Long-term monitoring of a marine geologic hydrocarbon source by a coastal air pollution station in Southern California

Hourly total hydrocarbon (THC) data, spanning 1990–2008 from a California air pollution station located near the Coal Oil Point (COP) seep field, were analyzed and clearly showed geologic CH₄ emissions as the dominant local source. Annual COP emissions are conservatively estimated as 0.015 Tg CH₄ year^?1 and represent a natural and concentrated geologic methane source (24 m³ m^?2 day^?1 gas flux at some active seeps, Clark et al., 2010). For a sense of the scale and potential importance to the regional Southern California methane budget, COP emits an amount equivalent to 8% of the estimated Los Angeles County anthropogenic emissions. Station THC measurements near COP showed a strong wind dependency with elevated levels closely correlated with a sonar-derived spatial distribution of seep field emissions. THC varied seasonally, with a maximum in January and minimum in July and a peak-to-peak amplitude of 0.24 ppm. The seasonal signal was more readily apparent midday (R² = 0.69 harmonic fit), compared to nighttime and morning (R² < 0.45). The bimodal diel THC pattern consisted of seasonally-modulated peaks in the morning and evening.THC temporal and spatial trends were consistent with both transport and source emission variations. Long-term, annual seep field emissions consistently decreased on a field-wide basis until the late 1990s, before increasing consistently, most likely as a function of underlying geologic processes. This study demonstrates the value of municipal air quality monitoring stations for insight into local greenhouse gas sources and highlights the non-negligible and variable contribution from marine geologic seepage.     

Air emission flux from contaminated dredged materials stored in a pilot-scale confined disposal facility

A pilot-scale field simulation was conducted to estimate the air emissions from contaminated dredged material stored in a confined disposal facility (CDF). Contaminated dredged material with a variety of organic chemicals, obtained from Indiana Harbor Canal, was used in the study. It was placed in an outdoor CDF simulator (i.e., a lysimeter of dimensions 4 ft x 4 ft x 2 ft). A portable, dynamic flux chamber was used to periodically measure emissions of various polynuclear aromatic hydrocarbons (PAHs). A weather station was set up to monitor and record the meteorological conditions during the experiment. The fluxes of several PAHs were monitored over time for 6 1/2 months. Initial 6-hr average fluxes varied from 2 to 20 ng/cm2/hr for six different PAHs. The flux values declined rapidly for all compounds soon after placement of the dredged material in the CDE Chemical concentrations derived from flux values were generally of low magnitude compared with ambient standards. Data obtained from the experiment were compared against those predicted using models for air emissions. Model simulations showed that initially the flux was largely from exposed pore water from saturated (wet) sediment, whereas the long-term flux was controlled by diffusion through the pore air of the unsaturated sediment. Model predictions generally overestimated the measured emissions. A rainfall event was simulated, and the dredged material was reworked to simulate that typical of a CDF operation. Increased flux was observed upon reworking the dredged material.     

Application of a combined measurement and modeling method to quantify windblown dust emissions from the exposed playa at Mono Lake, California

