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 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.     

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.     

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.     

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.     

Aerobic biodegradation of dichloroethenes by indigenous bacteria isolated from contaminated sites in Africa

The widespread use of tetrachloroethene (PCE) and trichloroethene (TCE) as dry cleaning solvents and degreasing agents for military and industrial applications has resulted in significant environmental contamination worldwide. Anaerobic biotransformation of PCE and TCE through reductive dechlorination frequently lead to the accumulation of dichloroethenes (DCEs), thus limiting the use of reductive dechlorination for the biotransformation of the compounds. In this study, seven bacteria indigenous to contaminated sites in Africa were characterized for DCE degradation under aerobic conditions. The specific growth rate constants of the bacterial isolates ranged between 0.346-0.552d(-1) and 0.461-0.667d(-1) in cis-DCE and trans-DCE, respectively. Gas chromatographic analysis revealed that up to 75% of the compounds were degraded within seven days with the degradation rate constants ranging between 0.167 and 0.198d(-1). The two compounds were also observed to be significantly degraded, simultaneously, rather than sequentially, when present as a mixture. Phylogenetic analysis of the 16S rRNA gene sequences of the bacterial isolates revealed their identity as well as their relation to other environmentally-important bacteria. The observed biodegradation of DCEs may contribute to PCE and TCE removal at the aerobic fringe of groundwater plumes undergoing reductive dechlorination in contaminated sites.     

Contaminated site remedial investigation and feasibility removal of chlorinated volatile organic compounds from groundwater by activated carbon fiber adsorption

Groundwater contaminated by dense, non-aqueous phase liquids (DNAPLs) such as chlorinated solvents has become a serious problem in some regions of Taiwan. The sources of these contaminants are due to industrial discharges. These chlorinated volatile organic compounds (VOCs) have been proven to be carcinogenic to humans. The groundwater is used for domestic drinking water supply in some cities of Taiwan and the severely contaminated groundwater has to be treated in order to meet the requirement of drinking water standards. This study covers two areas of work. In the first part, polluted groundwater samples were collected from the contaminated site and analytical results indicated measurable concentrations of 12 representative chlorinated VOCs in water samples. The primary VOCs detected included trichloroethene (TCE), tetrachloroethene (PCE), 1,1,2-trichloroethane (1,1,2-TCA), and 1,1-dichloroethene (1,1-DCE). Second, to remove VOCs groundwater was treated using adsorption on activated carbon fiber (ACF). This involved pumping groundwater through vessels containing ACF. Most VOCs, including TCE, PCE, 1,1,2-TCA, and DCE, were readily adsorbed onto ACF and are removed from the water stream. Our study showed that the technology was able to significantly reduce chlorinated VOCs concentrations in groundwater.     

Dissipation of oxytetracycline, chlortetracycline, tetracycline and doxycycline using HPLC-UV and LC/MS/MS under aquatic semi-field microcosm conditions

A mixture of four tetracyclines; oxytetracycline (OTC), chlortetracycline (CTC), tetracycline (TC), and doxycycline (DC) was applied in fifteen 12000l outdoor microcosms at four treatment levels plus controls each with three replicates (n = 3). The dissipation times of parent compounds were monitored and half-lives (DT50) of 1-4 days, depending on treatment level were recorded. This is in accordance with half-lives from previous findings in bench-top experiments. Parent compound DT50, were determined using HPLC-UV. Furthermore, the samples were analyzed for ten different tetracycline products using LC/MS/MS. Two products were found for chlortetracycline; 4-epi-anh-chlortetracyline and the iso-chlortetracycline. Iso-forms were only found for CTC and only at the highest treatment (300 microg l(-1)). The half-lives, trajectories, and relative amounts of the products were analogous for all four tetracyclines. DT50 for products were less than 1.2 days. Formation of 4-epi-anh-tetracyclines, occurred at neutral to weak alkaline conditions.     

