Analysis of VOCs in Ambient Air Using Multisorbent Packings for VOC Accumulation and Sample Drying

Abstract

Solid multisorbent packings have been characterized for trapping and release efficiency of trace (10-20 ppbv in humidified zero air) volatile organic compounds (VOCs). The use of a two-stage trapping system reduces sample water content typically by more than 95.5% while maintaining a trapping and release efficiency of 100% for 49 VOCs, including eight water-soluble VOCs. Three combinations of primary tube and focusing tube are examined in detail by using an atomic emission detector to monitor hydrogen as an indication of residual water vapor, and to monitor either chlorine, bromine, or carbon for target VOCs. Linearity of response to individual VOCs, the presence of artifacts, and a laboratory monitoring application are also discussed.     

Mitigation of odor causing emissions—Bench-scale investigation

Emissions of malodors are considered to be the greatest threat to the compost industry. In work presented here, several simple odor mitigation alternatives were investigated for their effectiveness in preventing the release of common odorants, such as terpenes, ammonia, and reduced sulfur compounds. The mitigation methods studied included the use of a blanket of finished compost, compost amendment mixed within the feedstock, odor neutralizing agents (ONAs), and oxygen release compounds (ORCs). Among the mitigation alternatives investigated in this study, the use of finished compost as a blanket and finished compost as an amendment yielded the most conclusive and significant results. Both of these alternatives yielded a substantial emission reduction for terpenes, ammonia, and reduced sulfur compounds. The application of finished compost blanket resulted in up to 95% reduction of terpene and 25% reduction of ammonia emissions. Blending the feedstock with finished compost also provided substantial reduction of terpene emissions ranging from 73.6 to 93.1% at the 24% blending ratio, and up to 85% ammonia reduction a the 35% blending ratio. Use of finished compost also provided 75% lower reduced sulfur compound emissions at the 12% blending ratio. Misting and application of odor neutralizing agents did not result in any consistent reduction in emissions for any of the odorous compounds tested.

Implications The odor emissions from composting are often considered to be the biggest threat to composting facilities. Because most facilities cannot afford enclosures and contained composting vessels, there is a need to inexpensively and effectively control the odor emissions from composting facilities. The findings of this research can lead the way for efforts to control odor easily and cost effectively. In fact, the application of a compost blanket for odor control is already gaining acceptance by the composting industry.     

Microwave Plasma Conversion of Volatile Organic Compounds

Abstract

A microwave-induced, steam/Ar/O₂ , plasma “torch” was operated at atmospheric pressure to determine the feasibility of destroying volatile organic compounds (VOCs) of concern. The plasma process can be coupled with adsorbent technology by providing steam as the fluid carrier for desorbing the VOCs from an adsorbent. Hence, N₂ can be excluded by using a relatively inexpensive carrier gas, and thermal formation of oxides of nitrogen (NO_x ) is avoided in the plasma.

The objectives of the study were to evaluate the technical feasibility of destroying VOCs from gas streams by using a commercially available microwave plasma torch and to examine whether significant byproducts were produced. Trichloroethene (TCE) and toluene (TOL) were added as representative VOCs of interest to a flow that contained Ar as a carrier gas in addition to O₂ and steam.The O₂ was necessary to ensure that undesirable byproducts were not formed in the process. Microwave power applied at 500–600 W was found to be sufficient to achieve the destruction of the test compounds, down to the detection limits of the gas chromatograph that was used in the analysis. Samples of the postmicrowave gases were collected on sorbent tubes for the analysis of dioxins and other byproducts. No hazardous byproducts were detected when sufficient O₂ was added to the flow. The destruction efficiency at a fixed microwave power improved with the addition of steam to the flow that passed through the torch.     

Biofiltration of a Mixture of Volatile Organic Emissions

ABSTRACT

Air biofiltration is now under active consideration for the removal of the volatile organic compounds (VOCs) from polluted airstreams. To optimize this emerging environmental technology and to understand compound removal mechanisms, a biofilter packed with peat was developed to treat a complex mixture of VOCs: oxygenated, aromatic, and chlorinated compounds. The removal efficiency of this process was high. The maximum elimination capacity (ECmax) obtained was ~120 g VOCs/m³ peat/hr. Referring to each of the mixture's components, the ECmax showed the limits in terms of biodegradability of VOCs, especially for the halogenated compounds and xylene.

A stratification of biodegradation was observed in the reactor. The oxygenated compounds were metabolized before the aromatic and halogenated ones. Two assumptions are suggested. There was a competition between bacterial communities. Different communities colonized the peat-based biofilter, one specialized for the elimination of oxygenated compounds, the others more specialized for elimination of aromatic and halogenated compounds. There was also substrate competition. Bacterial communities were the same over the height of the column, but the more easily biodegradable compounds were used first for the microorganism metabolism when they were present in the gaseous effluent.     

