Quality Assured Measurements of Animal Building Emissions: Gas Concentrations

Abstract

Comprehensive field studies were initiated in 2002 to measure emissions of ammonia (NH₃), hydrogen sulfide (H₂S), carbon dioxide (CO₂), methane (CH₄), nonmethane hydrocarbons (NMHC), particulate matter <10 µm in diameter, and total suspended particulate from swine and poultry production buildings in the United States.

This paper focuses on the quasicontinuous gas concentration measurement at multiple locations among paired barns in seven states. Documented principles, used in air pollution monitoring at industrial sources, were applied in developing quality assurance (QA) project plans for these studies. Air was sampled from multiple locations with each gas analyzed with one high quality commercial gas analyzer that was located in an environmentally controlled on-farm instrument shelter. A nominal 4 L/min gas sampling system was designed and constructed with Teflon wetted surfaces, bypass pumping, and sample line flow and pressure sensors. Three-way solenoids were used to automatically switch between multiple gas sampling lines with ≥10 min sampling intervals. Inside and outside gas sampling probes were between 10 and 115 m away from the analyzers. Analyzers used chemiluminescence, fluorescence, photoacoustic infrared, and photoionization detectors for NH₃, H₂S, CO₂, CH₄, and NMHC, respectively. Data were collected using personal computer-based data acquisition hardware and software. This paper discusses the methodology of gas concentration measurements and the unique challenges that livestock barns pose for achieving desired accuracy and precision, data representativeness, comparability and completeness, and instrument calibration and maintenance.     

Full-scale biofilter reduction efficiencies assessed using portable 24-hour sampling units

Portable 24-hr sampling units were used to collect air samples from eight biofilters on four animal feeding operations. The biofilters were located on a dairy, a swine nursery, and two swine finishing farms. Biofilter media characteristics (age, porosity, density, particle size, water absorption capacity, pressure drop) and ammonia (NH3), hydrogen sulfide (H2S), sulfur dioxide (SO2), methane (CH4), and nitrous oxide (N2O) reduction efficiencies of the biofilters were assessed. The deep bed biofilters at the dairy farm, which were in use for a few months, had the most porous media and lowest unit pressure drops. The average media porosity and density were 75% and 180 kg/m3, respectively. Reduction efficiencies of H2S and NH3 (biofilter 1: 64% NH3, 76% H2S; biofilter 2: 53% NH3, 85% H2S) were close to those reported for pilot-scale biofilters. No N2O production was measured at the dairy farm. The highest H2S, SO2, NH3, and CH4 reduction efficiencies were measured from a flat-bed biofilter at the swine nursery farm. However, the highest N2O generation (29.2%) was also measured from this biofilter. This flat-bed biofilter media was dense and had the lowest porosity. A garden sprinkler was used to add water to this biofilter, which may have filled media pores and caused N2O production under anaerobic conditions. Concentrations of H2S and NH3 were determined using the portable 24-hr sampling units and compared to ones measured with a semicontinuous gas sampling system at one farm. Flat-bed biofilters at the swine finishing farms also produced low amounts of N2O. The N2O production rate of the newer media (2 years old) with higher porosity was lower than that of older media (3 years old) (P = 0.042).     

The recovery of ammonia and hydrogen sulfide from ground-level area sources using dynamic isolation flux chambers: bench-scale studies

Controlled bench-scale laboratory experiments were conducted to evaluate the recovery of ammonia (NH3) and hydrogen sulfide (H2S) from dynamic isolation flux chambers. H2S (80-4000 ppb) and NH3 (5000-40,000 ppb) samples were diffused through the flux chamber to simulate ground level area source emissions while measuring the inlet and outlet flux chamber concentrations simultaneously. Results showed that the recovery of H2S during a 30-min sampling time was almost complete for concentrations >2000 ppb. At the lowest concentration of 80 ppb, 92.55% of the H2S could be recovered during the given sampling period. NH3 emissions exhibited similar behavior between concentrations of 5000-40,000 ppb. Within the 30-min sampling period, 92.62% of the 5000-ppb NH3 sample could be recovered. Complete recovery was achieved for concentrations >40,000 ppb. Predictive equations were developed for gas adsorption. From these equations, the maximum difference between chamber inlet and outlet concentrations of NH3 or H2S was predicted to be 7.5% at the lowest concentration used for either gas. In the calculation of emission factors for NH3 and H2S, no adsorption correction factor is recommended for concentrations >37,500 ppb and 2100 ppb for NH3 and H2S, respectively. The reported differences in outlet and inlet concentration above these ranges are outside the fullscale sensitivity of the gas sensing equipment. The use of 46-90 m of Teflon tubing with the flux chambers has apparently no effect on gas adsorption, because recovery was completed almost instantaneously at the beginning of the tests.     