Particulate matter < or =10 microm (PM10) emissions due to wind erosion can vary dramatically with changing surface conditions. Crust formation, mechanical disturbance, soil texture, moisture, and chemical content of the soil can affect the amount of dust emitted during a wind event. A refined method of quantifying windblown dust emissions was applied at Mono Lake, CA, to account for changing surface conditions. This method used a combination of real-time sand flux monitoring, ambient PM10 monitoring, and dispersion modeling to estimate dust emissions and their downwind impact. The method identified periods with high emissions and periods when the surface was stable (no sand flux), even though winds may have been high. A network of 25 Cox sand catchers (CSCs) was used to measure the mass of saltating particles to estimate sand flux rates across a 2-km2 area. Two electronic sensors (Sensits) were used to time-resolve the CSC sand mass to estimate hourly sand flux rates, and a perimeter tapered element oscillating microbalance (TEOM) monitor measured hourly PM10 concentrations. Hourly sand flux rates were related by dispersion modeling to hourly PM10 concentrations to back-calculate the ratio of vertical PM10 flux to horizontal sand flux (K-factors). Geometric mean K-factor values (K(f)) were found to change seasonally, ranging from 1.3 x 10(-5) to 5.1 x 10(-5) for sand flux measured at 15 cm above the surface (q15). Hourly PM10 emissions, F, were calculated by applying seasonal K-factors to sand flux measurements (F = K(f) x q15). The maximum hourly PM10 emission rate from the study area was 76 g/m2 x hr (10-m wind speed = 23.5 m/sec). Maximum daily PM10 emissions were estimated at 450 g/m2 x day, and annual emissions at 1095 g/m2 x yr. Hourly PM10 emissions were used by the U.S. Environmental Protection Agency (EPA) guideline AERMOD dispersion model to estimate downwind ambient impacts. Model predictions compared well with monitor concentrations, with hourly PM10 ranging from 16 to over 60,000 microg/m3 (slope = 0.89, R2 = 0.77).     

Effect of plastic tarps over raised-beds and potassium thiosulfate in furrows on chloropicrin emissions from drip fumigated fields

Plastic tarps are commonly used in raised bed strawberry production to minimize emissions of preplant soil fumigants and are left in place throughout the growing season as part of the standard cultural practices. Soil amendments with chemicals such as thiosulfate (S2O3(2-)) can reduce fumigant emissions. A field study was conducted near Santa Maria, CA to determine the effects of low density polyethylene (LDPE) and virtually impermeable film (VIF) over raised-beds and applying potassium thiosulfate (KTS) in furrows on reducing chloropicrin (CP) emissions from a strawberry field. Four fields (or treatments) were tested with 224 kg ha(-1) CP drip-applied threecm under the soil surface. The CP flux from bed tops and furrows and gas-phase concentrations under the tarps were monitored for five d. The CP emission flux and concentration under tarp were highest immediately following application. Diurnal temperature change affected CP concentration and emission fluxes (higher values during the day and lower at night). Slightly higher CP cumulative emission occurred using LDPE tarp (19%) compared to VIF (17%). Normalized flux (CP emission flux from the beds divided by CP concentration under the tarp) being estimated from field measurement was slightly higher for LDPE than VIF indicating different tarp permeability in the field. Because of extremely low emissions from the furrows (<0.2% of total emission loss), KTS application to furrow treatments did not show further emission reductions than non-KTS treatments. This indicates that emission reduction should focus on the tarp above raised-beds when fumigant was drip-applied near bed-surface.     

Workshop on the Intercomparison of Methodologies for Soil NOx Emissions: Summary of Discussion and Research Recommendations

A workshop on the intercomparison of methodologies for soil NO_x emissions was held on March 14-15, 1994 at North Carolina State University (NCSU) in Raleigh, North Carolina, in preparation for a field experiment tentatively scheduled for May-June, 1995 involving measurement of rural site NO_x emissions. The workshop was sponsored jointly by the U.S. Environmental Protection Agency (EPA) and NCSU. Representatives from several agencies will participate in the experiment, including the EPA, NASA, NOAA, DOE, NCAR, Atmospheric Science from the University of Maryland, and Atmospheric Sciences and Soil Sciences from NCSU. Approximately 50 workshop attendees, which included national experts on all aspects of flux measurement technologies, met for a day and a half to discuss techniques for measuring soil NO_x (= NO + NO₂) emissions and to suggest how to best incorporate these techniques into a field experiment to compare NO_x measuring methodologies. The need for more knowledge in the area of soil NO_x emissions is related to the uncertainty of the relationship between rural NO_x emissions and the production of tropospheric ozone. In particular, the role of nitrogen-based fertilizers spread over rural agricultural areas in the production or emission of NO_x is not well documented. To determine the best way to document and model these relationships, a full experimental comparison of NO_x emission measurement techniques over a rural agricultural area is needed. Thus, it was recommended that a study of the intercomparison of methodologies for soil NO_x emissions (both intensive field experiments and analysis) should be undertaken. The primary goal of this study will be to relate chamber techniques to micrometeorological flux estimates of NO_x. The study should include (i) an intensive four-to-six-week experiment for the intercomparison of methodologies for soil NO_x emissions, (ii) and soil and air quality characterization of the experimental site.     

