on temperature

Methyl bromide (CH3Br) is the most abundant brominated organic compound in the atmosphere. It is known to originate from natural and anthropogenic sources, although many uncertainties remain regarding strengths of both sources and sinks and the processes leading to its formation. In this study a potential new CH3Br source from vegetation has been examined, analogous to the recently discovered abiotic formation of methyl chloride from plant pectin. Several plant samples with known bromine content, including ash (Fraxinus excelsior), saltwort (Batis maritima), tomato reference material (NIST-1573a), hay reference material (IAEA V-10), and also bromine enriched pectin, were incubated in the temperature range of 25-50 degrees C and analyzed for CH3Br emission using gas chromatography/mass spectrometry. All plant samples inspected showed an exponential increase in CH3Br emission as a function of temperature increase, i.e., emissions were observed to approximately double with every 5 degrees C rise in temperature. Next to temperature, it was found that emissions of CH3Br were also dependent on the bromine content of the plants. The highest CH3Br release rates were found for the saltwort which contained the highest bromine concentration. Arrhenius plots confirmed that the observed emissions were from an abiotic origin. The contribution of abiotic CH3Br formation from vegetation to the global budget will vary geographically as a result of regional differences in both temperature and bromide content of terrestrial plants.     

SPI/MC关混可食膜的性能研究

研究了甲基纤维素(MC)对以甘油为增塑剂的大豆分离蛋白(SPI)膜物理性质的影响.结果表明:SPI膜的抗拉强度和表面疏水性随着MC添加量的增加而显著提高(P≤0.05),在添加量为20.0%(w/w,SPI)时相对于对照样分别提高了66.32%和25.39%;断裂伸长率随着MC添加量的增加而先增大后降低,在添加量为10.0%时最大;膜的透光率、水分含量、可溶性干物质总量和水蒸气透过系数随着MC添加量的增加而降低(P≤0.05),在添加量为20.0%时相对于对照样分别降低了41.58%、14.02%、26.55%和20.86%.     

A predictive tool for emissions from heavy-duty diesel vehicles

Traditional emissions inventories for trucks and buses have relied on diesel engine emissions certification data, in units of g/bhp-hr, processed to yield a value in g/mile without a detailed accounting of the vehicle activity. Research has revealed a variety of other options for inventory prediction, including the use of emissions factors based upon instantaneous engine power and instantaneous vehicle behavior. The objective of this paper is to provide tabular factors for use with vehicle activity information to describe the instantaneous emissions from each heavy-duty vehicle considered. To produce these tables, a large body of data was obtained from the research efforts of the West Virginia University-Transportable Heavy Duty Emissions Testing Laboratories (TransLabs). These data were available as continuous records of vehicle speed (hence also acceleration), vehicle power, and emissions of carbon monoxide (CO), oxides of nitrogen (NOx), and hydrocarbons (HC). Data for particulate matter (PM) were available only as a composite value for a whole vehicle test cycle, but using a best effort approach, the PM was distributed in time in proportion to the CO. Emissions values, in g/sec, were binned according to the speed and acceleration of a vehicle, and it was shown that the emissions could be predicted with reasonable accuracy by applying this table to the original speed and acceleration data. The test cycle used was found to have a significant effect on the emissions value predicted. Tables were created for vehicles grouped by type (large transit buses, small transit buses, and tractor-trailers) and by range of model year. These model year ranges were bounded by U.S. national changes in emissions standards. The result is that a suite of tables is available for application to emissions predictions for trucks and buses with known activity, or as modeled by TRANSIMS, a vehicle activity simulation model from Los Alamos National Laboratories.     

