Performance Audit Results for Volatile POHC Measurements

Audit materials containing principal organic hazardous constituents (POHCs) have been developed by EPA for use by federal, state, and local agencies or their contractors to assess the accuracy of measurement methods used during RCRA trial burn tests. Audit materials are currently available for 27gaseous organics in five, six, seven, and nine-component mixtures at parts-per-billion levels (7 to 10,000 ppb) in compressed gas cylinders in a balance gas of nitrogen. The criteria used for the selection of 27 gaseous organic compounds is described.

Stability studies indicate that all of the organics tested (with the exception of ethylene oxide and propylene oxide below 10 ppb levels) are stable enough to be used as reliable audit materials.

Subsequent to completion of the stability studies, 89 performance audits have been conducted with the audit materials to assess the accuracy of the Volatile Organic Sampling Train (VOST) and bag measurement methods during or prior to RCRA trial burn tests. A summary of the audits conducted for each POHC and the measurement system audited is shown in this paper. The audit results obtained with audit gases during RCRA trial burn tests are generally within ±50 percent of the audit concentrations.     

Summary of POHC Audit Results Using VOST and Bag Methods During RCRA Trial Burns

Audit materials containing Principal Organic Hazardous Constituents (POHCs) have been developed by EPA for use by Federal, State, and Local agencies or their contractors to assess the accuracy of measurement methods used during RCRA trial burn tests. Audit materials are currently available for 27 gaseous organics in five-, six-, seven-, and nine-component mixtures at ppb levels (7 to 10,000 ppb) in compressed gas cylinders in a balance gas of nitrogen. The logic used in selecting 27 gaseous organic compounds as audit materials and how these audit materials are successfully used in performance audits is described. Stability studies indicate that all of the organics tested (with the exception of ethylene oxide and propylene oxide below 10 ppb levels) are stable enough to be used as reliable audit materials. As of January 1990, 215 performance audits have been conducted to assess the accuracy of Volatile Organic Sampling Train (VOST) and bag measurement methods during or prior to RCRA trial burn tests. A summary of the audits conducted for each POHC, the measurement system audited, and the frequency of audits is described. The audit results obtained with audit gases are generally within ±50% of the audit concentrations.     

Evaluation of Selected Gaseous Halocarbons for Use in source Test Performance Audits

A repository of 38 gaseous organic compounds in compressed gas cylinders has been established by EPA. This repository was established to provide standards for source test performance audits, that is, quantitative quality assurance tests. Among these compounds are ten halogenated organic species, which are the focus of this paper.

Stability studies of all ten compounds have been performed to determine the feasibility of using them as performance audit standards. Results indicate that all of the halocarbons tested are adequately stable to be used as reliable audit standards.

Subsequent to completion of stability studies, four of the ten halocarbons were used in source test performance audits. Results are available at this time for two of the four compounds; the results show agreement within 10% of the concentrations previously established by Research Triangle Institute.     

A&WMA Honors Five Individuate and One Company In 1989 Awards Program

A repository of 39 and 34 gaseous organic compounds in compressed gas cylinders at PPM (5 to 700) and PPB levels (1 to 10,000) respectively has been established by EPA for use in performance audits. In this program, to ensure that the concentration of each gas standard has not changed, each standard is periodically analyzed for stability. The gas mixtures were initially analyzed once or twice by the manufacturer before shipment to Research Triangle Institute (RTI). The gas mixtures were then analyzed at RTI upon receipt from the gas manufacturer and then reanalyzed at 2, 6 and 12 months, and annually thereafter, to determine any change in concentration.

An examination of the stability data shows that concentrations for all the organics tested usually varied by less than 10 percent over a period of several years. Ethylene oxide and propylene oxide and trans 1, 4-dichloro-2-butene below the 10 ppb level have been found to be unstable. Six other compounds at the PPM level (aniline, cyclohexanone, p-dichlorobenzene, ethylamine 1, 2-dibromoethylene, and formaldehyde) have been found to be unstable in compressed gas cylinders.     