Tropospheric concentrations of the chlorinated solvents,tetrachloroethene and trichloroethene,measured in the remote northern hemisphere

A fully automated twin ECD gas chromatograph system with sample enriching adsorption–desorption primary stage was deployed on two field campaigns – Ny-Ålesund, Svalbard, Arctic Norway (July–September 1997), and the RRS Discovery CHAOS cruise of the northeast Atlantic (April–May 1998). Concentrations of an extensive set of halocarbons were detected at hourly intervals at pptv levels. We present here the results obtained for the chlorinated solvents, tetrachloroethene (PCE) and trichloroethene (TCE). Average baseline PCE and TCE concentrations of 1.77 and 0.12 pptv, respectively, were recorded in Ny-Ålesund. During pollution incidences, concentrations rose to 5.61 (PCE) and 3.18 pptv (TCE). The cruise data showed average concentrations ranging from 4.26 (PCE) and 1.66 pptv (TCE) for air masses originating over the North Atlantic and Arctic open oceans, to maxima of 15.59 (PCE) and 17.51 pptv (TCE) for polluted air masses from Northern Europe. The data sets emphasise the difficulties in defining remote sites for background tropospheric halocarbon measurements, as Ny-Ålesund research station proved to be a source of tetrachloroethene. The data also suggest possible oceanic emissions of trichloroethene in the sub-tropical ocean.     

Non-steady state partitioning of dry cleaning surfactants between tetrachloroethylene (PCE) and water in porous media

Trapped organic solvents, in both the vadose zone and below the water table, are frequent sources of environmental contamination. A common source of organic solvent contamination is spills, leaks, and improper solvent disposal associated with dry cleaning processes. Dry cleaning solvents, such as tetrachloroethylene (PCE), are typically enhanced with the addition of surfactants to improve cleaning performance. The objective of this work was to examine the partitioning behavior of surfactants from PCE in contact with water. The relative rates of surfactants partitioning and PCE dissolution are important for modeling the behavior of waste PCE in the subsurface, in that they influence the interfacial tension of the PCE, and how (or if) interfacial tension changes over time in the subsurface. The work described here uses a flow-through system to examine simultaneous partitioning and PCE dissolution in a porous medium. Results indicate that both nonylphenol ethoxylate nonionic surfactants and a sulfosuccinate anionic surfactant partition out of residual PCE much more rapidly than the PCE dissolves, suggesting that in many cases interfacial tension changes caused by partitioning may influence infiltration and distribution of PCE in the subsurface. Non-steady-state partitioning is found to be well-described by a linear driving force model incorporating measured surfactant partition coefficients.     

In situ sequenced bioremediation of mixed contaminants in groundwater

A mixture of chlorinated solvents (about 0.5-10 mg/l), including tetrachloroethene (PCE) and carbon tetrachloride (CT), together with a petroleum hydrocarbon, toluene (TOL), were introduced into a 24 m long x 2 m wide x 3 m deep isolated section (henceforth called a gate) of the Borden aquifer and subjected to sequential in situ treatment. An identical section of aquifer was similarly contaminated and allowed to self-remediate by natural attenuation, thus serving as a control. The control presents a rare opportunity to critically assess the performance of the treatment systems, and represents the first such study for sequenced in situ remediation. The first treatment step was anaerobic bioremediation. This was accomplished using a modified nutrient injection wall (NIW) to pulse benzoate and a nutrient solution into the aquifer, maximizing mixing by dispersion and minimizing fouling near the injection wells. In the anaerobic bioactive zone that developed, PCE, CT and chloroform (CF), a degradation product of CT, degraded with a half-lives of about 59, 5.9 and 1.7 days, respectively. The second step was aerobic bioremediation, using a biosparge system. TOL and cis-1,2 dichloroethene (cDCE), from PCE degradation, were found to degrade aerobically with half-lives of 17 and 15 days, respectively. Compared to natural attenuation, PCE and TOL removal rates were significantly better in the sequenced treatment gate. However, CT and CF were similarly and completely attenuated in both gates. It is believed that the presence of TOL helped sustain the reducing environment needed for the reduction of these two compounds.     

