High-Resolution Mass Spectrometry Identification of Novel Surfactant-Derived Sulfur-Containing Disinfection Byproducts from Gas Extraction Wastewater.

Introduction of oil and gas extraction wastewaters (OGWs) to surface water leads to elevated halide levels from geogenic bromide and iodide, as well as enhanced formation of brominated and iodinated disinfection byproducts (DBPs) when treated. OGWs contain high levels of chemical additives used to optimize extraction activities, such as surfactants, which have the potential to serve as organic DBP precursors in OGW-impacted water sources. We report the first identification of olefin sulfonate surfactant-derived DBPs from laboratory-disinfected gas extraction wastewater. Over 300 sulfur-containing DBPs, with 43 unique molecular formulas, were found by high-resolution mass spectrometry, following bench-scale chlor(am)ination. DBPs consisted of mostly brominated species, including bromohydrin sulfonates, dihalo-bromosulfonates, and bromosultone sulfonates, with chlorinated/iodinated analogues formed to a lesser extent. Disinfection of a commercial C12-olefin sulfonate surfactant mixture revealed dodecene sulfonate as a likely precursor for most detected DBPs; disulfur-containing DBPs, like bromosultone sulfonate and bromohydrin disulfonate, originated from olefin disulfonate species, present as side-products of olefin sulfonate production. Disinfection of wastewaters increased mammalian cytotoxicity several orders of magnitude, with chloraminated water being more toxic. This finding is important to OGW-impacted source waters because drinking water plants with high-bromide source waters may switch to chloramination to meet DBP regulations.

Mechanistic relationships between hepatic genotoxicity and carcinogenicity in male B6C3F1 mice treated with polycyclic aromatic hydrocarbon mixtures.

The genotoxicity of a complex mixture [neutral fraction (NF)] from a wood preserving waste and reconstituted mixture (RM) mimicking the NF with seven major polycyclic aromatic hydrocarbons (PAHs) and benzo(a)pyrene (BaP) was investigated by determining DNA adducts and tumor incidence in male B6C3F1 mice exposed to three different doses of the chemical mixtures. The peak values of DNA adducts were observed after 24 h, and the highest levels of PAH-DNA adducts were exhibited in mice administered NF + BaP, and the highest tumor incidence and mortality were also observed in this group. DNA adduct levels after 1, 7, or 21 days were significantly correlated with animal mortality and incidence of total tumors including liver, lung, and forestomach. However, only hepatic DNA adducts after 7 days significantly correlated with liver tumor incidence. Most proteins involved in DNA repair including ATM, pATR, Chk1, pChk1, DNA PKcs, XRCC1, FANCD2, Ku80, Mre11, and Brca2 were significantly lower in liver tumor tissue compared to non-tumor tissue. Expressions of proteins involved in apoptosis and cell cycle regulation were also significantly different in tumor versus non-tumor tissues, and it is possible that PAH-induced changes in these gene products are important for tumor development and growth.

Impacts of hydraulic fracturing wastewater from oil and gas industries on drinking water: Quantification of 69 disinfection by-products and calculated toxicity.

Oil and gas production generates large amounts of brine wastewater called "produced water" with various geogenic and synthetic contaminants. These brines are generally used in hydraulic fracturing operations to stimulate production. They are characterized by elevated halide levels, particularly geogenic bromide and iodide. Such salt concentrations in produced water may be as high as thousands of mg/L of bromide and tens of mg/L of iodide. Large volumes of produced water are stored, transported, reused in production operations, and ultimately disposed of by deep well injection into saline aquifers. Improper disposal may potentially contaminate shallow freshwater aquifers and impact drinking water sources. Because conventional produced water treatment typically does not remove halides, produced water contamination of groundwater aquifers may cause the formation of brominated and iodinated disinfection by-products (I-DBPs) at municipal water treatment plants. These compounds are of interest because of their higher toxicity relative to their chlorinated counterparts. This study reports a comprehensive analysis of 69 regulated and priority unregulated DBPs in simulated drinking waters fortified with 1 % (v/v) oil and gas wastewater. Impacted waters produced 1.3×-5× higher levels of total DBPs compared to river water after chlorination and chloramination. Individual DBP levels ranged from (<0.1-122 µg/L). Overall, chlorinated waters formed highest levels, including trihalomethanes that would exceed the U.S. EPA regulatory limit of 80 µg/L. Chloraminated waters had more I-DBP formation and highest levels of haloacetamides (23 µg/L) in impacted water. Calculated cytotoxicity and genotoxicity were higher for impacted waters treated with chlorine and chloramine than corresponding treated river waters. Chloraminated impacted waters had the highest calculated cytotoxicity, likely due to higher levels of more toxic I-DBPs and haloacetamides. These findings demonstrate that oil and gas wastewater if discharged to surface waters could adversely impact downstream drinking water supplies and potentially affect public health.

Exploring Demographic and Environmental Factors Related to Unintentional Pesticide Poisonings in Children and Adolescents in Texas.