Relationship between carbon dioxide/methane emissions and the water quality/sediment characteristics of Taiwan's main rivers

River and sediment have unique carbon dynamics and are important sources of the dominant greenhouse gases (GHG), carbon dioxide (CO2) and methane (CH4). To understand the relationship between CO2/CH4 emissions and water quality/sediment characteristics, we have investigated critical parameters in the river water. Eight parameters of water quality (dissolved oxygen, oxidation-reduction potential [ORP], chemical oxygen demand, biochemical oxygen demand [BOD5], suspended solid, nitrate [NO3-], NH4+, and bacteria) and four sediment characteristics (total organic carbon [TOC], total nitrogen [T-N], NO3-, and ammonium [NH4+]) were measured in two of the larger rivers in Taiwan, and relevant environmental conditions were recorded. The experimental results indicated that CO2 emissions from the river were mainly affected by BOD5 concentrations and the levels of bacteria. CH4 emissions, on the other hand, were greatly affected by the ORP in the river. The correlation between CO2 emissions and sediment characteristics was insignificant (R2 < 0.3). However, TOC and T-N in the sediment may lead to increases in CH4 emissions into the atmosphere. A deeper analysis of the relationship between the different parameters and GHG emissions by ANOVA and the multiple regression method revealed that CO2 emission (y) was significantly related to bacteria number (x1) and BOD concentration (X2). The regression equation takes the form y = 0.00032x1 + 3.18089x2 + 25.37304. Also, the regression relationship between CH4 emission (y) and ORP (x) in the river can be described as y = -0.825216x + 169.02257. The relationship between CH4 emission and sediment characteristics may be described as y = 5.073962x1(TOC) + 2.871245x2(T-N) - 12.3262. Extra sampling data were collected to examine the feasibility of the developed multiple regression equations. The experimental results suggest that the emissions of such GHGs as CO2 and CH4 from rivers can be predicted using the regression equations developed here. Moreover, the emissions may be reduced by manipulating the proper factors.     

Determining seasonal greenhouse gas emissions from ground-level area sources in a dairy operation in central Texas

Greenhouse gas (GHG) emissions from agricultural production operations are recognized as an important air quality issue. A new technique following the U.S. Environmental Protection Agency Method TO-14A was used to measure GHG emissions from ground-level area sources (GLAS) in a free-stall dairy operation in central Texas. The objective of this study was to quantify and report GHG emission rates (ERs) from the dairy during the summer and winter using this protocol. A weeklong sampling was performed during each season. A total of 75 and 66 chromatograms of air samples were acquired from six delineated GLAS (loafing pen, walkway, barn, silage pile, settling basin, and lagoon) of the same dairy during summer and winter, respectively. Three primary GHGs--methane (CH4), carbon dioxide (CO2), and nitrous oxide (N2O)--were identified from the dairy operation during the sampling periods. The estimated overall ERs for CH4, CO2, and N2O during the summer for this dairy were 274, 6005, and 7.96 g head(-1)day(-1), respectively. During the winter, the estimated overall CH4, CO2, and N2O ERs were 52, 7471, and 3.59 g head(-1)day(-1), respectively. The overall CH4 and N2O ERs during the summer were approximately 5.3 and 2.2 times higher than those in the winter for the free-stall dairy. These seasonal variations were likely due to fluctuations in ambient temperature, dairy manure loading rates, and manure microbial activity of GLAS. The annualized ERs for CH4, CO2, and N2O for this dairy were estimated to be 181, 6612, and 6.13 g head(-1)day(-1), respectively. Total GHG emissions calculated for this dairy with 500 cows were 2250 t of carbon dioxide equivalent (CO2e) per year.     