Dynamic flux chamber measurement of gaseous mercury emission fluxes over soils: Part 2—effect of flushing flow rate and verification of a two-resistance exchange interface simulation model

Both field and laboratory tests demonstrated that soil Hg emission fluxes measured by dynamic flux chamber (DFC) operations strongly depend on the flushing air flow rates used. The general trend is an increase in the fluxes with increasing flushing flow rates followed by an asymptotic approach to flux maximum at sufficiently high (optimum) flushing flow rates. This study indicates that the DFC measurements performed at low flushing flow rates can underestimate Hg emission fluxes over soils, especially Hg-enriched soils. High flushing flow rates therefore are recommended for accurate estimation of soil Hg emission fluxes by DFC operations. The dependence of DFC-measured soil Hg emission fluxes on flushing flow rate is a physical phenomenon inherent in DFC operations, regardless of DFC design and soil physical characteristics. Laboratory tests using DFCs over different soils confirmed the predictions of a two-resistance exchange interface model and demonstrated the capability of this model in quantitatively simulating Hg emissions from soils measured by DFC operations.     

Correlating emissions with time and temperature to predict worst-case emissions from open liquid area sources

The two primary factors influencing ambient air pollutant concentrations are emission rate and dispersion rate. Gaussian dispersion modeling studies for odors, and often other air pollutants, vary dispersion rates using hourly meteorological data. However, emission rates are typically held constant, based on one measured value. Using constant emission rates can be especially inaccurate for open liquid area sources, like wastewater treatment plant units, which have greater emissions during warmer weather, when volatilization and biological activity increase. If emission rates for a wastewater odor study are measured on a cooler day and input directly into a dispersion model as constant values, odor impact will likely be underestimated. Unfortunately, because of project schedules, not all emissions sampling from open liquid area sources can be conducted under worst-case summertime conditions. To address this problem, this paper presents a method of varying emission rates based on temperature and time of the day to predict worst-case emissions. Emissions are varied as a linear function of temperature, according to Henry's law, and a tenth order polynomial function of time. Equation coefficients are developed for a specific area source using concentration and temperature measurements, captured over a multiday period using a data-logging monitor. As a test case, time/temperature concentration correlation coefficients were estimated from field measurements of hydrogen sulfide (H2S) at the Rowlett Creek Wastewater Treatment Plant in Garland, TX. The correlations were then used to scale a flux chamber emission rate measurement according to hourly readings of time and temperature, to create an hourly emission rate file for input to the dispersion model ISCST3. ISCST3 was then used to predict hourly atmospheric concentrations of H2S. With emission rates varying hourly, ISCST3 predicted 384 acres of odor impact, compared with 103 acres for constant emissions. Because field sampling had been conducted on relatively cool days (85-90 degrees F), the constant emission rate underestimated odor impact significantly (by 73%).     