National crop loss assessment network: quality assurance program

A quality assurance program was incorporated into the National Crop Loss Assessment Network (NCLAN) program, designed to assess the economic impacts of gaseous air pollutants on major agricultural crops in the United States. To satisfy US EPA requirements that all environmental data collected be of known and documented quality, adequate for the intended use, the quality assurance program developed standardized research and monitoring protocols among sites, and included a range of audit and review procedures. The goal of the quality assurance program was to quantitatively describe the overall quality of data collected in terms of precision, accuracy, completeness, representativeness, and comparability. From this program, it can be concluded that (1) project data quality objectives were valuable for determining the acceptability of data from diverse sites, (2) standardized protocols ensured data comparability among research sites, (3) independent on-site audits served to evaluate protocol adherence, and (4) precision and accuracy measurements provided a way to assess data quality, determine data acceptability, and indicate the need for instrument adjustment or repair.     

Determination of Multiple Atmospheric Diffusion Coefficients Using the Carbon Hollow Tube Gas Chromatography Method

Gaseous organic species were collected by carbon hollow tube pairs. Diffusion coefficients (D_a) of anhydrous and hydrated organic species were then determined by measuring the ratio of each component that adsorbed in the collection tubes. In controlled experiments, the precision and accuracy of D_a determinations were 12 percent and 9.1 percent respectively. Ternary mixtures of airborne compounds were separated and quantified using gas chromatography. Observed D_as for each component of these mixtures were similar to those obtained for individual components. This method was applied to volatile organic species in marine air, soil air, and cigarette effluents.     

Bioremediation of trace organic compounds found in precious metals refineries' wastewaters: a review of potential options

Platinum group metal (PGM) refining processes produce large quantities of wastewater, which is contaminated with the compounds that make up the solvents/extractants mixtures used in the process. These compounds often include solvesso, beta-hydroxyxime, amines, amides and methyl isobutyl ketone. A process to clean up PGM refinery wastewaters so that they could be re-used in the refining process would greatly contribute to continual water storage problems and to cost reduction for the industry. Based on the concept that organic compounds that are produced biologically can be destroyed biologically, the use of biological processes for the treatment of organic compounds in other types of waste stream has been favoured in recent years, owing to their low cost and environmental acceptability. This review examines the available biotechnologies and their effectiveness for treating compounds likely to be contained in precious metal extraction process wastewaters. The processes examined include: biofilters, fluidized bed reactors, trickle-bed bioreactors, bioscrubbers, two-phase partitioning bioreactors, membrane bioreactors and activated sludge. Although all processes examined showed adequate to excellent removal of organic compounds from various gaseous and fewer liquid waste streams, there was a variation in their effectiveness. Variations in performance of laboratory-scale biological processes are probably due to the inherent change in the microbial population composition due to selection pressure, environmental conditions and the time allowed for adaptation to the organic compounds. However, if these factors are disregarded, it can be established that activated sludge and membrane bioreactors are the most promising processes for use in the treatment of PGM refinery wastewaters.     

Pilot-Scale Evaluation of an Incinerability Ranking System for Hazardous Organic Compounds

The U.S. Environmental Protection Agency’s (EPA) hazardous waste incinerator performance standards specify a minimum destruction and removal efficiency (DRE) for principal organic hazardous constituents (POHCs) designated in the incinerator waste feed. In the past, selection of appropriate POHCs for incinerator trial burns has been based largely on their heats of combustion. Attempting to improve upon this approach, the University of Dayton Research Institute (UDRI), under contract to the EPA Risk Reduction Engineering Laboratory, has developed a thermal stability-based ranking of compound "incinerability". The subject study was conducted to evaluate the laboratory-developed ranking system in a pilot-scale incinerator.

Mixtures of POHCs, spanning the ranking scale from most- to least-difficult to destroy (Class 1 to Class 7, respectively), were prepared and combined with a clay-based sorbent matrix. These mixtures were then fed into the rotary kiln incineration system at the U.S. EPA Incineration Research Facility (IRF). In a series of five tests, the following conditions were evaluated: baseline/ typical operation; thermal failure (quenching); mixing failure (overcharging); matrix failure (low feed H/CI ratio); and a worst-case combination of the three failure modes.

Under baseline conditions, mixing failure, and matrix failure, kiln-exit DREs for each compound were comparable from test to test. Operating conditions in these 3 modes appeared to be sufficient to effect considerable destruction (greater than 99.99 percent DRE) of all compounds. As a result, separation of the highest-ranked POHCs from the lowest-ranked POHCs according to observed DRE was not possible; a correlation between POHC ranking and DRE could not be confirmed.