Biotreatment of H2S- and NH3-containing waste gases by co-immobilized cells biofilter

Gas mixture of H2S and NH3 in this study has been the focus in the research area concerning gases generated from the animal husbandry and the anaerobic wastewater lagoons used for their treatment. A specific microflora (mixture of Thiobacillus thioparus CH11 for H2S and Nitrosomonas europaea for NH3) was immobilized with Ca-alginate and packed inside a glass column to decompose H2S and NH3. The biofilter packed with co-immobilized cells was continuously supplied with H2S and NH3 gas mixtures of various ratios, and the removal efficiency, removal kinetics, and pressure drop in the biofilter was monitored. The results showed that the efficiency remained above 95% regardless of the ratios of H2S and NH3 used. The NH3 concentration has little effect on H2S removal efficiency, however, both high NH3 and H2S concentrations significantly suppress the NH3 removal. Through product analysis, we found that controlling the inlet ratio of the H2S/NH3 could prevent the biofilter from acidification, and, therefore, enhance the operational stability. Conclusions from bioaerosol analysis and pressure drop in the biofilter suggest that the immobilized cell technique creates less environmental impact and improves pure culture operational stability. The criteria for the biofilter operation to meet the current H2S and NH3 emission standards were also established. To reach Taiwan's current ambient air standards of H2S and NH3 (0.1 and 1 ppm, respectively), the maximum inlet concentrations should not exceed 58 ppm for H2S and 164 ppm for NH3, and the residence time be kept at 72 s.     

Reducing ammonia emissions from laying-hen houses through dietary manipulation

Feed additives can change the microbiological environment of the animal digestive track, nutrient composition of feces, and its gaseous emissions. This 2-yr field study involving commercial laying-hen houses in central Iowa was conducted to assess the effects of feeding diets containing EcoCal and corn-dried distillers grain with solubles (DDGS) on ammonia (NH3), hydrogen sulfide (H2S), and greenhouse gas (CO2, CH4, and N2O) emissions. Three high-rise layer houses (256,600 W-36 hens per house) received standard industry diet (Control), a diet containing 7% EcoCal (EcoCal) or a diet containing 10% DDGS (DDGS). Gaseous emissions were continuously monitored during the period of December 2007 to December 2009, covering the full production cycle. The 24-month test results revealed that mean NH3 emission rates were 0.58 +/- 0.05, 0.82 +/- 0.04, and 0.96 +/- 0.05 g/hen/day for the EcoCal, DDGS, and Control diet, respectively. Namely, compared to the Control diet, the EcoCal and DDGS diets reduced NH3 emission by an average of 39.2% and 14.3%, respectively. The concurrent H2S emission rates were 5.39 +/- 0.46, 1.91 +/- 0.13, and 1.79 +/- 0.16 mg/ hen/day for the EcoCal, DDGS, and Control diet, respectively. CO2 emission rates were similar for the three diets, 87.3 +/- 1.37, 87.4 +/- 1.26, and 89.6 +/- 1.6 g/hen/day for EcoCal, DDGS, and Control, respectively (P = 0.45). The DDGS and EcoCal houses tended to emit less CH4 than the Control house (0.16 and 0.12 vs. 0.20 g/hen/day) during the monitored summer season. The efficacy of NH3 emission reduction by the EcoCal diet decreased with increasing outside temperature, varying from 72.2% in February 2009 to -7.10% in September 2008. Manure of the EcoCal diet contained 68% higher ammonia nitrogen (NH3-N) and 4.7 times higher sulfur content than that of the Control diet. Manure pH values were 8.0, 8.9, and 9.3 for EcoCal, DDGS, and Control diets, respectively. This extensive field study verifies that dietary manipulation provides a viable means to reduce NH3 emissions from modern laying-hen houses.     

Abatement of ammonia and hydrogen sulfide emissions from a swine lagoon using a polymer biocover

The purpose of this research was to determine the efficiency of a polymer biocover for the abatement of H2S and NH3 emissions from an east-central Missouri swine lagoon with a total surface area of 7800 m2. The flux rate of NH3, H2S, and CH4 was monitored continuously from two adjacent, circular (d = 66 m) control and treatment plots using a nonintrusive, micrometeorological method during three independent sampling periods that ranged between 52 and 149 hr. Abatement rates were observed to undergo a temporal acclimation event in which NH3 abatement efficiency improved from 17 to 54% (p = < 0.0001 to 0.0005) and H2S abatement efficiency improved from 23 to 58% (p < 0.0001) over a 3-month period. The increase in abatement efficiency for NH3 and H2S over the sampling period was correlated with the development of a stable anaerobic floc layer on the bottom surface of the biocover that reduced mass transfer of NH3 and H2S across the surface. Analysis of methanogenesis activity showed that the biocover enhanced the rate of anaerobic digestion by 25% when compared with the control. The biocover-enhanced anaerobic digestion process was shown to represent an effective mechanism to counteract the accumulation of methanogenic substrates in the biocovered lagoon.     