Air-surface exchange of mercury with soils amended with ash materials

Air-surface exchange of mercury (Hg) was measured from soil low in Hg (0.013 mg/kg) amended with four different ash materials: a wood ash containing -10% coal ash (0.070 mg/kg Hg), a mixture of two subbituminous coal fly ashes (0.075 mg/kg Hg), a subbituminous coal ash containing -10% petroleum coke ash (1.2 mg/kg Hg), and an ash from incinerated municipal sewage sludge (4.3 mg/kg Hg) using a dynamic flux chamber. Ash was added to soil to simulate agricultural supplements, soil stabilization, and pad layers used in livestock areas. For the agricultural amendment, -0.4% ash was well mixed into the soil. To make the stabilized soil that could be used for construction purposes, -20% ash was mixed into soil with water. The pad layer consisted of a wetted 1-cm layer of ash material on the soil surface. Diel trends of Hg flux were observed for all of the substrates with significantly higher Hg emissions during the day and negligible flux or deposition of Hg during the night. Hg fluxes, which were measured in the summer months, were best correlated with solar radiation, temperature, and air O3 concentrations. Mean Hg fluxes measured outdoors for unamended soils ranged from 19 to 140 ng/m2 day, whereas those for soil amended with ash to simulate an agricultural application ranged from 7.2 to 230 ng/m2 day. Fluxes for soil stabilized with ash ranged from 77 to 530 ng/m2 day and for soil with pads constructed of ash ranged from -50 to 90 ng/m2 day. Simple analytical tests (i.e., total Hg content, synthetic precipitation leaching procedure, heating, and indoor gas-exchange experiments) were performed to assess whether algorithms based on these tests could be used to predict Hg fluxes observed outdoors using the flux chamber. Based on this study, no consistent relationships could be developed. More work is needed to assess long-term and seasonal variations in Hg flux from (intact and disturbed) substrates before annual estimates of emissions can be developed.     

Emissions of PCDD and PCDF from combustion of forest fuels and sugarcane: a comparison between field measurements and simulations in a laboratory burn facility

Release of PCDD and PCDF from biomass combustion such as forest and agricultural crop fires has been nominated as an important source for these chemicals despite minimal characterisation. Available emission factors that have been experimentally determined in laboratory and field experiments vary by several orders of magnitude from <0.5 μg TEQ (t fuel consumed)⁻¹ to >100 μg TEQ (t fuel consumed)⁻¹. The aim of this study was to evaluate the effect of experimental methods on the emission factor.A portable field sampler was used to measure PCDD/PCDF emissions from forest fires and the same fuel when burnt over a brick hearth to eliminate potential soil effects. A laboratory burn facility was used to sample emissions from the same fuels. There was very good agreement in emission factors to air (EF_Air) for forest fuel (Duke Forest, NC) of 0.52 (range: 0.40-0.79), 0.59 (range: 0.18-1.2) and 0.75 (range: 0.27-1.2) μg TEQ_WHO2005 (t fuel consumed)⁻¹ for the in-field, over a brick hearth, and burn facility experiments, respectively. Similarly, experiments with sugarcane showed very good agreement with EF_Air of 1.1 (range: 0.40-2.2), 1.5 (range: 0.84-2.2) and 1.7 (range: 0.34-4.4) μg TEQ (t fuel consumed)⁻¹ for in-field, over a brick hearth, open field and burn facility experiments respectively. Field sampling and laboratory simulations were in good agreement, and no significant changes in emissions of PCDD/PCDF could be attributed to fuel storage and transport to laboratory test facilities.     

Impact of microbial activity on copper, lead and nickel mobilization during the bioremediation of soil PAHs

A fungal bioremediation method using P. frequentans removed up to 75% of phenanthrene with the addition of water and nutrients over a period of 30 d. During the bioremediation process, changes in metal behavior were monitored by an in situ technique (diffusive gradients in thin-films, DGT) and by soil solution chemistry. DGT provided absolute data on fluxes from the solid phase to the DGT device and relative trends of concentrations of the most labile metal species. DGT response indicated that bioremediation increases metal mobilization from the solid phase. Filtration provided data on the concentrations of solution phase (<0.45 microm) metal. In all case, metal fluxes and concentrations significantly increased after the bioremediation process began. Fluxes increased from <0.1 pg cm(-2)s(-1) before bioremediation to between 0.2 and 0.5 pg cm(-2)s(-1) after bioremediation. Metal concentrations in the soils solution (filtration at 0.45 microm) increased from 2 to 10 microg l(-1) (Cu), 1-4 microgl(-1) (Pb) and from 40 to 140 microg l(-1) (Ni) after bioremediation. Although over a short time period, these data strongly indicated that there was remobilization of metal from solid to solution (and thus to the DGT device) directly due to the bioremediation process. Although the mechanism was not unambiguously identified, it was shown not to be related to small changes in bulk pH over time and was attributed to the microbial action on the surface of the soil solid phase, releasing metal into solution. Additionally, differences in metal concentration and flux were observed in sterilized and non-sterilized soils and in the absence or presence of phenanthrene. The results indicated that the bioremediation of soil by P. frequentans increased the flux, lability and mobility of trace metal species and therefore the likely metal bioavailability to plants.     

