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Aromatic sensitizers and related compounds (SRCs) originating from thermal recording material as impurities in waste paper have been detected in aquatic environments near cities where the paper industry is flourishing. In the present study, the levels of exposure to such SRCs and the stable isotope ratios (δ13C and δ15N) in different fish species (Konosirus punctatus, Takifugu niphobles, and Tribolodon hakonensis) were analyzed. These fish species were collected from the vicinity of waste paper recycling plants in Japan. Eleven SRCs were identified in fish muscle at total concentration levels (ΣSRCs) of 64 to 818 ng/g wet weight (mean 181 ng/L wet wt). The dominant SRCs in the fish samples were 1,1-di(4-methylphenyl)ethane, 1,2-bis(3-methylphenoxy)ethane, and 1,4-dibenzyloxybenzene. Stable isotope ratios showed that, although three species feed on the same trophic level, K. punctatus and T. niphobles live in waters farther offshore than those in which T. hakonensis live. The contributions of various factors to the accumulation were also assessed. The lipid content (r2 = 0.512, p

The ability of some pulp mill effluents (PME) to act as reproductive and endocrine disrupters in fish is well documented in the literature. However, changes are not always consistent with regard to species, gender, hormones, or reproductive effects. In the present study, the presence of the first intersexed fish that, to our knowledge, has been found in a Canadian river exposed to PME, is reported. A field survey of the Wabigoon River near Dryden, Ontario, in the fall of 2000 found intersexed walleye (Sander vitreus vitreus) with significantly altered hormone levels and reduced gonad size. The Wabigoon River receives discharge from a bleached kraft pulp and paper mill and a municipal wastewater (MWW) plant. It also has historical sediment contamination (wood fiber mats) contributing to extended periods of low dissolved oxygen under low flow, drought conditions. A mesocosm-based partial life cycle test exposing fathead minnows (Pimephales promelas) to reference water, 20% effluent volume to river volume (v/v), 40% (v/v), or 60% (v/v) PME as well as a field survey of the walleye in the Wabigoon River were conducted. The only change in our mesocosm exposure was a decrease in testosterone in males with increasing effluent concentration and vitellogenin induction in males exposed to 60% (v/v) effluent. These results did not reflect the magnitude of endocrine disruption seen in the wild fish survey. Several hypotheses that may explain these discrepancies are proposed. Specifically, evidence is offered from published studies indicating that either hypoxia or MWW, alone or in combination with PME, may explain the discrepancy between our field experiment and the wild fish survey. The present study illustrates the complexities of multistressor receiving environments and the need for the development of cumulative effects assessment approaches. Environ. Toxicol. Chem. 2010;29:952–965. © 2010 SETAC

The Canadian environmental effects monitoring (EEM) program is a regulated, cyclical, industry-funded program designed to determine whether receiving water impacts exist when a mill is in compliance with its discharge limits. The results from three cycles of the fish monitoring program (1992 to 2004) are available from over 200 surveys of fish compared between sites located upstream and downstream of pulp and paper mill effluent outfalls. Previous meta-analyses have shown a national average response pattern across cycles characterized by an increase in endpoints measuring energy storage and growth and a decrease in a reproductive endpoint, consistent with a response of nutrient enrichment in combination with some form of metabolic disruption. Although the national average pattern of effects was temporally consistent, there was some variability in the magnitude of effects among cycles. Questions were raised as to whether the intercycle variability was due to changes in effluent quality or due, at least in part, to other factors. The present study compares responses over the first three cycles, and shows that the choice of sentinel species is likely to be a major contributing factor to the variability in observed effects. Subset analyses using studies from mills that used the same sentinel species across cycles reveal fairly uniform responses and little evidence of significant improvements in overall fish health from cycles one to three. However, a meta-analysis using 1991 data collected from 10 mills before the implementation of the EEM program and data from the same mills collected during cycles one to three of the program reveal significantly reduced effects on relative liver weight and potential improvements in other endpoints. Environ. Toxicol. Chem. 2010;29:440–452. © 2009 SETAC

