Abstract  The carcinogenicity and/or mutagenicity as well as structural features and relationships of the glycidylethers (principally phenyl-, butyl-, allyl-, and isopropyl-), dioxane, nitroalkanes (nitro methane, ethane and propane), dimethylformamide and allyl derivatives (chloride, alcohol and amine) were examined. Additionally, considerations of the production, use patterns, estimated populations at risk, TLV's and metabolism of the above agents were discussed.

Abstract  Increasing regulatory attention to 1,4-dioxane has prompted the United States Air Force (USAF) to evaluate potential environmental liabilities, primarily associated with legacy contamination, at an enterprise scale. Although accurately quantifying environmental liability is operationally difficult given limited historic environmental monitoring data, 1,4-dioxane is a known constituent (i.e., stabilizer) of chlorinated solvents, in particular 1,1,1-trichloroethane (TCA). Evidence regarding the co-occurrence of 1,4-dioxane and trichloroethylene (TCE), however, has been heavily debated. In fact, the prevailing opinion is that 1,4-dioxane was not a constituent of past TCE formulations and, therefore, these two contaminants would not likely co-occur in the same groundwater plume. Because historic handling, storage, and disposal practices of chlorinated solvents have resulted in widespread groundwater contamination at USAF installations, significant potential exists for unidentified1,4-dioxane contamination. Therefore, the objective of this investigation is to determine the extent to which 1,4-dioxane co-occurs with TCE compared to TCA, and if these chemicals are co-contaminants, whether or not there is significant correlation using available monitoring data. To accomplish these objectives, the USAF Environmental Restoration Program Information Management System (ERPIMS) was queried for all relevant records for groundwater monitoring wells (GMWs) with 1,4-dioxane, TCA, and TCE, on which both categorical and quantitative analyses were performed. Overall, ERPIMS contained 5,788 GMWs from 49 installations with records for 1,4-dioxane, TCE, and TCA analytes. 1,4-Dioxane was observed in 17.4% of the GMWs with detections for TCE and/or TCA, which accounted for 93.7% of all 1,4-dioxane detections, verifying that 1,4-dioxane is seldom found independent of chlorinated solvent contamination. Surprisingly, 64.4% of all 1,4-dioxane detections were associated with TCE independently. Given the extensive dataset, these results conclusively demonstrate for the first time that 1,4-dioxane is a relatively common groundwater co-contaminant with TCE. Trend analysis demonstrated a positive log-linear relationship where median 1,4-dioxane levels increased between ∼6% and ∼20% of the increase in TCE levels. In conclusion, this data mining exercise suggests that 1,4-dioxane has a probability of co-occurrence of ∼17% with either TCE and/or TCA. Given the challenges imposed by remediation of 1,4-dioxane and the pending promulgation of a federal regulatory standard, environmental project managers should utilize the information presented in this paper for prioritization of future characterization efforts to respond to the emerging issue. Importantly, site investigations should consider 1,4-dioxane a potential co-contaminant of TCE in groundwater plumes. Integr Environ Assess Manag © 2012 SETAC.

Abstract  Lactational transfer of chemicals to nursing infants is a concern for occupational physicians when women who are breast-feeding return to the workplace. Some work environments, such as paint shops, have atmospheric contamination from volatile organic chemicals (VOCs). Very little is known about the extent of exposure a nursing infant may receive from the mother's occupational exposure. A physiologically based pharmacokinetic model was developed for a lactating woman to estimate the amount of chemical that a nursing infant ingests for a given nursing schedule and maternal occupational exposure. Human blood/air and milk/air partition coefficients (PCs) were determined for 19 VOCs. Milk/blood PC values were above 3 for carbon tetrachloride, methylchloroform, perchloroethylene, and 1,4-dioxane, while the remaining 16 chemicals had milk/blood PC values of less than 3. Other model parameters, such as solid tissue PC values, metabolic rate constants, blood flow rates, and tissue volumes were taken from the literature and incorporated into the lactation model. In a simulated exposure of a lactating woman to a threshold limit value concentration of an individual chemical, only perchloroethylene, bromochloroethane, and 1,4-dioxane exceeded the U.S. Environmental Protection Agency non-cancer drinking water ingestion rates for children. Very little data exists on the pharmacokinetics of lactational transfer of volatile organics. More data are needed before the significance of the nursing exposure pathway can be adequately ascertained. Physiologically based pharmacokinetic models can play an important role in assessing lactational transfer of chemicals.

Abstract  1,4-Dioxane (dioxane) is an emerging groundwater contaminant that has significant regulatory implications and potential remediation costs, but our current understanding of its occurrence and behavior is limited. This study used intensive data mining to identify and evaluate >2000 sites in California where groundwater has been impacted by chlorinated solvents and/or dioxane. Dioxane was detected at 194 of these sites, with 95% containing one or more chlorinated solvents. Dioxane frequently co-occurs with 1,1,1-trichloroethene (1,1,1-TCA) (76% of the study sites), but despite this, no dioxane analyses were conducted at 332 (67%) of the sites where 1,1,1-TCA was detected. At sites where dioxane has been identified, plumes are dilute but not large (median maximal concentration of 365 mu g/L; median plume length of 269 m) and have been delineated to a similar extent as typically co-occurring chlorinated solvents. Furthermore, at sites where dioxane and chlorinated solvents co-occur, dioxane plumes are frequently shorter than the chlorinated solvent plumes (62%). The results suggest that dioxane has not migrated beyond chlorinated solvent plumes and existing monitoring networks at the majority of sites, and that the primary risk is the large number of sites where dioxane is likely to be present but has yet to be identified.

Abstract  There is a critical need to develop appropriate management strategies for 1,4-dioxane (dioxane) due to its widespread occurrence and perceived recalcitrance at groundwater sites where chlorinated solvents are present. A comprehensive evaluation of California state (GeoTracker) and Air Force monitoring records was used to provide significant evidence of dioxane attenuation at field sites. Temporal changes in the site-wide maximum concentrations were used to estimate source attenuation rates at the GeoTracker sites (median length of monitoring period = 6.8 years). While attenuation could not be established at all sites, statistically significant positive attenuation rates were confirmed at 22 sites. At sites where dioxane and chlorinated solvents were present, the median value of all statistically significant dioxane source attenuation rates (equivalent half-life = 31 months; n = 34) was lower than 1,1,1-trichloroethane (TCA) but similar to 1,1-dichloroethene (1,1-DCE) and trichloroethene (TCE). Dioxane attenuation rates were positively correlated with rates for 1,1-DCE and TCE but not TCA. At this set of sites, there was little evidence that chlorinated solvent remedial efforts (e.g., chemical oxidation, enhanced bioremediation) impacted dioxane attenuation. Attenuation rates based on well-specific records from the Air Force data set confirmed significant dioxane attenuation (131 out of 441 wells) at a similar frequency and extent (median equivalent half-life = 48 months) as observed at the California sites. Linear discriminant analysis established a positive correlation between dioxane attenuation and increasing concentrations of dissolved oxygen, while the same analysis found a negative correlation with metals and CVOC concentrations. The magnitude and prevalence of dioxane attenuation documented here suggest that natural attenuation may be used to manage some but not necessarily all dioxane-impacted sites.