Measurements of air–surface exchange rates of volatile organic compounds

Vertical gradients of volatile organic compounds (VOCs) were measured over a maize field and a soybean field in 1995 and 1996, respectively, in the Lower Coastal Plains of North Carolina. The measurements over the maize field were conducted in its early growth period, during May 1995, and the measurements over the soybean field were conducted in its middle and later growth periods during July through August 1996 at the same location. These measurements were combined with micrometeorological flux measurements to determine emission flux measurements for various VOCs. This measurement programme was part of project NOVA (Natural emissions of Oxidant precursors: Validation of techniques and Assessment) to estimate the flux of VOCs. Methanol was identified as the major biogenic compound for both years with the average flux of 3450 ± 1456 µg/m²/hr over maize and 3079 ± 2766 µg/m²/hr over soybean. Acetone is another compound that was identified as a biogenic compound for both years with the average flux of 425 ± 223 µg/m²/hr over maize and 2701 ± 1710 µg/m²/hr over soybean. In addition to biogenic compounds, a large number of aromatic compounds, including styrene and 1,2,4-trimethylbenzene, were also identified as emissions from the ground over the soybean field.     

Correlating Emissions with Time and Temperature to Predict Worst-Case Emissions from Open Liquid Area Sources

Abstract

The two primary factors influencing ambient air pollutant concentrations are emission rate and dispersion rate. Gaussian dispersion modeling studies for odors, and often other air pollutants, vary dispersion rates using hourly meteorological data. However, emission rates are typically held constant, based on one measured value. Using constant emission rates can be especially inaccurate for open liquid area sources, like wastewater treatment plant units, which have greater emissions during warmer weather, when volatilization and biological activity increase. If emission rates for a wastewater odor study are measured on a cooler day and input directly into a dispersion model as constant values, odor impact will likely be underestimated. Unfortunately, because of project schedules, not all emissions sampling from open liquid area sources can be conducted under worst-case summertime conditions. To address this problem, this paper presents a method of varying emission rates based on temperature and time of the day to predict worst-case emissions. Emissions are varied as a linear function of temperature, according to Henry’s law, and a tenth order polynomial function of time. Equation coefficients are developed for a specific area source using concentration and temperature measurements, captured over a multiday period using a data-logging monitor. As a test case, time/temperature concentration correlation coefficients were estimated from field measurements of hydrogen sulfide (H₂S) at the Rowlett Creek Wastewater Treatment Plant in Garland, TX. The correlations were then used to scale a flux chamber emission rate measurement according to hourly readings of time and temperature, to create an hourly emission rate file for input to the dispersion model ISCST3. ISCST3 was then used to predict hourly atmospheric concentrations of H₂S. With emission rates varying hourly, ISCST3 predicted 384 acres of odor impact, compared with 103 acres for constant emissions. Because field sampling had been conducted on relatively cool days (85–90 °F), the constant emission rate underestimated odor impact significantly (by 73%).     

Organic compound emissions from a landfarm used for oil and gas solid waste disposal

Solid or sludgy hydrocarbon waste is a by-product of oil and gas exploration and production. One commonly used method of disposing of this waste is landfarming. Landfarming involves spreading hydrocarbon waste on soils, tilling it into the soil, and allowing it to biodegrade. We used a dynamic flux chamber to measure fluxes of methane, a suite of 54 nonmethane hydrocarbons, and light alcohols from an active and a remediated landfarm in eastern Utah. Fluxes from the remediated landfarm were not different from a polytetrafluoroethylene (PTFE) sheet or from undisturbed soils in the region. Fluxes of methane, total nonmethane hydrocarbons, and alcohols from the landfarm in active use were 1.41 (0.37, 4.19) (mean and 95% confidence limits), 197.90 (114.72, 370.46), and 4.17 (0.03, 15.89) mg m^?2 hr^?1, respectively. Hydrocarbon fluxes were dominated by alkanes, especially those with six or more carbons. A 2-ha landfarm with fluxes of the magnitude we observed in this study would emit 95.3 (54.3, 179.7) kg day^?1 of total hydrocarbons, including 11.2 (4.3, 33.9) kg day^?1 of BTEX (benzene, toluene, ethylbenzene, and xylenes).