A correlation between predicted and observed incinerability was more evident for the thermal failure and worst-case conditions. Kiln-exit DREs for the four POHCs predicted to be most stable (those in Classes 1 and 2) ranged from 99% to 99.99% under these conditions, and were generally lower than DREs for the POHCs predicted to be more easily destroyed. Statistically significant correlations above the 99 percent and 93 percent confidence intervals were identified for the thermal-failure and worst-case tests, respectively.     

On the Occurrence of Transient Puffs in a Rotary Kiln Incinerator Simulator II. Contained Liquid Wastes on Sorbent

The generation of transient puffs resulting from the batch introduction of liquid waste into a 73 kW (250,000 Btu/h) rotary kiln incinerator simulator was investigated. The liquid was added onto a sorbent, enclosed in cylindrical cardboard containers that were introduced into the combustion chamber one at a time. A statistically designed parametric investigation determined the effects of liquid mass, liquid composition, kiln temperature, and kiln rotation speed on the total magnitude and instantaneous intensity of the pollutant puff leaving the kiln. Liquid "wastes" investigated included toluene, methylene chloride, carbon tetrachloride, and No. 5 fuel oil. Transient puffs from these wastes were monitored using on-line measurements for FID-measurable hydrocarbons, CO, and integrated particulate filter loadings, although the suitability of any one of these indicators depended on the chemical nature of the waste involved.

Results demonstrate that puffs formed during transient conditions are generated easily, even with small quantities of wastes and with the kiln operating at 100 percent excess air. High kiln temperatures and increased kiln rotation speeds exacerbated the generation of puffs, due to increased liquid evaporation rates. Transient puffs may contain hazardous products of incomplete combustion (PICs) even though adequate destruction and removal efficiencies are achieved. Mixtures of chlorinated and nonchlorinated principal organic hazardous constituents (POHCs) in the waste can lead to the formation of more diverse chlorinated compounds than are formed from a single chlorinated POHC such as carbon tetrachloride alone.

This paper is the second of a series. Its companion paper, Part I, which has been published previously,¹ is concerned with solid plastic wastes.     

Uptake and localization of gaseous phenol and p-cresol in plant leaves

Understanding foliar uptake processes for organic air pollutants is critical to predicting the fate of these compounds, including their entry into the food chain and their susceptibility to plant-, microbe-, and light-mediated degradation. We characterized the uptake kinetics for gaseous phenol and p-cresol into the leaves of maize seedlings in a closed system over periods up to 23h. When leaves were exposed to mixtures of phenol and p-cresol (3-50microg l(-1) each), the air concentrations of the compounds rapidly decreased, showing residence times of 4-6h. The stomata of the leaves were mostly or completely closed, suggesting that uptake was primarily through the cuticle. The involvement of a cuticular uptake pathway was confirmed based on increased uptake into two cuticular mutants of maize. Models of the uptake data suggested that, at the concentrations used, phenol and p-cresol were taken up in a biphasic manner, consistent with previous two-compartment models for foliar uptake of lipophilic compounds via a cuticular pathway. These models also indicated that phenol was taken up at a slightly faster rate than p-cresol. To begin to understand the fate of these compounds, we examined the location of (14)C in leaves exposed to (14)C-phenol. Significantly more (14)C accumulated in the terminal centimeter than in the central and basal regions of the leaves on both a mass and area basis. This is the first demonstration that a gaseous organic compound, or its breakdown products, accumulates in a spatially non-uniform manner in leaves following foliar uptake. These findings support a role for plants as natural, or deliberate, attenuators of airborne pollutants, and suggest potential availability of these compounds to the leaf surface microflora.     

Effects of organic matter on the distribution of uranium in soil and plant matrices

This work studied interactions of uranium with pure organic compounds, such as glutathione, and more complex mixtures, such as humic acid and aqueous plant extracts. High performance liquid chromatography with UV absorption interfaced to inductively coupled plasma mass spectrometry sequential detection was used to detect organouranium complexes in a variety of soils and plant materials, indicating that nearly 100% of the uranium extracted from certain plant tissues was bound to organic ligands. In addition, soil sorption experiments indicated that humic acid generally decreased uranium sorption to soils and promoted subsequent desorption of uranium because of uranium partitioning to the organic phase. These experiments demonstrate that organic compounds influence the mobility and chemistry of uranium in the environment.     

