Tetrachloroethylene Emissions and Exposure in Dry Cleaning

ABSTRACT

Tetrachloroethylene (PCE) emissions and the exposure of workers in six commercial and three industrial dry-cleaning establishments that use dry-to-dry machines were determined. The personal samples and area samples [8-hr time-weighted average (TWA) and short-term exposure] were collected with charcoal tubes and passive monitors. The temporal variation of PCE concentration in the workplace air was monitored using a Fourier transform infrared analyzer (FTIR). The PCE emission rates were determined by multiplying the average PCE concentration in the room and the total airflow rate in the room. The PCE emissions were related to the cleaning rate in units of kg/hr.

The operators' mean TWA exposure in commercial shops and industrial establishments was 28 (4.1 ppm) and 32 mg/m³ (4.6 ppm), and the pressers' exposure was 3.4 (0.5 ppm) and 7.7 mg/m³ (1.1 ppm), respectively. The customer service personnel had the lowest TWA exposure with a mean value of 0.8 mg/m³ (0.1 ppm). The highest peak concentration (2300 mg/m³; 334 ppm) was observed during cleaning of the lint and button trap, during which operation respirators were used. The PCE emission rates ranged from 4 to 118 g/hr corresponding to emission factors (mass of solvent evaporated per mass of cleaned cloths) of 0.3–3.6 g/kg. The workers' exposure to PCE was below the occupational limit values in the United States [according to the American Conference of Governmental Industrial Hygienists (ACGIH)] and in Finland. The outdoor PCE emissions were clearly below the limit values given in the European Union volatile organic compound (VOC) directive requirements.     

Tetrachloroethylene emissions and exposure in dry cleaning

Tetrachloroethylene (PCE) emissions and the exposure of workers in six commercial and three industrial dry-cleaning establishments that use dry-to-dry machines were determined. The personal samples and area samples [8-hr time-weighted average (TWA) and short-term exposure] were collected with charcoal tubes and passive monitors. The temporal variation of PCE concentration in the workplace air was monitored using a Fourier transform infrared analyzer (FTIR). The PCE emission rates were determined by multiplying the average PCE concentration in the room and the total airflow rate in the room. The PCE emissions were related to the cleaning rate in units of kg/hr. The operators' mean TWA exposure in commercial shops and industrial establishments was 28 (4.1 ppm) and 32 mg/m3 (4.6 ppm), and the pressers' exposure was 3.4 (0.5 ppm) and 7.7 mg/m3 (1.1 ppm), respectively. The customer service personnel had the lowest TWA exposure with a mean value of 0.8 mg/m3 (0.1 ppm). The highest peak concentration (2300 mg/m3; 334 ppm) was observed during cleaning of the lint and button trap, during which operation respirators were used. The PCE emission rates ranged from 4 to 118 g/hr corresponding to emission factors (mass of solvent evaporated per mass of cleaned cloths) of 0.3-3.6 g/kg. The workers' exposure to PCE was below the occupational limit values in the United States [according to the American Conference of Governmental Industrial Hygienists (ACGIH)] and in Finland. The outdoor PCE emissions were clearly below the limit values given in the European Union volatile organic compound (VOC) directive requirements.     

Environmental Issues—Persistent Problems and Emerging Challenges

Abstract

A field study was performed to evaluate indoor air concentrations and vapor intrusion (VI) of tetrachloroethylene (PCE) and other chlorinated solvents at a commercial retail site in Dallas, TX. The building is approximately 40 yr old and once housed a dry cleaning operation. Results from an initial site characterization were used to select sampling locations for the VI study. The general approach for evaluating VI was to collect time-integrated canister samples for off-site U.S. Environmental Protection Agency Method TO-15 analyses. PCE and other chlorinated solvents were measured in shallow soil gas, subslab soil-gas, indoor air, and ambient air. The subslab soil gas exhibited relatively high values: PCE ≤2,600,000 parts per billion by volume (ppbv) and trichloroethylene ≤170 ppbv. The attenuation factor, the ratio of indoor air and subslab soil-gas concentrations, was unusually low: approximately 5 x 10^-6 based on the maximum subslab soil-gas concentration of PCE and 1.4 x 10^-5 based on average values.     