Implications: Solid and sludgy hydrocarbon waste from the oil and gas industry is often disposed of by landfarming, in which wastes are tilled into soil and allowed to decompose. We show that a land farm in Utah emitted a variety of organic compounds into the atmosphere, including hazardous air pollutants and compounds that form ozone. We calculate that a 2-ha landfarm facility would emit 95.0 ± 66.0 kg day^?1 of total hydrocarbons, including 11.1 ± 1.5 kg day^?1 of BTEX (benzene, toluene, ethylbenzene, and xylenes).     

Characterizing ammonia emissions from swine farms in eastern North Carolina: part 2--potential environmentally superior technologies for waste treatment

The need for developing environmentally superior and sustainable solutions for managing the animal waste at commercial swine farms in eastern North Carolina has been recognized in recent years. Program OPEN (Odor, Pathogens, and Emissions of Nitrogen), funded by the North Carolina State University Animal and Poultry Waste Management Center (APWMC), was initiated and charged with the evaluation of potential environmentally superior technologies (ESTs) that have been developed and implemented at selected swine farms or facilities. The OPEN program has demonstrated the effectiveness of a new paradigm for policy-relevant environmental research related to North Carolina's animal waste management programs. This new paradigm is based on a commitment to improve scientific understanding associated with a wide array of environmental issues (i.e., issues related to the movement of N from animal waste into air, water, and soil media; the transmission of odor and odorants; disease-transmitting vectors; and airborne pathogens). The primary focus of this paper is on emissions of ammonia (NH3) from some potential ESTs that were being evaluated at full-scale swine facilities. During 2-week-long periods in two different seasons (warm and cold), NH3 fluxes from water-holding structures and NH3 emissions from animal houses or barns were measured at six potential EST sites: (1) Barham farm--in-ground ambient temperature anaerobic digester/energy recovery/greenhouse vegetable production system; (2) BOC #93 farm--upflow biofiltration system--EKOKAN; (3) Carrolls farm--aerobic blanket system--ISSUES-ABS; (4) Corbett #1 farm--solids separation/ gasification for energy and ash recovery centralized system--BEST; (5) Corbett #2 farm--solid separation/ reciprocating water technology--ReCip; and (6) Vestal farm--Recycling of Nutrient, Energy and Water System--ISSUES-RENEW. The ESTs were compared with similar measurements made at two conventional lagoon and spray technology (LST) farms (Moore farm and Stokes farm). A flow-through dynamic chamber system and two sets of open-path Fourier transform infrared (OP-FTIR) spectrometers measured NH3 fluxes continuously from water-holding structures and emissions from housing units at the EST and conventional LST sites. A statistical-observational model for lagoon NH3 flux was developed using a multiple linear regression analysis of 15-min averaged NH3 flux data against the relevant environmental parameters measured at the two conventional farms during two different seasons of the year. This was used to compare the water-holding structures at ESTs with those from lagoons at conventional sites under similar environmental conditions. Percentage reductions in NH3 emissions from different components of each potential EST, as well as the whole farm on which the EST was located were evaluated from the estimated emissions from water-holding structures, barns, etc., all normalized by the appropriate nitrogen excretion rate at the potential EST farm, as well as from the appropriate conventional farm. This study showed that ammonia emissions were reduced by all but one potential EST for both experimental periods. However, on the basis of our evaluation results and analysis and available information in the scientific literature, the evaluated alternative technologies may require additional technical modifications to be qualified as unconditional ESTs relative to NH3 emissions reductions.     