Emissions of volatile organic compounds from building materials and consumer products

EPA's TEAM Study of personal exposure to volatile organic compounds (VOC) in air and drinking water of 650 residents of seven U.S. cities resulted in the identification of a number of possible sources encountered in peoples' normal daily activities and in their homes. A follow-up EPA study of publicaccess buildings implicated other potential sources of exposure. To learn more about these potential sources, 15 building materials and common consumer products were analyzed using a headspace technique to detect organic emissions and to compare relative amounts. About 10–100 organic compounds were detected offgassing from each material. Four mixtures of materials were then chosen for detailed study: paint on sheetrock; carpet and carpet glue; wallpaper and adhesives; cleansers and a spray pesticide. The materials were applied as normally used, allowed to age 1 week (except for the cleansers and pesticides, which were used normally during the monitoring period), and placed in an environmentally controlled chamber. Organic vapors were collected on Tenax-GC over a 4-h period and analyzed by GC-MS techniques. Emission rates and chamber concentrations were calculated for 17 target chemicals chosen for their toxic, carcinogenic or mutagenic properties. Thirteen of the 17 chemicals were emitted by one or more of the materials. Elevated concentrations of chloroform, carbon tetrachloride, 1,1,1-trichloroethane, n-decane, n-undecane, p-dichlorobenzene, 1,2-dichloroethane and styrene were produced by the four mixtures of materials tested. For some chemicals, these amounts were sufficient to account for a significant fraction of the elevated concentrations observed in previous indoor air studies. We conclude that common materials found in nearly every home and place of business may cause elevated exposures to toxic chemicals.     

Evaluation and analysis of household hazardous substances in Kuwait

Many of the products we use for housework, gardening, home improvement, or car maintenance contain hazardous materials that endanger our health as well as pollute the environment. Inappropriate use, storage, and disposal of hazardous household products can cause injuries, poisoning, and air pollution. The objectives of this paper were to determine the type and the quantity of hazardous materials most commonly used at homes; the level of awareness concerning the disposal of these substances; and the extent of hazardous substance related accidents and injuries occurring at homes. The study concludes with useful recommendations on public education and awareness programs.     

Relevance of enantiomeric separations in environmental science

A significant number of all organic chemicals that are released into the environment are racemic mixtures. Most environmental regulations and scientific environmental studies treat racemic mixtures as though they were single, pure compounds. This can lead to incorrect toxicological, distribution, degradation and other data. A series of new enantioselective chromatographic techniques have been developed that allow the facile separation and quantitation of chiral compounds of environmental importance. Nineteen racemic compounds that have been or currently are being released to the environment are resolved. These include: rodenticides--Warfarin, Coumachlor and Coumafuryl; insecticides--Crufomate, Bulan, Fonofos, Mitotane; insect repellent--Ethohexadiol; herbicides and fungicides--Ancymidol, Silvex, Napropamide, phenyl mercuric lactate, 2-[3-chlorophenoxy]propionamide, and 2-chloropropionic acid; and halocarbons-1,2-dichloropropane, 2-bromo-1-chloropropane, 1,2-dibromo-3-chloropropane, 2,3-dichlorobutane and alpha-1,2,3,4,5,6-hexachlorocyclohexane. Several examples are given to illustrate the importance of enantioselective measurements of these and other compounds. Choosing the proper chromatographic technique and chiral stationary phase based on analyte structure is also discussed.     

Laboratory Evaluations of the Thermal Degradation Properties of Toxic Organic Materials in Sewage Sludge

Laboratory thermal decomposition studies were performed to evaluate potential emissions from sewage sludge incinerators. Precisely controlled thermal decomposition experiments were conducted on sludge spiked with mixtures of hazardous organic compounds, on mixtures of pure compounds without sludge, and on unspiked sludge. Experiments were conducted in nitrogen and air atmospheres with gas phase reaction times of 2.0 seconds over the temperature range 300°C-1000°C.

It was found that sludge inhibited the decomposition of moderately stable spiked contaminants but accelerated the decomposition of the most stable components. This effect was attributed to radical scavengers produced by the sludge matrix at lower temperatures which then decomposed at higher temperatures. A multiple hearth simulation study suggested that most of the organic material present In the sludge matrix is vaporized within the upper hearths that are held at lower temperatures and may consequently escape from such incinerators undestroyed. A number of stable byproducts resulted from the sludge decomposition that may be of environmental concern.     