A History of the Production and Use of Carbon Tetrachloride,Tetrachloroethylene, Trichloroethylene and 1,1,1-Trichloroethane in the United States: Part 1--Historical Background; Carbon Tetrachloride and Tetrachloroethylene

Carbon tetrachloride (CTC), tetrachloroethylene (PCE), trichloroethylene (TCE) and 1,1,1-trichloroethane (TCA) were four of the most widely used cleaning and degreasing solvents in the United States. These compounds were also used in a wide variety of other applications. The history of the production and use of these four compounds is linked to the development and growth of the United States' synthetic organic chemical industry, and historical events that affected the development and use of chlorinated solvents in general. Part 1 of this article includes a discussion of the historical background common to each of the four solvents, followed by discussion on the history of CTC and PCE. In the early years of the 20th century, CTC became the first of the four solvents to come into widespread use. CTC was used as a replacement for petroleum distillates in the dry-cleaning industry, but was later replaced by PCE. In the 1990s, CTC was phased out under the Montreal Protocol due to its role in stratospheric ozone depletion.     

A History of the Production and Use of Carbon Tetrachloride,Tetrachloroethylene, Trichloroethylene and 1,1,1-Trichloroethane in the United States: Part 1—Historical Background; Carbon Tetrachloride and Tetrachloroethylene

Carbon tetrachloride (CTC), tetrachloroethylene (PCE), trichloroethylene (TCE) and 1,1,1-trichloroethane (TCA) were four of the most widely used cleaning and degreasing solvents in the United States. These compounds were also used in a wide variety of other applications. The history of the production and use of these four compounds is linked to the development and growth of the United States' synthetic organic chemical industry, and historical events that affected the development and use of chlorinated solvents in general. Part 1 of this article includes a discussion of the historical background common to each of the four solvents, followed by discussion on the history of CTC and PCE. In the early years of the 20th century, CTC became the first of the four solvents to come into widespread use. CTC was used as a replacement for petroleum distillates in the dry-cleaning industry, but was later replaced by PCE. In the 1990s, CTC was phased out under the Montreal Protocol due to its role in stratospheric ozone depletion.     

Day-of-Week Patterns in Toxic Air Contaminants in Southern California

Abstract

Day-of-week mean ambient concentrations were computed for six high-cancer-risk toxic air contaminants (TACs): 1,3-butadiene, benzene, acetaldehyde, formalde-hyde, carbon tetrachloride (CCl₄), and perchloroethylene. Data from six urban sites in southern California, from 1989 through 2001, were analyzed. Graphical displays were used to search for repeated patterns. Benzene and 1,3-butadiene, emitted mainly by mobile sources, exhibit distinctly lower concentrations on Sundays and slightly lower concentrations on Saturdays and Wednesdays. Acetaldehyde and formaldehyde show some trace of a weekly pattern similar to that of benzene and 1,3-butadiene, but the pattern is not strongly marked. Perchloroethylene, used primarily as a dry-cleaning solvent, is also distinctly lower on Sundays. CCl₄ does not show a dayof-week pattern.     

Microwave-induced nanoscale zero-valent iron degradation of perchloroethylene and pentachlorophenol

Microwave (MW) is applied to enhance perchloroethylene (PCE) or pentachlorophenol (PCP) removal using zero-valent iron (ZVI; Fe⁰) as the dielectric medium. ZVI has a much higher dielectric loss factor (39.5) than other media; it is capable of absorbing MW radiation rapidly to speed up the release of electrons, leading to rises of the ZVI particle surface temperature. If the MW power is continued, excessive electricity will accumulated inside ZVI particles, resulting in sparks. The results show that during the initial 5 sec (700 W), the linear aliphatic PCE has a faster decomposing rate than the ringed PCP (82.0% vs. 4.8%) because less energy is required for decomposing the linear-chlorine bond (90 kcal mol^?1) than ring-chlorine bonds (95 kcal mol^?1). Later, the removal rate for either PCE or PCP remains the same when the exposure time is between 5 and 60 sec. Without MW irradiation, linear PCE molecules have larger surface area to contact ZVI, and hence they have better removal efficiencies than PCP molecules. Using Fe⁰ as a microwave dielectric medium to treat PCE or PCP is a new and worthwhile treatment technology; it is environmentally friendly, and its use will eliminate the secondary pollution.

Implications Nanoscale iron particles are characterized by high surface-area-to-volume ratios, high specific surface area, and high surface reactivity. With a much higher dielectric loss factor, it is capable of absorbing MW radiation rapidly to speed up the release of electrons, leading to rise in temperature. The time needed to achieve a satisfactory treatment is also reduced, leading to significant saving of energy consumption to make this method cost-effective and also environmentally friendly for the industry to pursuit sustainable development.     