Decomposition of volatile organic compounds using gliding arc discharge plasma

ABSTRACT

This work provides a systematic review on the decomposition of volatile organic pollutants in flue gas through the gliding arc (GA) plasma technology. To begin with, the basic mechanisms of GA plasma generation are summarized and three characteristic stages existed during the GA plasma generation process are revealed: gas breakdown stage, equilibrium stage, and non-equilibrium stage. Then, the types of GA reactors are comparatively illustrated. Possible destruction mechanisms of volatile organic compounds (VOCs) by GA plasma are discussed by taking chloroform, benzene, and methanol as examples. Furthermore, the effects of many operating parameters on the VOCs destruction efficiency are comprehensively analyzed. Simultaneously, the product distribution, energy cost, technical and economic during the whole decomposition process are considered. Finally, the advantages and disadvantages of GA plasma and its further development trend are concluded from the academic and industrial application of GA plasma in VOCs decomposition.

Implications: This paper comprehensively describes the principle, characteristics, research progress and engineering application examples of the degradation of volatile organics by gliding arc discharge plasma, so that readers can fully understand the degradation of volatile organics by gliding arc discharge plasma and provide theoretical basis for the industrial application of the degradation of volatile organics by gliding arc discharge plasma.     

Comments on the NAS Report: Odors From Stationary and Mobile Sources

ABSTRACT

Solid phase microextraction (SPME) presents many advantages over conventional analytical methods by combining sampling, preconcentration, and direct transfer of the analytes into a standard gas chromatograph (GC). Since its commercial introduction in the early 1990s, SPME has been successfully applied to the sampling and analysis of environmental samples. This paper presents an overview of the current methods for air sampling and analysis with SPME using both grab and time-weighted average (TWA) modes. Methods include total volatile organic compounds (TVOCs), formaldehyde, and several target volatile organic compounds (VOCs). Field sampling data obtained with these methods in indoor air were validated with conventional methods based on sorbent tubes. The advantages and challenges associated with SPME for air sampling are also discussed. SPME is accurate, fast, sensitive, versatile, and cost-efficient, and could serve as a powerful alternative to conventional methods used by the research, industrial, regulatory, and academic communities.     

Kinetics of Catalytic Oxidation of Benzene,n-Hexane,and Emission Gas from a Refinery Oil/Water Separator over a Chromium Oxide Catalyst

ABSTRACT

With the advances made in the past decade, catalytic incineration of volatile organic compounds (VOCs) has become the technology of choice in a wide range of pollution abatement strategies. In this study, a test was undertaken for the catalytic incineration, over a chromium oxide (Cr₂O₃) catalyst, of n-hexane, benzene, and an emission air/vapor mixture collected from an oil/water separator of a refinery. Reactions were carried out by controlling the feed stream to constant VOC concentrations and temperatures, in the ranges of 1300–14,700 mg/m³ and 240–400 ° C, respectively. The destruction efficiency for each of the three VOCs as a function of influent gas temperature and empty bed gas residence time was obtained.

Results indicate that n-hexane and the oil vapor with a composition of straight- and branch-chain aliphatic hydrocarbons exhibited similar catalytic incineration effects, while benzene required a higher incineration temperature or longer gas retention time to achieve comparable results.

In the range of the VOC concentrations studied, at a given gas residence time, increasing the operating temperature of the catalyst bed increased the destruction efficiency. However, the much higher temperatures required for a destruction efficiency of over 99% may be not cost-effective and are not suggested. A first-order kinetics with respect to VOC concentration and an Arrhenius temperature dependence of the kinetic constant appeared to be an adequate representation for the catalytic oxidation of these volatile organics. Activation energy and kinetic constants were estimated for each of the VOCs. Low-temperature destruction of the target volatile organics could be achieved by using the Cr₂O₃ catalyst.     

Development of Emission Factors for Polyamide Processing

ABSTRACT

Emission factors for selected volatile organic compounds (VOCs) and particulate material were developed during processing of commercial grades of polyamide 6, polyamide 66, and polyamide 66/6 resins. A small commercial-type extruder was used, and melt temperatures ranged from 475 to 550 °F. An emission factor was calculated for each substance measured and is reported as pounds released to the atmosphere per million pounds of polymer resin processed. Scaled to production volumes, these emission factors can be used by processors to estimate emission quantities from similar polyamide extrusion operations.     

