Occurrence of halogenated transformation products of selected pharmaceuticals and personal care products in secondary and tertiary treated wastewaters from southern California.

Final effluent samples from 10 southern California (United States) wastewater treatment facilities, employing four distinct treatment schemes, were surveyed for selected pharmaceuticals, personal care products (PPCPs), alkylphenols, and 21 of their halogenated disinfection byproducts. Chlorinated and brominated standards and isotopically labeled internal standards were synthesized and purified to confirm and more accurately quantify selected disinfection byproducts of salicylic acid, bisphenol A, gemfibrozil, naproxen, diclofenac, technical 4-nonylphenol, and 4-tert-octylphenol using high-performance liquid chromatography and tandem mass spectrometry. Concentrations of parent compounds ranged from <10 to 3830 ng/L (gemfibrozil), and those of chloro/bromo byproducts ranged from <4 to 370 ng/L (dibromo nonylphenol). The highest concentrations of parent compounds were measured in effluent that was not subjected to tertiary treatment. The chlorinated and brominated byproduct concentration may be affected by the influent concentration of parent compounds, hydraulic retention times, and chlorine contact times. Salicylic acid was readily halogenated, which is evident from the ratio of halogenated to nonhalogenated species. There were no measured chlorinated byproducts of bisphenol A despite occasionally high concentrations of the parent compound. Not surprisingly, higher concentrations of most brominated species were measured in the treatment plant with the highest bromide concentrations. These results demonstrate the occurrence of novel halogenated byproducts of PPCPs that have limited toxicological data and significant uncertainty with regard to their risk to ecological systems.

The relationships of biochemical endpoints to histopathology and population metrics in feral flatfish species collected near the municipal wastewater outfall of Orange County, California, USA.

In July 2000, 330 individuals of three flatfish species were collected from reference locations and nine sites surrounding the outfall of the Orange County (CA, USA) Sanitation District (OCSD) municipal wastewater discharge. Species included hornyhead turbot (Pleuronichthys verticalis), English sole (Pleuronectes vetulus), and bigmouth sole (Hippoglossina stomata). Livers of sampled animals were examined for the expression of vitellogenin (in males), cytochrome P450 1A (CYP1A), and DNA damage (comet assay). Biliary fluorescent aromatic compounds (FACs) were also measured. Comparisons with tissue and sediment contaminant residues, liver histopathology, and population estimates were assessed to determine whether relationships exist between levels of biological organization. The CYP1A results indicated exposure to planar aromatic hydrocarbons at one nearshore site. Regression analysis of all English sole CYP1A to total sediment polychlorinated biphenyls (PCBs) (r2 = 0.97; p < 0.05) indicated a significant correlation. Widespread exposure to estrogens was observed at all sites without correlation to the abundance of the three species examined. Fluorescent aromatic compounds demonstrated no correlation to CYP1A expression. Overall, histopathology and biochemical endpoints did not indicate significant adverse effects in fish at the OCSD outfall.

Evaluation of reproductive endocrine status in hornyhead turbot sampled from Southern California's urbanized coastal environments.

As part of a regionwide collaboration to determine the occurrence of contaminants and biological effects in coastal ecosystems offshore of urban southern California, the present study characterized the reproductive endocrinology of an indigenous flatfish, the hornyhead turbot (Pleuronichthys verticalis), and compared groups sampled from different study sites representing varying degrees of pollution to screen for potential endocrine disruptive effects. Turbot were sampled from locations near the coastal discharge sites of four large municipal wastewater treatment plants (WWTPs) located between Los Angeles and San Diego, California, USA, and were compared with fish sampled from three far-field reference locations in the region. Despite environmental presence of both legacy contaminants and contaminants of emerging concern and evidence for fish exposure to several classes of contaminants, both males and females generally exhibited coordinated seasonal reproductive cycles at all study sites. Patterns observed included peaks in sex steroids (17ß-estradiol, testosterone, 11-ketotestosterone) in the spring and low levels in the fall, changes corresponding to similarly timed gonadal changes and plasma vitellogenin concentrations in females. Comparisons between fish captured at the different study sites demonstrated some regional differences in plasma levels of estrogens and androgens, indicative of location-associated effects on the endocrine system. The observed differences, however, could not be linked to the ocean discharge locations of four of the largest WWTPs in the world.

Liver lesions in demersal fishes near a large ocean outfall on the San Pedro Shelf, California.

The prevalence of toxicopathic liver lesions in demersal fish on the San Pedro Shelf, California was determined for a 15-year period (1988-2003). Fish livers were sampled at fixed locations as part of the Orange County Sanitation Districts (OCSD) ocean monitoring program. Histopathological examination of selected fish liver tissues was studied to determine whether the wastewater discharge had affected fish health. The prevalence of toxicopathic lesion classes neoplasms (NEO), preneoplastic foci of cellular alteration (FCA), and hydropic vacuolation (HYDVAC) varied among species and locations. For all species sampled, severe lesions occurred in 6.2% of the fish examined (n=7,694). HYDVAC (4.1%) was the most common toxicopathic lesion type followed by FCA (1.4%) and NEO (0.7%). HYDVAC occurred only in white croaker (Genyonemus lineatus), accounting for 84.8% of the toxicopathic lesions for this species. Prevalence of HYDVAC, NEO, and FCA in white croaker was 15.2, 2.0, and 0.7%, respectively. The prevalence of HYDVAC and NEO in white croaker increased with age and size but there was no sexual difference. A linear regression model was used for hypothesis testing to account for significant differences in fish size (and age for croakers) at the different sampling locations. This analysis showed that for HYDVAC there was no spatial or location effect for lesion rate or size/age of onset. For NEO, the model predicted that white croaker near the wastewater outfall may acquire these lesions at a smaller size/younger age, and at a higher rate, than at other sites. However, this result may be biased due to the unequal size frequency distributions and the low prevalence of NEO in white croaker at the different sampling sites. Bigmouth sole (Hippoglossina stomata) had a prevalence of FCA and NEO of 1.3 and 0.35%, respectively, but the prevalence and distribution of lesions was too few for statistical testing. There was no sexual difference for lesion prevalence in hornyhead turbot (Pleuronichthys verticalis) and the prevalence of FCA and NEO was 3.4 and 0.37%, respectively. FCA prevalence increased with size in hornyhead turbot and there were no significant spatial differences for lesion rates and fish size at lesion onset. Overall, consistent spatial differences for lesion prevalence were not demonstrated and highlight the analytical difficulties of detecting a possible point source impact when the effect is rare, correlated with the size/age structure of the population, and may be caused by exposure to unknown multiple sources. Thus, the usefulness of liver histopathology as a point-source monitoring tool is best applied to where the spatial scale of impact generally exceeds the home range of the target species.