Simulation of stack plume opacity

The visual impact of primary particles emitted from stacks is regulated according to stack opacity criteria. In-stack monitoring of the flue gas opacity allows plant operators to ensure that the plant meets U.S. Environmental Protection Agency opacity regulations. However, the emission of condensable gases such as SO3 (that hydrolyzes to H2SO4), HCl, and NH3, which may lead to particle formation after their release from the stack, makes the prediction of stack plume opacity more difficult. We present here a computer simulation model that calculates the opacity due to both primary particles emitted from the stack and secondary particles formed in the atmosphere after the release of condensable gases from the stack. A comprehensive treatment of the plume rise due to buoyancy and momentum is used to calculate the location at which the condensed water plume has evaporated (i.e., where opacity regulations apply). Conversion of H2SO4 to particulate sulfate occurs through nucleation and condensation on primary particles. A thermodynamic aerosol equilibrium model is used to calculate the amount of ammonium, chloride, and water present in the particulate phase with the condensed sulfate. The model calculates the stack plume opacity due to both primary and secondary particles. Examples of model simulations are presented for three scenarios that differ by the emission control equipment installed at the power plant: (1) electrostatic precipitators (ESP), (2) ESP and flue gas desulfurization, and (3) ESP and selective catalytic reduction. The calculated opacity is most sensitive to the primary particulate emissions. For the conditions considered here, SO3 emissions showed only a small effect, except if one assumes that most H2SO4 condenses on primary particles. Condensation of NH4Cl occurs only at high NH3 emission rates (about 25 ppm stack concentration).     

Air emissions of ammonia and methane from livestock operations: valuation and policy options

The animal husbandry industry is a major emitter of ammonia (NH3), which is a precursor of fine particulate matter (PM2.5)--arguably, the number-one environment-related public health threat facing the nation. The industry is also a major emitter of methane (CH4), which is an important greenhouse gas (GHG). We present an integrated process model of the engineering economics of technologies to reduce NH3 and CH4 emissions at dairy operations in California. Three policy options are explored: PM offset credits for NH3 control, GHG offset credits for CH4 control, and expanded net metering policies to provide revenue for the sale of electricity generated from captured methane (CH4) gas. Individually these policies vary substantially in the economic incentives they provide for farm operators to reduce emissions. We report on initial steps to fully develop the integrated process model that will provide guidance for policy-makers.     

Non-controlled biogenic emissions to the atmosphere from Lazareto landfill, Tenerife, Canary Islands