Comparison between acetate and hydrogen as electron donors and implications for the reductive dehalogenation of PCE and TCE

Bioremediation by reductive dehalogenation of groundwater contaminated with tetrachloroethene (PCE) or trichloroethene (TCE) is generally carried out through the addition of a fermentable electron donor such as lactate, benzoate, carbohydrates or vegetable oil. These fermentable donors are converted by fermenting organisms into acetate and hydrogen, either of which might be used by dehalogenating microorganisms. Comparisons were made between H2 and acetate on the rate and extent of reductive dehalogenation of PCE. PCE dehalogenation with H2 alone was complete to ethene, but with acetate alone it generally proceeded only about half as fast and only to cis-1,2-dichloroethene (cDCE). Additionally, acetate was not used as an electron donor in the presence of H2. These findings suggest the fermentable electron donor requirement for PCE dehalogenation to ethene can be reduced up to 50% by separating PCE dehalogenation into two stages, the first of which uses acetate for the conversion of PCE to cDCE, and the second uses H2 for the conversion of cDCE to ethene. This can be implemented with a recycle system in which the fermentable substrate is added down-gradient, where the hydrogen being produced by fermentation effects cDCE conversion into ethene. The acetate produced is recycled up-gradient to achieve PCE conversion into cDCE. With the lower electron donor usage required, potential problems of aquifer clogging, excess methane production, and high groundwater chemical oxygen demand (COD) can be greatly reduced.     

Removal and Destruction of Organic Contaminants in Water Using Adsorption,Steam Regeneration,and Photocatalytic Oxidation: A Pilot-Scale Study

ABSTRACT

The overall objective of this pilot-scale study is to investigate the technical feasibility of the removal and destruction of organic contaminants in water using adsorption and photocatalytic oxidation. The process consists of two consecutive operational steps: (1) removal of organic contaminants using fixed-bed adsorption; and (2) regeneration of spent adsorbent using photocatalysis or steam, followed by decontamination of steam condensate using photocatalysis. The pilot-scale study was conducted to evaluate these options at a water treatment plant in Wausau (Wisconsin) for treatment of groundwater contaminated with tetrachloroethene (PCE), trichloroethene (TCE), cis-dichloroethene (cis-DCE), toluene, ethylbenzene (EB), and xylenes. The adsorbents used were F-400 GAC and Ambersorb 563.

In the first treatment strategy, the adsorbents were impregnated with photocatalyst and used for the removal of aqueous organics. The spent adsorbents were then exposed to ultraviolet light to achieve photocatalytic regeneration. Regeneration of adsorbents using photocatalysis was observed to be not effective, probably because the impregnated photocatalyst was fouled by background organic matter present in the groundwater matrix.

In the second treatment strategy, the spent adsorbents were regenerated using steam, followed by cleanup of steam condensate using photocatalysis. Four cycles of adsorption and three cycles of steam regeneration were performed. Ambersorb 563 adsorbent was successfully regenerated using saturated steam at 160 °C within 20 hours. The steam condensate was treated using fixed-bed photo-catalysis using 1% Pt-TiO₂ photocatalyst supported on silica gel. After 35 minutes of empty bed contact time, more than 95% removal of TCE, cis-DCE, toluene, EB, and xylenes was achieved, and more than 75% removal of PCE was observed.

In the case of activated carbon adsorbent, steam regeneration was not effective, and a significant loss in adsorbent capacity was observed.     

A History of the Production and Use of Carbon Tetrachloride,Tetrachloroethylene, Trichloroethylene and 1,1,1-Trichloroethane in the United States: Part 2--Trichloroethylene and 1,1,1-Trichloroethane

Carbon tetrachloride (CTC), tetrachloroethylene (PCE), trichloroethylene (TCE) and 1,1,1-trichloroethane (TCA) were four of the most widely used cleaning and degreasing solvents in the United States. Part 2 of this article describes the history of TCE and TCA. TCE production in the United States began in the early 1920s. TCE was used as a replacement for petroleum distillates in the dry-cleaning industry, and became the solvent of choice for vapor degreasing in the 1930s. TCE's use as a degreaser decreased in the 1960s due to toxicity concerns and the increasing popularity of TCA. Significant TCA use began in the 1950s with the development of suitable stabilizer formulations. In the 1990s, TCA was phased out under the Montreal Protocol due to its role in stratospheric ozone depletion.     