Air-Surface Exchange of Mercury with Soils Amended with Ash Materials

Abstract

Air-surface exchange of mercury (Hg) was measured from soil low in Hg (0.013 mg/kg) amended with four different ash materials: a wood ash containing ～10% coal ash (0.070 mg/kg Hg), a mixture of two subbituminous coal fly ashes (0.075 mg/kg Hg), a subbituminous coal ash containing ～10% petroleum coke ash (1.2 mg/kg Hg), and an ash from incinerated municipal sewage sludge (4.3 mg/kg Hg) using a dynamic flux chamber. Ash was added to soil to simulate agricultural supplements, soil stabilization, and pad layers used in livestock areas. For the agricultural amendment, ～0.4% ash was well mixed into the soil. To make the stabilized soil that could be used for construction purposes, ～20% ash was mixed into soil with water. The pad layer consisted of a wetted 1-cm layer of ash material on the soil surface. Diel trends of Hg flux were observed for all of the substrates with significantly higher Hg emissions during the day and negligible flux or deposition of Hg during the night. Hg fluxes, which were measured in the summer months, were best correlated with solar radiation, temperature, and air O₃ concentrations. Mean Hg fluxes measured outdoors for unamended soils ranged from 19 to 140 ng/m² day, whereas those for soil amended with ash to simulate an agricultural application ranged from 7.2 to 230 ng/m² day. Fluxes for soil stabilized with ash ranged from 77 to 530 ng/m² day and for soil with pads constructed of ash ranged from ?50 to 90 ng/m² day. Simple analytical tests (i.e., total Hg content, synthetic precipitation leaching procedure, heating, and indoor gas-exchange experiments) were performed to assess whether algorithms based on these tests could be used to predict Hg fluxes observed outdoors using the flux chamber. Based on this study, no consistent relationships could be developed. More work is needed to assess long-term and seasonal variations in Hg flux from (intact and disturbed) substrates before annual estimates of emissions can be developed.     

Dynamic flux chamber measurement of gaseous mercury emission fluxes over soils. Part 1: simulation of gaseous mercury emissions from soils using a two-resistance exchange interface model

A two-resistance exchange interface model (TREIM) was developed to simulate gaseous mercury (Hg) emissions from soils measured by dynamic flux chamber (DFC) operations. The model is based on mass balance principles and a Hg air/soil exchange theory that considers the influence of flushing flow rate on Hg air/soil exchange. We used this model to examine the effect of the flushing flow rate and understand the optimum conditions for DFC measurements of Hg emission fluxes over soils. Our model simulations indicate that the flushing flow rate is a most critical operation condition. We recommend adoption of high flushing flow rates (e.g., ∼15–40 l min⁻¹ for DFCs of common design) based on our simulation findings that underestimation of actual emission fluxes can occur at low flushing flow rates. The biased low fluxes are caused by suppression of emission potential resulting from internal accumulation of emitted Hg and by higher exchange resistance both at low flushing flow rates. This model provides a useful means for estimating maximum steady-state fluxes and soil air Hg concentrations and for adjustment of the fluxes measured under different operating conditions. The model also finds its value in understanding mechanical processes of Hg emissions from soils.     

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.     

Emissions and demonstration of an emission control technology for small two-stroke utility engines

Small utility engines represent an important contribution to the emissions inventory and have been subjected to increasingly stringent regulations in recent years. For this project, a Tanaka two-stroke engine was tested in its original condition and with a modified fuel/oil injection system. The modified fuel/oil injection system applied to the Tanaka two-stroke engine resulted in significant emissions reductions of approximately 52% for carbon monoxide (CO), 70% for total hydrocarbons (THC), 70% for particulate matter (PM), and 67% for the regulated THC + nitrogen oxides metric. This technology met the California Air Resources Board's 2000 model-year regulations for all pollutants, with the exception of slightly higher PM emissions. Two additional two-stroke engines were tested under a new condition and after at least 100 hr of use to examine the effects of deterioration on in-use, two-stroke engines. For one engine, CO and PM emissions more than tripled after 162 hr of operation in the field, with smaller increases also observed for THC (20%). For the second engine, significant repairs were required throughout the 100 operating hours, which counteracted the effects of the emissions deterioration and resulted in lower CO and THC emissions.     