GOAL, SCOPE AND BACKGROUND: [corrected] Historically, landfills have been the simplest form of eliminating urban solid waste with the minimum cost. They have been the most usual method for discarding solid waste. However, landfills are considered authentic biochemical reactors that introduce large amounts of contaminants into the environment in the form of gas and leachates. The dynamics of generation and the movement of gas in landfills depend on the input and output parameters, as well as on the structure of the landfill and the kind of waste. The input parameters include water introduced through natural or artificial processes, the characteristics of the urban solid waste, and the input of atmospheric air. The main output parameters for these biochemical reactors include the gases and the leachates that are potentially pollutants for the environment. Control systems are designed and installed to minimize the impact on the environment. However, these systems are not perfect and a significant amount of landfill gas could be released to the atmosphere through the surface in a diffuse form, also known as Non-controlled emission. In this paper, the results of the Non-controlled biogenic gas emissions from the Lazareto landfill in Tenerife, Canary Islands, are presented. The purpose of this study was to evaluate the concentration of CH4 and CO2 in the soil gas of the landfill cover, the CH4 and CO2 efflux from the surface of the landfill and, finally, to compare these parameters with other similar landfills. In this way, a better understanding of the process that controls biogenic gas emissions in landfills is expected. METHODS: A Non-controlled biogenic gas emission survey of 281 sampling sites was carried out during February and March, 2002. The sampling sites were selected in order to obtain a well-distributed sampling grid. Surface landfill CO2 efflux measurements were carried out at each sampling site on the surface landfill together with soil gas collection and ground temperatures at a depth of 30-40 cm.The CH4 efflux was computed from CO2 efflux and from the ratio CH4/CO2 in the soil gas. Soil gas samples were collected at a depth of 30-40 cm using a metallic probe and 20 cc hypodermic syringes, and later stored in evacuated 10 cc vacutainers for laboratory analysis of bulk composition. The gas sample was introduced in a vacutainer filled with deionized water and displacing the water until the vacutainer was filled with the gas sample in order to avoid air contamination from entering. The surface landfill temperature of the landfill was measured at a depth of 40 cm using a digital thermometer type OMEGA 871A. Landfill gases, CO2 and CH4, were analyzed within 24 hours using a double channel VARIAN micro-GC QUAD CP-2002P, with a 10 meter PORAPLOT-Q column, a TCD detector, and He as a carrier gas. The analysis temperature was 40 degrees C and the injection time was 10 msec. Surface landfill CO2 efflux measurements were performed using a portable NDIR spectrophotometer Licor-800 according to the accumulation chamber method (Chiodini et al. 1996). The data treatment, aimed at drawing the flux map and computing the total gas output, was based on the application of stochastic simulation algorithms provided by the GSLIB program (Deutsch and Journel 1998). RESULTS: Diffuse CH4 and CO2 efflux values range from negligible values up to 7,148 and 30,573 g m(-2) d(-1), respectively. The spatial distribution of the concentration and efflux of CO2, CH4 and soil temperature, show three areas of maximum activity in the landfill, suggesting a non-uniform pattern of diffuse degassing. This correlation between high emissions and concentration of CO2, CH4 and soil temperatures suggests that the areas of higher microbial activity and exothermic reactions are releasing CO2 and CH4 to the atmosphere from the landfill. Taking into consideration the spatial distribution of the CO2 and CH4 efflux values as well as the extension of the landfill, the Non-controlled emission of CO2 and CH4 to the atmosphere by the Lazareto's landfill are of 167 +/- 13.3 and 16 +/- 2.5 t d(-1), respectively. DISCUSSION: The patterns of gas flow within the landfill seem to be affected by boundary materials at the sides. The basalt layers have a low permeability and the gas flow in these areas is extensive. In this area, where a basalt layer does not exist, the flow gas diffuses toward the sea and the flux emissions at the landfill surface are lower. This behavior reflects the possible dissolution of gases into water and the deflection of gases towards the surface at the basalt boundary. The proximity to the sea, the installation of a palm tree garden and, as a result, the contribution of water coming from the watering of this garden has reactivated the system. The introduction of sea water into the landfill and the type of boundary could be defining the superficial gas discharges. CONCLUSIONS: Results from this study indicate that the spatial distribution of Non-controlled emission of CO2 and CH4 at the Lazareto's landfill shows a non-uniform pattern of diffuse degassing. The northeast, central and northwest areas of the Lazareto's landfill are the three areas of high emissions and concentration of CO2 and CH4, and high temperatures. The correlation between high emissions and the concentration of CO2, CH4, and the high temperatures suggest that the areas of higher microbial activity and exothermic reactions are releasing more CO2 and CH4 to the atmosphere from the landfill. A high concentration of CO2 is probably due to the presence of methanotrophic bacteria in the soil atmosphere of the landfill. Patterns of gas flow within the landfill seem to be affected by boundary materials (basalt layers) of low permeability, and side boundaries of the flux emissions at the surface are higher. At the sides of seawater and sediment boundaries, flux emissions at the landfill surface are lower. This behavior reflects a possible dissolution of gases into the water and the deflection of gases towards the surface at the basalt boundary. With this study, we can compare the data obtained in this landfill with other landfills and observe the different levels of emission. The proximity to the sea and the installation of the palm tree garden palms and, as a result, the contribution of water coming from the watering of this garden has reactivated the system. Many landfills worldwide located in similar settings could experience similar gas production processes. RECOMMENDATIONS AND PERSPECTIVES: The need for investigating and monitoring sea water and sediment quality in these landfills is advisable. Concentrations and fluxes of contaminants and their impact in the area should be assessed. With this study we can compare the data obtained in these landfills with other landfills and observe the different levels of emission.     