Determination of bioconcentration potential of tetrachloroethylene in marine algae by 13C

The use of stable isotope of organic-carbon, organic-¹³C, as a tracer for the determination of the concentration of tetrachloroethylene (PCE), C_A, in Heterosigma akashiwo and Skeletonema costatum was examined. C_A determined by the ¹³C and GC methods showed good agreement with each other. This suggests that it is reasonable and reliable to determine the bioconcentration potentail of PCE in marine algae. Fitting values of bioconcentration potentail parameters, including uptake rate constant k₁, elimination rate constant k₂ and bioconcentration factor on the basis of dry weight BCF_D, were done not only to the time course for PCE uptake by the algae with the bioconcentration model, but also to experimental data for “percent inhibition(%)∼exposure concentration of PCE∼time” with the combined bioconcentration and probability model. The values obtained from the bioconcentration model were consistent with those from the combined bioconcentration and probability model. With the parameters (such as k₁, k₂, growth rate constant k_G, critical concentration of HOCs in the organism resulting in growth inhibition C_A¹ and spread factor S) the variability in toxicity (such as EC₁₀, EC₅₀, EC₇₀) can be estimated from the combined bioconcentration and probability model, which fits well with the experimental observations.     

不同共代谢基质下四氯乙烯厌氧生物降解研究

分别用葡萄糖、乳酸盐和醋酸盐作为驯化好的厌氧污泥的共代谢基质 ,对四氯乙烯 ( PCE)的降解进行研究。结果表明 ,PCE是通过还原脱氯发生生物降解的。实验的回归结果表明 ,反应均符合一级动力学方程 ;反应速率常数的大小依次为 k乳酸盐 >k葡萄糖 >k醋酸盐 ;以乳酸盐作为共代谢基质时 ,PCE的降解速率较快 ,在实验条件下乳酸盐是最合适的共代谢基质     

Sustainable Development by Design: Review of Life Cycle Design and Related Approaches

Abstract

The quality of stationary source emission factors is typically described using data quality ratings, which provide no quantification of the precision of the emission factor for an average source, nor of the variability from one source to another within a category. Variability refers to actual differences caused by differences in feedstock composition, design, maintenance, and operation. Uncertainty refers to lack of knowledge regarding the true emissions. A general methodology for the quantification of variability and uncertainty in emission factors, activity factors, and emission inventories (EIs) is described, featuring the use of bootstrap simulation and related techniques. The methodology is demonstrated via a case study for a selected example of NO_x emissions from coal-fired power plants. A prototype software tool was developed to implement the methodology. The range of interunit variability in selected activity and emission factors was shown to be as much as a factor of 4, and the range of uncertainty in mean emissions is shown to depend on the interunit variability and sample size. The uncertainty in the total inventory of ?16 to +19% was attributed primarily to one technology group, suggesting priorities for collecting data and improving the inventory. The implications for decision-making are discussed.     

Some Heavy-Metal Pollutants in the Air of Naples

ABSTRACT

In this paper, assumptions regarding future land use as a key uncertainty is considered and its impact on risk analysis for contaminated sites is assessed. Risks are assessed for two land use scenarios (current-use industrial and future-use residential) using probabilistic models that incorporate uncertainty and variability in the exposure parameters. Residual risks are calculated for both industrial and residential cleanup standards. A Superfund site in northern California is considered.

In general, for the unremediated case, the future-use residential scenarios produce larger risks (1 to 3 orders of magnitude) than current- (continued) use industrial scenarios. For the Superfund site studied, the residual risks calculated for the remedy selected was not sufficiently protective of future-use residents in that it did not meet .S. Environmental Protection Agency (EPA) risk goals, but was protective of current-use workers, even though the cleanup criteria were based on residential use. Alternative risk management practices, such as deed restrictions, can be used in such cases.     

Concentration of tetrachloroethylene in indoor air at a former dry cleaner facility as a function of subsurface contamination: a case study

A field study was performed to evaluate indoor air concentrations and vapor intrusion (VI) of tetrachloroethylene (PCE) and other chlorinated solvents at a commercial retail site in Dallas, TX. The building is approximately 40 yr old and once housed a dry cleaning operation. Results from an initial site characterization were used to select sampling locations for the VI study. The general approach for evaluating VI was to collect time-integrated canister samples for off-site U.S. Environmental Protection Agency Method TO-15 analyses. PCE and other chlorinated solvents were measured in shallow soil gas, subslab soil-gas, indoor air, and ambient air. The subslab soil gas exhibited relatively high values: PCE < or =2,600,000 parts per billion by volume (ppbv) and trichloroethylene < or =170 ppbv. The attenuation factor, the ratio of indoor air and subslab soil-gas concentrations, was unusually low: approximately 5 x 10(-6) based on the maximum subslab soil-gas concentration of PCE and 1.4 x 10(-5) based on average values.     