Laboratory evaluations of the thermal degradation properties of toxic organic materials in sewage sludge

Laboratory thermal decomposition studies were performed to evaluate potential emissions from sewage sludge incinerators. Precisely controlled thermal decomposition experiments were conducted on sludge spiked with mixtures of hazardous organic compounds, on mixtures of pure compounds without sludge, and on unspiked sludge. Experiments were conducted in nitrogen and air atmospheres with gas phase reaction times of 2.0 seconds over the temperature range 300 degrees C-1000 degrees C. It was found that sludge inhibited the decomposition of moderately stable spiked contaminants but accelerated the decomposition of the most stable components. This effect was attributed to radical scavengers produced by the sludge matrix at lower temperatures which then decomposed at higher temperatures. A multiple hearth simulation study suggested that most of the organic material present in the sludge matrix is vaporized within the upper hearths that are held at lower temperatures and may consequently escape from such incinerators undestroyed. A number of stable byproducts resulted from the sludge decomposition that may be of environmental concern.     

Product Guide/1975

Measurements conducted on full-scale hazardous waste incinerators have occasionally shown a relationship between carbon monoxide (CO) emissions and emissions of toxic organic compounds. In this study, four mixtures of chlorinated C₁ and C₂ hydrocarbons were diluted in commercial-grade heptane and burned in a water-cooled turbulent flame reactor (TFR) under two different excess air levels. No correlation between CO and organic emissions could be discerned. Reasons for this lack of observable correlations are discussed in terms of combustion and chemical reaction kinetic theory.     

Utilization of Dry Calcium Based Flue Gas Desulfurization Waste as a Hazardous Waste Fixation Agent

Several designated hazardous wastes (metal plating waste, oil sludge, heavy metal processing sludge) were studied relative to potential detoxification using dry calcium based FGD sludges. The FGD waste was generated from a pilot scale system which utilized slurried lime, a spray drier, and a bag filter. Following detailed physical and chemical identification of the raw FGD and hazardous wastes, various mixtures were prepared and cured. In all cases, even with the organic sludge, a rigid structural material evolved due to the pozzolanic reactions occurring from the wetted dry FGD waste. Structural characteristics, physical character, and chemical leaching effects were evaluated. The solids were leached via both EPA-RCRA and ASTM proposed leaching procedures. In all cases, the hazardous constituents were retained and not leached. Finally, the feasibility of using dry FGD wastes as fixating materials is discussed.     

An Evaluation of the Semi-VOST Method for Determining Emissions from Hazardous Waste Incinerators

The Semi-Volatile Organic Sampling Train method was investigated to determine its reliability and to determine the bias and precision of the method when used to determine emissions from hazardous waste incinerators. Experiments showed that the matrix and sampling variables usually involved in sampling emissions from a hazardous waste incinerator had no significant effect on the recovery of 11 different organic compounds. Significant losses of the sampled compounds can occur during sample preparation. The degree of loss appears to be directly related to the compounds, vapor pressure. These losses can be corrected for by adding deuterated surrogates to the sample and analyzing the surrogates along with the native compounds.

The bias determination was based on dynamic spiking of the sampling train with five deuterated organic compounds selected from Appendix VIII of the Resource Conservation and Recovery Act regulations. The results show biases of from -1 ± 8 percent to -18 ± 27 percent for chlorinated and nonchlorinated compounds. Pyridine, a water-soluble compound, showed a larger bias of-29 ± 13 percent. Particular attention to the recovery of water soluble compounds is necessary to minimize bias in their determinations. Further work is needed to determine the reliability of laboratory-determined retention volumes that are used to determine sampling conditions.     

Post-rehabilitation environmental hazard of Cu, Zn, As and Pb at the derelict Conrad Mine, eastern Australia

A post-rehabilitation audit of the derelict Conrad base metal mine, eastern Australia, indicates ongoing environmental hazard regarding acid mine drainage and concentrations of arsenic and lead to 3 wt% in the soil and sediment. In order to rehabilitate remote contaminated sites effectively, on-site analyses should be carried out to ensure that the materials used to rehabilitate the site are not contaminant-bearing. Understanding the geomorphic setting of the rehabilitated areas is also important in understanding where, and for what period, contaminated materials might be stored in fluvial systems downstream of mine workings. Chemical and geomorphic audits should form a fundamental part of all rehabilitation works to ensure favourable environmental outcomes.