Remote sensing-based estimates of annual and seasonal emissions from crop residue burning in the contiguous United States

Crop residue burning is an extensive agricultural practice in the contiguous United States (CONUS). This analysis presents the results of a remote sensing-based study of crop residue burning emissions in the CONUS for the time period 2003-2007 for the atmospheric species of carbon dioxide (CO2), methane (CH4), carbon monoxide (CO), nitrogen dioxide (NO2, sulfur dioxide (SO2), PM2.5 (particulate matter [PM] < or = 2.5 microm in aerodynamic diameter), and PM10 (PM < or = 10 microm in aerodynamic diameter). Cropland burned area and associated crop types were derived from Moderate Resolution Imaging Spectroradiometer (MODIS) products. Emission factors, fuel load, and combustion completeness estimates were derived from the scientific literature, governmental reports, and expert knowledge. Emissions were calculated using the bottom-up approach in which emissions are the product of burned area, fuel load, and combustion completeness for each specific crop type. On average, annual crop residue burning in the CONUS emitted 6.1 Tg of CO2, 8.9 Gg of CH4, 232.4 Gg of CO, 10.6 Gg of NO2, 4.4 Gg of SO2, 20.9 Gg of PM2.5, and 28.5 Gg of PM10. These emissions remained fairly consistent, with an average interannual variability of crop residue burning emissions of +/- 10%. The states with the highest emissions were Arkansas, California, Florida, Idaho, Texas, and Washington. Most emissions were clustered in the southeastern United States, the Great Plains, and the Pacific Northwest. Air quality and carbon emissions were concentrated in the spring, summer, and fall, with an exception because of winter harvesting of sugarcane in Florida, Louisiana, and Texas. Sugarcane, wheat, and rice residues accounted for approximately 70% of all crop residue burning and associated emissions. Estimates of CO and CH4 from agricultural waste burning by the U.S. Environmental Protection Agency were 73 and 78% higher than the CO and CH4 emission estimates from this analysis, respectively. This analysis also showed that crop residue burning emissions are a minor source of CH4 emissions (< 1%) compared with the CH4 emissions from other agricultural sources, specifically enteric fermentation, manure management, and rice cultivation.     

Quality-assured measurements of animal building emissions: particulate matter concentrations

Federally funded, multistate field studies were initiated in 2002 to measure emissions of particulate matter (PM) < 10 microm (PM10) and total suspended particulate (TSP), ammonia, hydrogen sulfide, carbon dioxide, methane, nonmethane hydrocarbons, and odor from swine and poultry production buildings in the United States. This paper describes the use of a continuous PM analyzer based on the tapered element oscillating microbalance (TEOM). In these studies, the TEOM was used to measure PM emissions at identical locations in paired barns. Measuring PM concentrations in swine and poultry barns, compared with measuring PM in ambient air, required more frequent maintenance of the TEOM. External screens were used to prevent rapid plugging of the insect screen in the PM10 preseparator inlet. Minute means of mass concentrations exhibited a sinusoidal pattern that followed the variation of relative humidity, indicating that mass concentration measurements were affected by water vapor condensation onto and evaporation of moisture from the TEOM filter. Filter loading increased the humidity effect, most likely because of increased water vapor adsorption capacity of added PM. In a single layer barn study, collocated TEOMs, equipped with TSP and PM10 inlets, corresponded well when placed near the inlets of exhaust fans in a layer barn. Initial data showed that average daily mean concentrations of TSP, PM10, and PM2.5 concentrations at a layer barn were 1440 +/- 182 microg/m3 (n = 2), 553 +/- 79 microg/m3 (n = 4), and 33 +/- 75 microg/m3 (n = 1), respectively. The daily mean TSP concentration (n = 1) of a swine barn sprinkled with soybean oil was 67% lower than an untreated swine barn, which had a daily mean TSP concentration of 1143 +/- 619 microg/m3. The daily mean ambient TSP concentration (n = 1) near the swine barns was 25 +/- 8 microg/m3. Concentrations of PM inside the swine barns were correlated to pig activity.     

Application and field validation of a continuous nonmethane organic carbon analyzer.

Nonmethane organic carbon (NMOC) is a measure of total organic carbon except for that from CH4. We recently reported the development of online instrumentation for continuous NMOC monitoring. This instrument, referred to as C-NMOC, uses a microsorbent trap in combination with a gas-sampling valve as the sampling interface. A conventional oxidation/reduction NMOC detector is used for quantitation. In addition to being an online concentrator and an injector, the microtrap serves as a separator that isolates NMOC from H2O, CO, CO2, CH4, and other background gases. Therefore, the C-NMOC is able to handle high concentrations of background gases commonly found in stack emissions and has detection limits in the ppb levels. This paper reports the results of field validation and testing of a C-NMOC analyzer at a coatings facility in the eastern United States. The instrument was able to monitor the process transients in real time, based on which corrective actions could be taken. It demonstrated good accuracy, high precision, and long-term stability.     