VOC Recovery through Microwave Regeneration of Adsorbents: Comparative Economic Feasibility Studies

ABSTRACT

Microwave regeneration of adsorbents facilitates the recovery of volatile organic compounds (VOCs) by decoupling the bed heating from the stripping gas. This makes possible the creation of a highly-concentrated regeneration effluent from which the VOCs can be recovered by condensation at near-ambient temperatures. The economic feasibility of two novel microwave-regenerated adsorption systems was evaluated by systematically comparing the capital and operating costs of the proposed systems with 10 conventional VOC control technologies. The microwave systems were found to have similar capital and operating costs to conventional steam regeneration systems and, therefore, may present an attractive alternative for recovering water-miscible solvents. In general, the cost of the microwave subsystem is a relatively small component of the overall system costs, and the microwave power requirements are within the range of commercially available generators, even for large emission streams.     

Development of Emission Factors for Polycarbonate Processing

Abstract

Emission factors for selected volatile organic compounds (VOCs) and particulate emissions were developed while processing eight commercial grades of polycarbonate (PC) and one grade of a PC/acrylonitrile-butadiene-styrene (ABS) blend. A small commercial-type extruder was used, and the extrusion temperature was held constant at 304 °C. An emission factor was calculated for each substance measured and is reported as pounds released to the atmosphere/million pounds of polymer resin processed [ppm (wt/wt)]. Scaled to production volumes, these emission factors can be used by processors to estimate emission quantities from similar PC processing operations.     

The addition of modified attapulgite reduces the emission of nitrous oxide and ammonia from aerobically composted chicken manure

The acceleration of the composting process and the improvement of compost quality have been explored by evaluating the efficacy of various additives, inoculating with specific microorganisms and the application of various biosurfactants. The magnesium-aluminum silicate attapulgite is a low-cost potential composting additive, but its effects on aerobic composting are unknown. This study investigated the effects of attapulgite application on compost production and quality during the aerobic composting of chicken manure. Addition of attapulgite significantly increased the temperature (p < 0.05) while it reduced compost total organic carbon (TOC) and seed germination indices (GIs) throughout the process. Its addition enhanced nitrate concentrations, promoted organic matter degradation, increased seed germination indices, and accelerated the composting process. Interestingly, attapulgite addition did not increase the population of ammonia-oxidizing bacteria. These results suggest that attapulgite is a good additive for the composting industry.

Implications: We investigated the addition of two forms of attapulgite during aerobic composting of chicken manure to determine their effects under strict composting environmental parameter control. Our results provides primary evidence that attapulgite may have potential for application in the composting industry.

All treatments showed no increase within the first 15 days. However, emissions increased for all treatments within 15–45 days, reaching approximately 6300, 2000, and 4000 mg/m² from the control, artifactitious attapulgite, and raw attapulgite treatments, respectively.     

Measuring Concentrations of Volatile Organic Compounds in Vinyl Flooring

ABSTRACT

The initial solid-phase concentration of volatile organic compounds (VOCs) is a key parameter influencing the emission characteristics of many indoor materials. Solid-phase measurements are typically made using solvent extraction or thermal headspace analysis. The high temperatures and chemical solvents associated with these methods can modify the physical structure of polymeric materials and, consequently, affect mass transfer characteristics.

To measure solid-phase concentrations under conditions resembling those in which the material would be installed in an indoor environment, a new technique was developed for measuring VOC concentrations in vinyl flooring (VF) and similar materials. A 0.09-m² section of new VF was punched randomly to produce ~200 0.78-cm² disks. The disks were milled to a powder at -140 °C to simultaneously homogenize the material and reduce the diffusion path length without loss of VOCs. VOCs were extracted from the VF particles at room temperature by fluidized-bed desorption (FBD) and by direct thermal desorption (DTD) at elevated temperatures. The VOCs in the extraction gas from FBD and DTD were collected on sorbent tubes and analyzed by gas chromatog-raphy/mass spectrometry (GC/MS). Seven VOCs emitted by VF were quantified. Concentration measurements by FBD ranged from 5.1 |ig/g VF for n-hexadecane to 130 |Jg/g VF for phenol. Concentrations measured by DTD were higher than concentrations measured by FBD. Differences between FBD and DTD results may be explained using free-volume and dual-mobility sorption theory, but further research is necessary to more completely characterize the complex nature of a diffusant in a polymer matrix.     

The Role of Viscosity in Fabric Filtration

Abstract

An approach for measuring point-source emissions of volatile organic compounds (VOCs), acidic vapors, and other species is presented. The amount emitted is determined by directly measuring the actual weight gain of an adsorbent bed over a period of time, which is a cumulative rather than a grabbed sample. As a result, wide fluctuations of concentration and erratic flow behavior during sampling are accommodated with no apparent effect on the accuracy of the measured emission rate. The emission rate is determined by a mass balance including the mass change of the sorbent, as well as the influent and effluent humidities.

