Influences of Wastewater Treatment on the Occurrence of Parabens, p-Hydroxybenzoic Acid and Their Chlorinated and Hydroxylated Transformation Products in the Brazos River (Texas, USA).

Parabens are ubiquitous, being found in surface waters around the world. Although little is known about the release of paraben transformation products and fate of transformation products in surface water. This study evaluates both parabens and paraben transformation products in the Brazos River upstream and downstream of a wastewater facility located in Waco, Texas. Concentrations of thirteen compounds were reported in this study, five parent parabens and eight paraben disinfection by-products. Analyte concentrations were spatially evaluated to determine if release of wastewater effluent affects their concentrations in the river. Two Brazos River tributaries were also sampled to determine if they released parabens and related compounds to the Brazos. Sampling occurred weekly for one year with at least 40 samples collected at each site. Analyses were completed for both yearly and seasonal data. Sites downstream of wastewater treatment outfalls had lower concentrations of methyl paraben during the yearly analysis and across multiple seasons in the seasonal analysis with average yearly annual methyl paraben concentrations decreasing from 0.83 ng/L at site 3 to 0.09 ng/L at site 4. Para-hydroxybenzoic acid was the compound present in greatest concentration at most sites across most seasons, with the highest average annual concentration of 10.30 ng/L at site 2. Spatial changes in para-hydroxybenzoic acid varied by season, with seasonal trends only identifiable after normalization by flow. Dichlorinated paraben concentrations increased in the river at sites downstream of wastewater treatment with a yearly average dichlorinated methyl paraben concentration of 0.490 ng/L at site 3 to 1.53 at site 4, just downstream of the major wastewater treatment plant. Concentration increases indicate that wastewater effluent contains sufficiently high dichlorinated paraben concentrations to effect concentrations downstream of effluent discharges. Dichlorinated species also persisted in the environment, with no significant decreases at sites further downstream during any season with an annual average dichlorinated methyl paraben concentration of 1.23 ng/L at site 6. Methyl paraben concentrations decreased at the site furthest downstream to a concentration of 0.081 ng/L, while dichlorinated methyl paraben concentrations remained stable with a concentration of 1.10 ng/L at the site furthest downstream. Due to the dichlorinated species being released in higher concentrations in effluent than parents and being more resistant to degradation, the dichlorinated parabens are more likely to be environmentally relevant than are parent parabens.

Evaluating seasonal differences in paraben transformation at two different wastewater treatment plants in Texas and comparing parent compound transformation to byproduct formation.

Parabens are commonly used preservatives that are weakly estrogenic. Wastewater effluent is the greatest contributor to the spread of parabens into rivers and other surface water. While previous studies indicate parabens are well removed in wastewater treatment by way of transformation, not much is known about the paraben transformation products. This study evaluates paraben transformation and release at two different wastewater treatment plants in Texas. Paraben concentrations were quantified for influent and effluent by season and by year at both treatment plants. Both seasonal and annual transformation rates were compared between the two wastewater treatment plants. Compounds were compared to evaluate differences in transformation rates and to determine if decreases in parent product concentrations are correlated to changes in transformation product concentrations. The study took place over one year and evaluated each season. Spring had higher influent concentrations and transformation rates at treatment plant 1, while summer had higher influent concentrations and transformation rates at treatment plant 2. PHBA was present in greatest amounts in influent and effluent at both sites with average yearly influent concentrations at 223.9 pM at plant 1 and 211.4 pM at plant 2. Transformation rates of parent parabens were greater at plant 1 with concentration of all three shorter chained parabens decreasing by over 50% after treatment. Formation of dichlorinated transformation products were greater at plant 1 with concentrations of Cl2MeP increasing by 1200% after treatment and Cl2EtP increasing by 940%. While shorter chained parabens generally had a greater transformation rate, no correlations were found between decreases in methyl and ethyl parabens and the formation of their respective dichlorinated transformation products.

Land use, season, and parasitism predict metal concentrations in Australian flying fox fur.

Urban-living wildlife can be exposed to metal contaminants dispersed into the environment through industrial, residential, and agricultural applications. Metal exposure carries lethal and sublethal consequences for animals; in particular, heavy metals (e.g. arsenic, lead, mercury) can damage organs and act as carcinogens. Many bat species reside and forage in human-modified habitats and could be exposed to contaminants in air, water, and food. We quantified metal concentrations in fur samples from three flying fox species (Pteropus fruit bats) captured at eight sites in eastern Australia. For subsets of bats, we assessed ectoparasite burden, haemoparasite infection, and viral infection, and performed white blood cell differential counts. We examined relationships among metal concentrations, environmental predictors (season, land use surrounding capture site), and individual predictors (species, sex, age, body condition, parasitism, neutrophil:lymphocyte ratio). As expected, bats captured at sites with greater human impact had higher metal loads. At one site with seasonal sampling, bats had higher metal concentrations in winter than in summer, possibly owing to changes in food availability and foraging. Relationships between ectoparasites and metal concentrations were mixed, suggesting multiple causal mechanisms. There was no association between overall metal load and neutrophil:lymphocyte ratio, but mercury concentrations were positively correlated with this ratio, which is associated with stress in other vertebrate taxa. Comparison of our findings to those of previous flying fox studies revealed potentially harmful levels of several metals; in particular, endangered spectacled flying foxes (P. conspicillatus) exhibited high concentrations of cadmium and lead. Because some bats harbor pathogens transmissible to humans and animals, future research should explore interactions between metal exposure, immunity, and infection to assess consequences for bat and human health.

Identifying potential paraben transformation products and evaluating changes in toxicity as a result of transformation.

Parabens are a class of compounds often used as preservatives in personal care products, pharmaceuticals, and food. They have received attention recently due to findings that demonstrate estrogenic impacts and other adverse effects of parabens. Release into wastewater effluent is considered a major contributor to the spread of parabens into surface water. Current regulations in areas such as Japan, Europe, and Southeast Asia limit the concentrations of parabens that can be used in formulations but do not address concentrations discharged into waterbodies. Recent studies suggest that parent parabens are effectively eliminated by transformation during the wastewater treatment processes. Common tertiary treatments include ultrafiltration, chlorination, UV disinfection and ozonation. Ultrafiltration is used to remove solids before a disinfection step. Of the disinfection steps, ozonation is often the most effective at removing parabens. Not much is known about the toxicities of paraben transformation products. Of the transformation products, chlorinated parabens and PHBA are the most studied. Previous studies have shown that chlorinated parabens have greatly reduced estrogen agonistic activity when compared with the activity of parents. However, more recent studies have found that halogenated parabens actually have estrogen antagonistic activity. Further research involving chlorinated parabens could include other toxic endpoints. No known studies have evaluated adverse effects of oxygenated parabens. Parabens can interact with chlorine residues in the environment and form chlorinated products, this will occur at a faster rate during chlorination. Ozonation will oxidize parabens and UV disinfection can both oxidize and halogenate parabens. All studies determining potential transformation products have been done in laboratory settings or specific conditions. Further research is needed to determine if these transformations occur in situ. PRACTITIONER POINTS: Common chemical processes utilized by wastewater treatment facilities are effective at transforming parabens. Paraben transformation products are released in greater concentration in effluent than parent paraben compounds. Halogenated transformation products have been identified as estrogen receptor antagonists.