Production of hydrogen-rich gas from methane by thermal plasma reform

This study investigated the reforming characteristics and optimum operating condition of the high-temperature plasma torch (so called plasmatron) for hydrogen-rich gas (syngas) production. At the optimum condition, the composition of produced syngas was 45.4% hydrogen (H2), 6.9% carbon monoxide (CO), 1.5% carbon dioxide (CO2), and 1.1% acetylene (C2H2). The H2/CO ratio was 6.6, hydrogen yield was 78.8%, and the energy conversion rate was 63.6%. To obtain the optimum operating condition, parametric studies were carried out examining the effects of O2/CH4 ratio, steam/CH4 ratio, and Ni catalyst addition in reactor. When the steam/CH4 ratio was 1.23, the production of hydrogen was maximized and the methane conversion rate was 99.7%. The syngas composition was determined to be 50.4% H2, 5.7% CO, 13.8% CO2, and 1.1% C2H2. The H2/CO ratio was 9.7, hydrogen yield was 93.7%, and the energy conversion rate was 78.8%. Hydrogen production with catalyst was effective, compared with no catalyst.     

Quality assured measurements of animal building emissions: odor concentrations

Standard protocols for sampling and measuring odor emissions from livestock buildings are needed to guide scientists, consultants, regulators, and policy-makers. A federally funded, multistate project has conducted field studies in six states to measure emissions of odor, coarse particulate matter (PM(10)), total suspended particulates, hydrogen sulfide, ammonia, and carbon dioxide from swine and poultry production buildings. The focus of this paper is on the intermittent measurement of odor concentrations at nearly identical pairs of buildings in each state and on protocols to minimize variations in these measurements. Air was collected from pig and poultry barns in small (10 L) Tedlar bags through a gas sampling system located in an instrument trailer housing gas and dust analyzers. The samples were analyzed within 30 hr by a dynamic dilution forced-choice olfactometer (a dilution apparatus). The olfactometers (AC'SCENT International Olfactometer, St. Croix Sensory, Inc.) used by all participating laboratories meet the olfactometry standards (American Society for Testing and Materials and European Committee for Standardization [CEN]) in the United States and Europe. Trained panelists (four to eight) at each laboratory measured odor concentrations (dilution to thresholds [DT]) from the bag samples. Odor emissions were calculated by multiplying odor concentration differences between inlet and outlet air by standardized (20 degrees C and 1 atm) building airflow rates.     

Performance of a semi-industrial scale gasification process for the destruction of polychlorinated biphenyls

A semi-industrial scale test was conducted to thermally treat mixtures of spent oil and askarels at a concentration of 50,000 ppm and 100,000 ppm of polychlorinated biphenyls (PCBs) under a reductive atmosphere. In average, the dry-basis composition of the synthesis gas (syngas) obtained from the gasification process was: hydrogen 46%, CO 34%, CO2 18%, and CH4 0.8%. PCBs, polychlorinated dibenzo-p-dioxins, and polychlorinated dibenzofurans (PCDDs/PCDFs) in the gas stream were analyzed by high-resolution gas chromatography (GC)-mass spectrometry. The coplanar PCBs congeners 77, 105, 118, 156/ 157, and 167 were detected in the syngas at concentrations < 2 x 10(-7) mg/m3 (at 298 K, 1 atm, dry basis, 7% O2). The chlorine released in the destruction of the PCBs was transformed to hydrogen chloride and separated from the gas by an alkaline wet scrubber. The concentration of PCBs in the water leaving the scrubber was below the detection limit of 0.002 mg/L, whereas the destruction and removal efficiency was > 99.9999% for both tests conducted. The concentration of PCDDs/PCDFs in the syngas were 8.1 x 10(-6) ng-toxic equivalent (TEQ)/m3 and 7.1 x 10(-6) ng-TEQ/m3 (at 298 K, 1 atm, dry basis, 7% O2) for the tests at 50,000 ppm and 100,000 ppm PCBs, respectively. The only PCDD/F congener detected in the gas was the octachloro-dibenzo-p-dioxin, which has a toxic equivalent factor of 0.001. The results obtained for other pollutants (e.g., metals and particulate matter) meet the maximum allowed emission limits according to Mexican, U.S., and European regulations for the thermal treatment of hazardous waste (excluding CO, which is a major component of the syngas, and total hydrocarbons, which mainly represent the presence of CH4).     