Validation tests used a known mass flow rate of vapor in a carrier gas, which was compared with the amount measured. The vapor was a single VOC, a mixture of VOCs, or a mixture of a VOC with water. Conditions studied were the compound or mixture of compounds, concentration, carrier gas, flow rate, and adsorbent. In some tests the VOC was admitted intermittently. The VOCs included n-hexane, acetone, toluene, vinyl acetate, and 1,1,1 trichloroethane. For 105 tests, the average absolute discrepancy of the delivered and measured emission rates was 6.8% and the standard deviation was 3.4%.     

Effect of Inoculating Flower Stalks and Vegetable Waste with Ligno-cellulolytic Microorganisms on the Composting Process

Abstract

A lab-scale composting experiment was carried out using vegetable and flower stalks waste to study the effectiveness of ligno-cellulolytic microorganisms (LCMs) obtained from the previous isolation on composting process, especially on enhancement of biodegradation rate of these organic materials. The addition of LCMs to compost showed promised to be a valuable asset by rendering timely benefits in efficiency, maturity, and quality of the composting. This was evidenced by a significant increase of temperature, O₂ consumption and CO₂ emission, and population density of LCMs in compost mass compared with that of biotic (addition of culture of horse feces) and abiotic (1% molasses amendment) treatments, as well as control trial. The phytotoxicity assay showed that the substrate became mature after 60 days’ composting. The LCMs inoculation enhanced the biodegradation of the composting materials as evidenced by an increasing screening ratio (1.2 cm sieve pore) of 34.5% in the treated trail, compared with that of control, which elucidated that big advantage of adding selected inoculants over other treatment, and screening ratio is a reasonable index to compare the quality of different compost. However, the inoculation seemed to have no significant effect on the moisture content, pH, and the final organic carbon of the composting materials.     

Evaluation of an In Situ,On-Line Purging System for the Cone Penetrometer

Abstract

Materials that will be used to construct an in situ, on-line purging system for the cone penetrometer were evaluated. Transfer efficiencies for volatile organic compounds (VOCs) through stainless steel, nickel, aluminum, and Teflon® tubings were determined using a gas-phase mixture of VOCs containing trichloromethane, tetrachloromethane, 1,1,1- trichloroethane, tetrachloroethene, hexane, benzene, toluene, and 1,2-dimethylbenzene. The water content of the gas stream had an insignificant effect on the quantitative transfer of VOCs through Teflon® tubing but was critical to efficiently transfer the compounds through metal tubing, particularly nickel. Transfer efficiencies for all eight analytes in moist gas streams through stainless steel were greater than 95%. Toluene, tetrachloroethene, and 1,2-dimethylbenzene were transferred with 93%, 81%, and 80% efficiency, respectively, when they were drawn through Teflon® PFA (perfluoroalkoxy) tubing. In general, the retention of the VOCs by Teflon® increases with decreasing aqueous solubility of the analyte. The efficiencies at which VOCs were purged from aqueous standards in Teflon® PFA, Type 304 stainless steel, and glass vessels were similar. Stainless steel was superior to nickel, aluminum, and the Teflon® polymers as a material for an in situ, on-line purging system for the cone penetrometer.     

Determination of Volatile Organic Compounds in the Atmosphere Using Two Complementary Analysis Techniques

ABSTRACT

During a preliminary field campaign of volatile organic compound (VOC) measurements carried out in an urban area, two complementary analysis techniques were applied to establish the technical and scientific bases for a strategy to monitor and control VOCs and photochemical oxidants in the Autonomous Community of the Basque Country. Integrated sampling was conducted using Tenax sorbent tubes and laboratory analysis by gas chromatography, and grab sampling and in situ analysis also were conducted using a portable gas chromatograph. With the first technique, monocyclic aromatic hydrocarbons appeared as the compounds with the higher mean concentrations. The second technique allowed the systematic analysis of eight chlorinated and aromatic hydrocarbons. Results of comparing both techniques, as well as the additional information obtained with the second technique, are included.     

Sampling and Analysis of Volatile Organic Compounds Evolved During Thermal Processing of Acrylonitrile Butadiene Styrene Composite Resins

Abstract

The evaluation of emissions of volatile organic compounds (VOCs) during processing of resins is of interest to resin manufacturers and resin processors. An accurate estimate of the VOCs emitted from resin processing has been difficult due to the wide variation in processing facilities. This study was designed to estimate the emissions in terms of mass of emitted VOC per mass of resin processed.