大豆蛋白和羧甲基葡甘聚糖共混膜的制备和性能

为了提高大豆蛋白膜的机械和阻湿性能,制备了大豆分离蛋白/羧甲基葡甘聚糖共混膜。用红外光谱、透光率测试、扫描电镜测定表征了其结构,测试了共混膜的力学、抗潮、阻气等性能。结果表明,大豆分离蛋白与羧甲基葡甘聚糖有良好的相互作用,共混膜的力学性能、抗潮性能及阻气性能均有明显提高,其中拉伸强度较羧甲基葡甘聚糖提高了117.6%,吸湿增重较羧甲基葡甘聚糖下降了19.02%,透湿系数下降了40.97%。     

Estimates of increased black carbon emissions from electrostatic precipitators during powdered activated carbon injection for mercury emissions control

The behavior of mercury sorbents within electrostatic precipitators (ESPs) is not well-understood, despite a decade or more of full-scale testing. Recent laboratory results suggest that powdered activated carbon exhibits somewhat different collection behavior than fly ash in an ESP and particulate filters located at the outlet of ESPs have shown evidence of powdered activated carbon penetration during full-scale tests of sorbent injection for mercury emissions control. The present analysis considers a range of assumed differential ESP collection efficiencies for powdered activated carbon as compared to fly ash. Estimated emission rates of submicrometer powdered activated carbon are compared to estimated emission rates of particulate carbon on submicrometer fly ash, each corresponding to its respective collection efficiency. To the extent that any emitted powdered activated carbon exhibits size and optical characteristics similar to black carbon, such emissions could effectively constitute an increase in black carbon emissions from coal-based stationary power generation. The results reveal that even for the low injection rates associated with chemically impregnated carbons, submicrometer particulate carbon emissions can easily double if the submicrometer fraction of the native fly ash has a low carbon content. Increasing sorbent injection rates, larger collection efficiency differentials as compared to fly ash, and decreasing sorbent particle size all lead to increases in the estimated submicrometer particulate carbon emissions.     

Development and application of a mobile laboratory for measuring emissions from diesel engines. 1. Regulated gaseous emissions

Information about in-use emissions from diesel engines remains a critical issue for inventory development and policy design. Toward that end, we have developed and verified the first mobile laboratory that measures on-road or real-world emissions from engines at the quality level specified in the U.S. Congress Code of Federal Regulations. This unique mobile laboratory provides information on integrated and modal regulated gaseous emission rates and integrated emission rates for speciated volatile and semivolatile organic compounds and particulate matter during real-world operation. Total emissions are captured and collected from the HDD vehicle that is pulling the mobile laboratory. While primarily intended to accumulate data from HDD vehicles, it may also be used to measure emission rates from stationary diesel sources such as back-up generators. This paper describes the development of the mobile laboratory, its measurement capabilities, and the verification process and provides the first data on total capture gaseous on-road emission measurements following the California Air Resources Board (ARB) 4-mode driving cycle, the hot urban dynamometer driving schedule (UDDS), the modified 5-mode cycle, and a 53.2-mi highway chase experiment. NOx mass emission rates (g mi(-1)) for the ARB 4-mode driving cycle, the hot UDDS driving cycle, and the chase experimentwerefoundto exceed current emission factor estimates for the engine type tested by approximately 50%. It was determined that congested traffic flow as well as "off-Federal Test Procedure cycle" emissions can lead to significant increases in per mile NOx emission rates for HDD vehicles.     

Evaluation of methods for measuring particulate matter emissions from gas turbines

The project SAMPLE evaluated methods for measuring particle properties in the exhaust of aircraft engines with respect to the development of standardized operation procedures for particulate matter measurement in aviation industry. Filter-based off-line mass methods included gravimetry and chemical analysis of carbonaceous species by combustion methods. Online mass methods were based on light absorption measurement or used size distribution measurements obtained from an electrical mobility analyzer approach. Number concentrations were determined using different condensation particle counters (CPC). Total mass from filter-based methods balanced gravimetric mass within 8% error. Carbonaceous matter accounted for 70% of gravimetric mass while the remaining 30% were attributed to hydrated sulfate and noncarbonaceous organic matter fractions. Online methods were closely correlated over the entire range of emission levels studied in the tests. Elemental carbon from combustion methods and black carbon from optical methods deviated by maximum 5% with respect to mass for low to medium emission levels, whereas for high emission levels a systematic deviation between online methods and filter based methods was found which is attributed to sampling effects. CPC based instruments proved highly reproducible for number concentration measurements with a maximum interinstrument standard deviation of 7.5%.     