Characterizing ammonia emissions from swine farms in eastern North Carolina: part 1--conventional lagoon and spray technology for waste treatment

Ammonia (NH3) fluxes from waste treatment lagoons and barns at two conventional swine farms in eastern North Carolina were measured. The waste treatment lagoon data were analyzed to elucidate the temporal (seasonal and diurnal) variability and to derive regression relationships between NH3 flux and lagoon temperature, pH and ammonium content of the lagoon, and the most relevant meteorological parameters. NH3 fluxes were measured at various sampling locations on the lagoons by a flowthrough dynamic chamber system interfaced to an environmentally controlled mobile laboratory. Two sets of open-path Fourier transform infrared (FTIR) spectrometers were also used to measure NH3 concentrations for estimating NH3 emissions from the animal housing units (barns) at the lagoon and spray technology (LST) sites. Two different types of ventilation systems were used at the two farms. Moore farm used fan ventilation, and Stokes farm used natural ventilation. The early fall and winter season intensive measurement campaigns were conducted during September 9 to October 11, 2002 (lagoon temperature ranged from 21.2 to 33.6 degrees C) and January 6 to February 2, 2003 (lagoon temperature ranged from 1.7 to 12 degrees C), respectively. Significant differences in seasonal NH3 fluxes from the waste treatment lagoons were found at both farms. Typical diurnal variation of NH3 flux with its maximum value in the afternoon was observed during both experimental periods. Exponentially increasing flux with increasing surface lagoon temperature was observed, and a linear regression relationship between logarithm of NH3 flux and lagoon surface temperature (T1) was obtained. Correlations between lagoon NH3 flux and chemical parameters, such as pH, total Kjeldahl nitrogen (TKN), and total ammoniacal nitrogen (TAN) were found to be statistically insignificant or weak. In addition to lagoon surface temperature, the difference (D) between air temperature and the lagoon surface temperature was also found to influence the NH3 flux, especially when D > 0 (i.e., air hotter than lagoon). This hot-air effect is included in the statistical-observational model obtained in this study, which was used further in the companion study (Part II), to compare the emissions from potential environmental superior technologies to evaluate the effectiveness of each technology.     

Dry deposition, ionic species measured and source interpretation during seasonal cycle at offshore areas near Taiwan Strait

The characterization for water-soluble species of total suspended particulate (TSP), dry deposition flux, and dry deposition velocity (V(d)) were studied at Taichung Harbor (TH) and Wuchi traffic sampling sites at offshore sampling site near Taiwan Strait of central Taiwan during March 2004-January 2005. The average concentrations of TSP and dry deposition flux at the TH sampling site were higher than at the WT sampling site during the sampling period. The samples collected were analyzed by a ion chromatography (DIONEX-100) for the ionic species (Cl(-), SO(4)(2-), NO(3)(-), NH(4)(+), Na(+), Ca(2+), and Mg(2+)) analysis. The dominant ionic species for TSP are SO(4)(2-), NO(3)(-), and NH(4)(+) of the total mass of the inorganic ions at both sampling sites. In addition, the results indicated that the NH(4)(+), NO(3)(-) and SO(4)(2-) showed higher concentrations in winter and lower in summer for both TH and Wuchi sampling sites. Statistical methods such as correlation coefficient and principal component analysis were also used to identify the possible pollutant source.     

NO removal by reducing agents and additives in the selective non-catalytic reduction (SNCR) process

The effect of the additives on the selective non-catalytic reduction (SNCR) reaction has been determined in a three-stage laboratory scale reactor. The optimum reaction temperature is lowered and the reaction temperature window is widened with increasing concentrations of the gas additives (CO, CH4). The optimum reaction temperature is lowered and the maximum NO removal efficiency decreases with increasing the concentration of alcohol additives (CH3OH, C2H5OH). The addition of phenol lowers the optimum reaction temperature about 100-150 degrees C similar to that of the toluene addition. The volatile organic compounds (VOCs: C6H5OH, C7H8) can be utilized in the SNCR process to enhance NO reduction and removed at the same time. A previously proposed simple kinetic model can successfully apply the NO reduction by NH3 and the present additives.