14C‐labeled aflatoxin B1 prepared with yeastlike cultures of Aspergillus parasiticus

Abstract

A simple method was developed to produce ¹⁴C‐labeled aflatoxin B₁ by using the yeastlike phase of Aspergillus parasiticus NRRL 2999. Yeastlike cultures resulted from absence of manganese in a synthetic medium. Sodium acetate‐1‐¹⁴C had a 0.22% average incorporation; sodium acetate‐1,2‐¹⁴C, 0.70%. The average yield of labeled B₁ was 10 mg/500 ml medium with an average specific activity of either 63.3 mCi/mole (C‐l label) or 194.3 mCi/mole (C‐1, 2 label).     

A mass balance study of the phytoremediation of perchloroethylene-contaminated groundwater

A mass balance study was performed under controlled field conditions to investigate the phytoremediation of perchloroethylene (PCE) by hybrid poplar trees. Water containing 7–14 mg L^?1 PCE was added to the test bed. Perchloroethylene, trichloroethylene, and cis-dichloroethylene were detected in the effluent at an average of 0.12 mg L^?1, 3.9 mg L^?1, and 1.9 mg L^?1, respectively. The total mass of chlorinated ethenes in the water was reduced by 99%. Over 95% of the recovered chlorine was as free chloride in the soil, indicating near-complete dehalogenation of the PCE. Transpiration, volatilization, and accumulation in the trees were all found to be minor loss mechanisms. In contrast, 98% of PCE applied to an unplanted soil chamber was recovered as PCE in the effluent water or volatilized into the air. These results suggest that phytoremediation can be an effective method for treating PCE-contaminated groundwater in field applications.     

A History of the Production and Use of Carbon Tetrachloride,Tetrachloroethylene, Trichloroethylene and 1,1,1-Trichloroethane in the United States: Part 2—Trichloroethylene and 1,1,1-Trichloroethane

Carbon tetrachloride (CTC), tetrachloroethylene (PCE), trichloroethylene (TCE) and 1,1,1-trichloroethane (TCA) were four of the most widely used cleaning and degreasing solvents in the United States. Part 2 of this article describes the history of TCE and TCA. TCE production in the United States began in the early 1920s. TCE was used as a replacement for petroleum distillates in the dry-cleaning industry, and became the solvent of choice for vapor degreasing in the 1930s. TCE’s use as a degreaser decreased in the 1960s due to toxicity concerns and the increasing popularity of TCA. Significant TCA use began in the 1950s with the development of suitable stabilizer formulations. In the 1990s, TCA was phased out under the Montreal Protocol due to its role in stratospheric ozone depletion.     

Photochemical Reactivity of Perchloroethylene: A New Appraisal

Perchloroethylene (PCE), a solvent used in dry cleaning, has been suspected of contributing significantly to photochemical ozone/oxidant (O₃/O_x) problems in urban atmospheres. Past evidence, however, was neither complete nor consistent. To interpret more conclusively the past evidence, and further understand PCE's role in the O₃O_x problem, a smog chamber testing program was conducted. The program's objectives were: (a) to explain the mechanism of the PCE reaction in smog chamber atmospheres, and (b) to extrapolate the smog chamber findings regarding PCE reactivity to the real atmosphere. Results showed that in smog chambers, PCE reacts and forms O₃/O_x following what appears to be a Cl instigated photooxidation mechanism rather than the OH initiated mechanism accepted in current smog chemistry. The evidence, collectively, strongly supported this conclusion even though the source of Cl atoms could not be identified with confidence. It was further concluded that in the real atmosphere neither the Cl instigated nor the OH instigated photooxidations of PCE can generate substantial concentrations of O₃/O_x. In fact, PCE contributes less to the ambient O₃/O_x problem than equal concentrations of ethane.     

不同共代谢基质对四氯乙烯的厌氧生物降解研究

用驯化好的厌氧污泥对葡萄糖、乳酸盐和醋酸盐作为电子供体时四氯乙烯(PCE)的降解进行研究。实验结果表明,PCE是通过还原脱氯发生生物降解的。实验的回归结果表明,反应均符合一级动力学反应速率,常数的大小依次为k乳酸>k葡萄糖>k醋酸。表明乳酸盐作为电子供体时PCE的降解速率较快,说明在实验条件下乳酸盐是最合适的电子供体。并且在整个实验过程中由共代谢基质提供的电子供体不是PCE降解的限制因素。