There is limited literature on the frequency and distribution of pesticide exposures, specifically with respect to demographic and environmental factors in the United States. The purpose of this exploratory study was to investigate geographic trends and factors associated with unintentional pesticide exposures in children and adolescents in Texas. The study used an ecological design with secondary data. A spatial scan statistic, based on a Poisson regression model, was employed to identify spatial clusters of unintentional pesticide-related poison center exposures. Next, logistic regression models were constructed to identify potential demographic and environmental factors associated with unintentional pesticide-related poison center exposures. There were 59,477 unintentional pesticide-related poison center exposures from 2000 to 2013. The spatial scan statistic found a change in the number of counties in the identified clusters (e.g. , aggregation of counties with higher than expected exposures) for two time periods (2000-2006; 2007-2013). Based on the logistic regression models, factors associated with unintentional pesticide-related poison center exposures were percent black or African American population, year structure built, and percent moved in the past 12 months. In conclusion, this study found certain demographic and environmental factors may be associated with unintentional pesticide-related poison center exposures. Through understanding trends and associated factors, public health professionals can design interventions for populations at higher risk of pesticide exposures. This study also supports the use of spatial methods being utilized to expand upon current analysis of poison center data. Future research should confirm and build upon these findings.

Pesticide-Related Hospitalizations Among Children and Teenagers in Texas, 2004-2013.

OBJECTIVE: Acute exposure to pesticides is associated with nausea, headaches, rashes, eye irritation, seizures, and, in severe cases, death. We characterized pesticide-related hospitalizations in Texas among children and teenagers for 2004-2013 to characterize exposures in this population, which is less well understood than pesticide exposure among adults. METHODS: We abstracted information on pesticide-related hospitalizations from hospitalization data using pesticide-related International Classification of Diseases, Ninth Revision, Clinical Modification (ICD-9-CM) codes and E-codes. We calculated the prevalence of pesticide-related hospitalizations among children and teenagers aged #19 years for all hospitalizations, unintentional exposures, intentional exposures, pesticide classifications, and illness severity. We also calculated age- and sex-specific prevalence of pesticide-related hospitalizations among children. RESULTS: The prevalence of pesticide-related hospitalizations among children and teenagers was 2.1 per 100,000 population. The prevalence of pesticide-related hospitalizations per 100,000 population was 2.7 for boys and 1.5 for girls. The age-specific prevalence per 100,000 population was 5.3 for children aged 0-4 years, 0.3 for children and teenagers aged 5-14 years, and 2.3 for teenagers aged 15-19 years. Children aged 0-4 years had the highest prevalence of unintentional exposures, whereas teenagers aged 15-19 years had the highest prevalence of intentional exposures. Commonly reported pesticide categories were organophosphates/carbamates, disinfectants, rodenticides, and other pesticides (e.g., pyrethrins, pyrethroids). Of the 158 pesticide-related hospitalizations, most were coded as having minor (n=86) or moderate (n=40) illness severity. CONCLUSION: Characterizing the prevalence of pesticide-related hospitalizations among children and teenagers leads to a better understanding of the burden of pesticide exposures, including the type of pesticides used and the severity of potential health effects. This study found differences in the frequency of pesticide-related hospitalizations by sex, age, and intent (e.g., unintentional vs. intentional).

Pesticide-related poison center exposures in children and adolescents aged ≤19 years in Texas, 2000-2013.

CONTEXT: Although national poison center data show that pesticides were the 8th most commonly reported substance category (3.27%) for children aged ≤5 years in 2014, there is limited information on childhood and adolescent pesticide exposures. OBJECTIVE: This study assessed pesticide-related poison center exposures in children and adolescents aged ≤19 years from 2000-2013 in Texas to characterize the potential burden of pesticides. MATERIALS AND METHODS: Pesticide-related poison center exposures among children and adolescents aged ≤19 years reported to Texas poison centers were identified. The distribution of exposures was estimated by gender, age category, medical outcome, management site, exposure route, and pesticide category. RESULTS: From 2000 to 2013, there were 61,147 pesticide-related poison center exposures in children and adolescents aged ≤19 years. The prevalence was highest among males at 864.24 per 100,000 population. The prevalence of unintentional exposures was highest among children aged ≤5 years at 2310.69 per 100,000 population, whereas the prevalence of intentional exposures was highest among adolescents aged 13-19 years at 13.82 per 100,000 population. A majority of medical outcomes reported were classified as having no effect (30.24%) and not followed, but minimal clinical effects possible (42.74%). Of all the exposures, 81.24% were managed on site. However, 57% of intentional exposures were referred to or treated at a health-care facility. The most common routes of exposure were ingestion (80.83%) and dermal (17.21%). The most common pesticide categories included rodenticides (30.02%), pyrethrins/pyrethroids (20.69%), and other and unspecified insecticides (18.14%). DISCUSSION: The study found differences in the frequency of exposures by intent for sex and age categories, and identified the most common medical outcomes, management site, exposure route, and pesticide category. CONCLUSION: Through characterizing pesticide-related poison center exposures, future interventions can be designed to address groups with higher prevalence of exposure.