Sulfur Gas Emissions From Stored Flue Gas Desulfurization Sludges

The emissions of volatile sulfur-containing compounds from 13 flue gas desulfurization (FGD) sludge field storage sites have been characterized. Sulfur gas emissions from the sludge surfaces were determined by measuring the sulfur gas enhancement of sulfur-free sweep air passing through a dynamic emission flux chamber placed over selected sampling sites. Samples of the enclosure sweep air were cryogenically concentrated in surface-deactivated Pyrex “U” traps. Analyses were conducted by wall-coated, open-tubular, capillary column, cyrogenic gas chromatography using a sulfur-selective, flame photometric detector. Several major variables associated with FGD sludge production processes were examined in relation to the measured range and variations in sulfur fluxes including: (a) the sulfur dioxide scrubbing reagent used, (b) sludge sulfite oxidation, (c) “unfixed” or “fixed” FGD sludge, and (d) ponding or landfill storage. The composition and concentration of the measured sulfur gas emissions were found to vary with the type of sludge, the effectiveness of rainwater drainage from the landfill surface, the method of impoundment, and the sulfate/sulfite ratio of the sludge. Hydrogen sulfide, carbonyl sulfide, dimethyl sulfide, carbon disulfide, and dimethyl disulfide were identified in varying concentrations and ratios in the FGD sludge emissions. In addition, up to four unidentified organo- sulfur compounds were found in the emissions from four FGD sludges. The sulfur flux from one FGD storage pond was analyzed by gas chromatography-single ion monitoring mass spectrometry. In addition to the four identified sulfur compounds, this flux contained large concentrations of benzene, toluene, and α-pinene. The measured, total sulfur emissions ranged from less than 0.01 to nearly 0.3 kg of sulfur per day for an equivalent 100 acre (40.5 hectare) sludge impoundment surface.     

Idle emissions from heavy-duty diesel and natural gas vehicles at high altitude

Idle emissions of total hydrocarbon (THC), CO, NOx, and particulate matter (PM) were measured from 24 heavy-duty diesel-fueled (12 trucks and 12 buses) and 4 heavy-duty compressed natural gas (CNG)-fueled vehicles. The volatile organic fraction (VOF) of PM and aldehyde emissions were also measured for many of the diesel vehicles. Experiments were conducted at 1609 m above sea level using a full exhaust flow dilution tunnel method identical to that used for heavy-duty engine Federal Test Procedure (FTP) testing. Diesel trucks averaged 0.170 g/min THC, 1.183 g/min CO, 1.416 g/min NOx, and 0.030 g/min PM. Diesel buses averaged 0.137 g/min THC, 1.326 g/min CO, 2.015 g/min NOx, and 0.048 g/min PM. Results are compared to idle emission factors from the MOBILE5 and PART5 inventory models. The models significantly (45-75%) overestimate emissions of THC and CO in comparison with results measured from the fleet of vehicles examined in this study. Measured NOx emissions were significantly higher (30-100%) than model predictions. For the pre-1999 (pre-consent decree) truck engines examined in this study, idle NOx emissions increased with model year with a linear fit (r2 = 0.6). PART5 nationwide fleet average emissions are within 1 order of magnitude of emissions for the group of vehicles tested in this study. Aldehyde emissions for bus idling averaged 6 mg/min. The VOF averaged 19% of total PM for buses and 49% for trucks. CNG vehicle idle emissions averaged 1.435 g/min for THC, 1.119 g/min for CO, 0.267 g/min for NOx, and 0.003 g/min for PM. The g/min PM emissions are only a small fraction of g/min PM emissions during vehicle driving. However, idle emissions of NOx, CO, and THC are significant in comparison with driving emissions.