Development of a biobarrier for the remediation of PCE-contaminated aquifer

The industrial solvent tetrachloroethylene (PCE) is among the most ubiquitous chlorinated compounds found in groundwater contamination. The objective of this study was to develop a biobarrier system, which includes a peat layer to enhance the anaerobic reductive dechlorination of PCE in situ. Peat was used to supply primary substrate (electron donor) continuously. A laboratory-scale column experiment was conducted to evaluate the feasibility of this proposed system or PCE removal. This experiment was performed using a series of continuous-flow glass columns including a soil column, a peat column, followed by two consecutive soil columns. Anaerobic acclimated sludges were inoculated in all three soil columns to provide microbial consortia for PCE biodegradation. Simulated PCE-contaminated groundwater with a flow rate of 0.25 l/day was pumped into this system. Effluent samples from each column were analyzed for PCE and its degradation byproducts (trichloroethylene (TCE), cis-dichloroethylene (cis-DCE), vinyl chloride (VC), ethylene (ETH), and ethane). Results show that the decrease in PCE concentrations and production of PCE byproducts were observed over a 65-day operating period. Up to 98% of PCE removal efficiency was obtained in this passive system. Results indicate that the continuously released organics from peat column enhanced PCE biotransformation. Thus, the developed biobarrier treatment scheme has the potential to be developed into a cost-effective in situ PCE-remediation technology, and can be utilized as an interim step to aid in system scale-up.     

Natural attenuation of chlorinated solvents at Area 6, Dover Air Force Base: groundwater biogeochemistry

Monitored natural attenuation (MNA) has recently emerged as a viable groundwater remediation technology in the United States. Area 6 at Dover Air Force Base (Dover, DE) was chosen as a test site to examine the potential for MNA of tetrachloroethene (PCE) and trichloroethene (TCE) in groundwater and aquifer sediments. A "lines of evidence" approach was used to document the occurrence of natural attenuation. Chlorinated hydrocarbon and biogeochemical data were used to develop a site-specific conceptual model where both anaerobic and aerobic biological processes are responsible for the destruction of PCE, TCE, and daughter metabolites. An examination of groundwater biogeochemical data showed a region of depleted dissolved oxygen with elevated dissolved methane and hydrogen concentrations. Reductive dechlorination likely dominated in the anaerobic portion of the aquifer where PCE and TCE levels were observed to decrease with a simultaneous increase in cis-1,2-dichloroethene (cis-DCE), vinyl chloride (VC), ethene, and dissolved chloride. Near the anaerobic/ aerobic interface, concentrations of cis-DCE and VC decreased to below detection limits, presumably due to aerobic biotransformation processes. Therefore, the contaminant and daughter product plumes present at the site appear to have been naturally atteuated by a combination of active anaerobic and aerobic biotransformation processes.     

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.     