A collection and analysis method was developed and validated for the determination of VOCs present in the emissions of thermally processed acrylonitrile butadiene styrene (ABS) resins. Four composite resins were blended from automotive, general molding, pipe, and refrigeration grade ABS resins obtained from the manufacturers. Emission samples were collected in evacuated 6-L Summa canisters and then analyzed using gas chromatography/flame ionization detection/mass selective detection (GC/FID/MSD). Levels were determined for nine target analytes detected in canister samples, and for total VOCs detected by an inline GC/FID. The emissions evolved from the extrusion of each composite resin were expressed in terms of mass of VOCs per mass of processed resin. Styrene was the principal volatile emission from all the composite resins. VOCs analyzed from the pipe resin sample contained the highest level of styrene at 402 μg/g. An additional collection and detection method was used to determine the presence of aerosols in the emissions. This method involved collecting particulates on glass fiber filters, extracting them with solvents, and analyzing them using gas chromatography/mass spectrometry (GC/MS). No significant levels of any of the target analytes were detected on the filters.     

Emission Characteristics of Volatile Organic Compounds from Semiconductor Manufacturing

Abstract

A huge amount of volatile organic compounds (VOCs) is produced and emitted with waste gases from semiconductor manufacturing processes, such as cleaning, etching, and developing. VOC emissions from semiconductor factories located at Science-Based Industrial Park, Hsin-chu, Taiwan, were measured and characterized in this study. A total of nine typical semiconductor fabricators (fabs) were monitored over a 12-month period (October 2000-September 2001). A flame ionization analyzer was employed to measure the VOC emission rate continuously in a real-time fashion. The amount of chemical use was adopted from the data that were reported to the Environmental Protection Bureau in Hsin-chu County as per the regulation of the Taiwan Environmental Protection Administration. The VOC emission factor, defined as the emission rate (kg/month) divided by the amount of chemical use (L/month), was determined to be 0.038 ± 0.016 kg/L. A linear regression equation is proposed to fit the data with the correlation coefficient (R²) = 0.863. The emission profiles of VOCs, which were drawn using the gas chromatograph/mass spectrometer analysis method, show that isopropyl alcohol is the dominant compound in most of the fabs.     

A New Method for the Rapid Determination of Volatile Organic Compound Breakthrough Times for a Sorbent at Concentrations Relevant to Indoor Air Quality

Abstract

The use of sorbents has been proposed to remove volatile organic compounds (VOCs) present in ambient air at concentrations in the parts-per-billion (ppb) range, which is typical of indoor air quality applications. Sorbent materials, such as granular activated carbon and molecular sieves, are used to remove VOCs from gas streams in industrial applications, where VOC concentrations are typically in the parts-per-million range. A method for evaluating the VOC removal performance of sorbent materials using toluene concentrations in the ppb range is described. Breakthrough times for toluene at concentrations from 2 to 7500 ppb are presented for a hydrophobic molecular sieve at 25% relative humidity. By increasing the ratio of challenge gas flow rate to the mass of the sorbent bed and decreasing both the mass of sorbent in the bed and the sorbent particle size, this method reduces the required experimental times by a factor of up to several hundred compared with the proposed American Society of Heating, Refrigerating, and Air-Conditioning Engineers method, ASHRAE 145P, making sorbent performance evaluation for ppb-range VOC removal more convenient. The method can be applied to screen sorbent materials for application in the removal of VOCs from indoor air.     

Effect of Substrate Henry’s Constant on Biofilter Performance

Abstract

Butanol, ether, toluene, and hexane, which have Henry's constants ranging from 0.0005 to 53, were used to investigate the effects of substrate solubility or availability on the removal of volatile organic compounds (VOCs) in trickle-bed biofilters. Results from this study suggest that, although removal of a VOC generally increases with a decrease in its Henry's constant, an optimal Henry's constant range for biofiltration may exist. For the treatment of VOCs with high Henry's constant values, such as hexane and toluene, the transfer of VOCs between the vapor and liquid phases or between the vapor phase and the biofilm is a rate-determining step. However, oxygen (O₂) transfer may become a rate-limiting step in treating VOCs with low Henry's constants, such as butanol, especially at high organic loadings. The results demonstrated that in a gas-phase aerobic biofilter, nitrate can serve both as a growth-controlling nutrient and as an electron acceptor in a biofilm for the respiration of VOCs with low Henry's constants. Microbial communities within the biofilters were examined using denaturing gradient gel electrophoresis to provide a more complete picture of the effect of O₂ limitation and denitrification on biofilter performance.