Simple models for assessing migration from food-packaging films

Owing to their simplicity, two migration models based on Fick's Second Law have been frequently used for the assessment of migration of additives and contaminants from food-packaging films. While the two models are known to provide accurate estimates of diffusion coefficients for complete migration, they could generate considerable estimation errors for significantly partitioned migration. In this paper, the applicability of the two models to partitioned migration is defined by examining the assumptions and derivations of the two models as well as their errors in estimating diffusion coefficients. Furthermore, a simple migration model, based on more realistic assumptions than the two models, is proposed. The proposed model can provide far better estimates of diffusion coefficients for partitioned migration than the two models.     

Direct injection GC method for measuring light hydrocarbon emissions from cooling-tower water

A Direct Injection GC method for quantifying low levels of light hydrocarbons (C6 and below) in cooling water has been developed. It is intended to overcome the limitations of the currently available technology. The principle of this method is to use a stripper column in a GC to strip waterfrom the hydrocarbons prior to entering the separation column. No sample preparation is required since the water sample is introduced directly into the GC. Method validation indicates that the Direct Injection GC method offers approximately 15 min analysis time with excellent precision and recovery. The calibration studies with ethylene and propylene show that both liquid and gas standards are suitable for routine calibration and calibration verification. The sampling method using zero headspace traditional VOA (Volatile Organic Analysis) vials and a sample chiller has also been validated. It is apparent that the sampling method is sufficient to minimize the potential for losses of light hydrocarbons, and samples can be held at 4 degrees C for up to 7 days with more than 93% recovery. The Direct Injection GC method also offers <1 ppb (w/v) level method detection limits for ethylene, propylene, and benzene. It is superior to the existing El Paso stripper method. In addition to lower detection limits for ethylene and propylene, the Direct Injection GC method quantifies individual light hydrocarbons in cooling water, provides better recoveries, and requires less maintenance and setup costs. Since the instrumentation and supplies are readily available, this technique could easily be established as a standard or alternative method for routine emission monitoring and leak detection of light hydrocarbons in cooling-tower water.     

Measurement of N2, N2O, NO, and CO2 emissions from soil with the gas-flow-soil-core technique

Here we describe a newly designed system with three stand-alone working incubation vessels for simultaneous measurements of N(2), N(2)O, NO, and CO(2) emissions from soil. Due to the use of a new micro thermal conductivity detector and the redesign of vessels and gas sampling a so-far unmatched sensitivity (0.23 μg N(2)-N h(-1) kg(-1) ds or 8.1 μg N(2)-N m(-2) h(-1)) for detecting N(2) gas emissions and repeatability of experiments could be achieved. We further tested different incubation methods to improve the quantification of N(2) emission via denitrification following the initialization of soil anaerobiosis. The best results with regard to the establishment of a full N balance (i.e., the changes in mineral N content being offset by simultaneous emission of N gases) were obtained when the anaerobic soil incubation at 25 °C was preceded by soil gas exchange under aerobic conditions at a lower incubation temperature. The ratios of N and C gas emission changed very dynamically following the initialization of anaerobiosis. For soil NO(3)(-) contents of 50 mg N kg(-1) dry soil (ds) and dissolved organic carbon (DOC) concentrations of approximately 300 mg C kg(-1) ds, the cumulative emissions of N(2), N(2)O, and NO were 24.3 ± 0.1, 12.6 ± 0.4, and 10.1 ± 0.3 mg N kg(-1) ds, respectively. Thus, N gas emissions accounted (on average) for 46.2% (N(2)), 24.0% (N(2)O), and 19.2% (NO) of the observed changes in soil NO(3)(-). The maximum N(2) emission reached 1200 μg N h(-1) kg(-1) ds, whereas the peak emissions of N(2)O and NO were lower by a factor of 2-3. The overall N(2):N(2)O and NO:N(2)O molar ratios were 1.6-10.0 and 1.6-2.3, respectively. The measurement system provides a reliable tool for studying denitrification in soil because it offers insights into the dynamics and magnitude of gaseous N emissions due to denitrification under various incubation conditions.