Anaerobic transformations and bioremediation of chlorinated solvents

Chlorinated aliphatic compounds, notably the chlorinated solvents, are common contaminants in soil and groundwater at hazardous waste sites. While these compounds are often recalcitrant, under favorable conditions they can be transformed and degraded through microbially mediated processes. There is great interest in understanding the transformations that are observed at contaminated sites and in manipulating these systems to achieve remediation. An important class of transformations occurs in anaerobic environments. Many of the transformations are reductive, and many yield useful energy to specific anaerobic bacteria. They include reductive dechlorination, dehydrochlorination and dichloroelemination. Of these, reductive dechlorination is often a growth-supporting reaction, while the others may be abiological or catalyzed by biological molecules. The reactions may result in chlorinated products, but there are often reaction sequences leading to completely dechlorinated products. The behavior of carbon tetrachloride (CT), 1,1,2,2-tetrachloroethane (TeCA) and the chloroethenes, perchloroethylene (PCE) and trichloroethylene (TCE), illustrate the range of anaerobic transformations that are possible, as well as the limited transformation that often is seen in the environment. CT undergoes reductive and substitutive reactions that are catalyzed by biological molecules but do not support bacterial growth. The anaerobic degradation of TeCA, which is a major contaminant at a site near Tacoma, WA, USA, provides examples of each type of transformation, and the products formed are consistent with the chlorinated compounds that are found in groundwater extraction wells. A laboratory study, using anaerobic sludge that had been fed chlorinated compounds, a cell-free extract from the sludge, and killed controls, showed that TeCA was transformed to four products and that these were further transformed, suggesting that it might be possible to degrade TeCA to innocuous products. Reductive dechlorination of PCE and TCE has been studied in many laboratories. Studies with mixed anaerobic consortia and with several dehalogenating bacteria, including strain 195 (. Isolation of a bacterium that reductively dechlorinates tetrachloroethane to ethane. Science 276, 1568-1571) that transforms PCE to ethene, have demonstrated that reductive dechlorination supports growth of the novel bacteria that carry out the reactions. Hydrogen has been shown to be an electron donor for the bacterial dehalogenation reactions, and kinetic and thermodynamic considerations indicate that dehalogenators can compete in some, but not all, anaerobic environments, pointing to applications of in situ bioremediation and to its limitations. Selected field studies of anaerobic transformations help delineate the applications of this type of bioremediation.     

Analytical methods for the determination of alachlor, metolachlor, simazine and atrazine mobility in soils

A method for the determination of the mobility of the herbicides, alachlor, metolachlor, simazine and atrazine in soil is described. The method is based on the use of soil thin-layer chromatography (TLC) and does not require the use of radiolabelled compounds. Soil on the TLC plate after development was separated into various bands, the material in each band was extracted with solvents and analyzed by gas chromatography.     

四氯化碳的生产与应用及其淘汰策略

四氯化碳是一种消耗臭氧层物质,其生产和消费都面临着严峻的淘汰形势.简要叙述了四氯化碳的生产技术,以四氯化碳为原料生产大宗化学品和精细化学品的转化技术,四氯化碳作为化工助剂在我国的应用情况以及相应的淘汰方法和技术进展.     

Transfer of methyl chloroform, trichloroethylene and tetrachloroethylene to milk, tissues and expired air following intraruminal or oral administration in lactating goats and milk-fed kids

The distribution of methyl chloroform was determined (MCF), trichloroethylene (TRI) and tetrachloroethylene (PCE) in milk, tissues and expired air by intraruminally administering 0.625 ml kg(-0.75) of an equal-volume mixture of the three compounds to lactating goats. The milk secreted during 24 h after the intraruminal administration contained 1.42 mg of MCF, 1.87 mg of TRI, 6.43 mg of PCE and 0.33 mg of trichloroethanol (TCE). MCF, TRI and PCE appeared in the blood less than 30 min after administration. Oral administration of these chemicals to milk-fed kids showed that at 3.5 h post-administration, the liver contained these chemicals in greatest abundance. The adaptation of milk-fed kids to 3 weeks administration of small amounts of propylene glycol stimulated the metabolic conversion of TRI to TCE. There were linear relationships between the blood concentrations of these chemicals and the expiration rates after oral administration of 0.4 ml kg(-1) of each chemical to milk-fed kids. The expiration rates of MCF, TRI and PCE were 605, 122 and 46 microg min(-1) kg(-1) at 2 microg ml(-1) blood concentrations of MCF, TRI and PCE, respectively. These results suggested that MCF is little metabolized, being most readily exhaled in expired air, while PCE demonstrates the greatest tissue-partitioning, being largely secreted into the milk or retained in the liver. TRI can be extensively metabolized to other compounds such as TCE in milk-fed kids.     

Analytical methods for the determination of alachlor,metolachlor, simazine and atrazine mobility in soils

Abstract

A method for the determination of the mobility of the herbicides, alachlor, metolachlor, simazine and atrazine in soil is described . The method is based on the use of soil thin‐layer chromatography (TLC) and does not require the use of radiolabelled compounds. Soil on the TLC plate after development was separated into various bands, the material in each band was extracted with solvents and analyzed by gas chromatography.