For the last 20 years, studies conducted in North America, Scandinavia, and New Zealand have shown that pulp and paper mill effluents affect fish reproduction. Despite the level of effort applied, few leads are available regarding the factors responsible. Effluents affect reproduction in multiple fish species, as evidenced by decreased gonad size, decreased circulating and gonadal production of reproductive steroids, altered expression of secondary sex characteristics, and decreased egg production. Several studies also have shown that effluent constituents are capable of accumulating in fish and binding to sex steroid receptors/ binding proteins. Studies aimed at isolating biologically active substances within the pulping and papermaking process have provided clues about their source, and work has progressed in identifying opportunities for in-mill treatment technologies. Following comparisons of manufacturing processes and fish responses before and after process changes, it can be concluded that effluent from all types of mill processes are capable of affecting fish reproduction and that any improvements could not be attributed to a specific process modification (because mills normally performed multiple modifications simultaneously). Improved reproductive performance in fish generally was associated with reduced use of molecular chlorine, improved condensate handling, and liquor spill control. Effluent biotreatment has been effective in reducing some effects, but biotreated effluents also have shown no difference or an exacerbation of effects. The role of biotreatment in relation to effects on fish reproduction remains unclear and needs to be resolved.

Eight phenolics were detected in samples collected from areas where paper-recycling process water is discharged. The detected concentration levels were up to 270 microg/L and 230 microg/g in water samples and sediment samples, respectively, obtained from both the outfall of the paper-recycling process water and its downstream areas. In particular, totarol (compound 4), 2,4-bis(1-phenylethyl)phenol (compound 6), 4,4'-butylidenebis(6-t-butyl-m-cresol) (compound 7), 2,4-bis(1-phenylethyl)-6-chlorophenol (compound 8), and 4-hydroxy-4'-isopropoxydiphenyl sulfone (compound 9) were identified for the first time as environmental pollutants. The estrogenicities of the identified compounds were assessed by yeast two-hybrid assays incorporating either the human or medaka fish (Oryzias latipes) estrogen receptor alpha (hERalpha and medERalpha, respectively) and an estrogen receptor competitive enzyme-linked immunosorbent assay (ER-ELISA) both with and without metabolic activation by a rat liver S9 mix. Bisphenol A (compound 3) and 2-naphthol (compound 1) exhibited activity in the assays of both hERalpha and medERalpha without the S9 mix. The relative activity (%) to 17beta-estradiol was 0.0015% for compound 3 and 0.0009% for compound 1 in the hERalpha assay and 0.027% for compound 3 and 0.0093% for compound 1 in the medERalpha assay. These compounds were attenuated by the S9 mix. The binding affinity was evaluated using an ER-ELISA. Compounds 3, 4, 6, and 7 exhibited affinity without the S9 mix. After exposure to the S9 mix, however, the binding affinity of compound 7 was eliminated by the S9 mix; those of compounds 3, 4, and 6 were attenuated; and that of compound 8 exhibited affinity. A comprehensive assessment of the estrogenicities of the phenolics originating from thermal paper and their implications for an aquatic environment may require an examination of the components of the phenolics, as in the present study.

In previous experiments, bleached kraft chemical recovery condensates generated during softwood pulp production have been identified as a primary source of substances causing testosterone depressions in mummichog (Fundulus heteroclitus). Recent toxicity identification evaluations have encountered inconsistencies in the potential of condensates and fractions to reduce steroid concentrations between three repeated exposures. To assess the sources of these inconsistencies, temporal assessments of condensate extractives and analytical methodologies were evaluated. Condensates were collected during a six-month period, extracted by solid-phase extraction (SPE), and analyzed by gas chromatography–mass spectrometry and gas chromatography–flame photometric detection. All unique extractives were cataloged by mass spectra, peak area, and gas chromatographic retention time, and nine were confirmed and quantified against authentic standards. Confirmed components included phenolic guaiacyl–based lignin degradation products, sulfur (S8), three diterpenoids, and a dimethoxy stilbene. Concentrations of confirmed condensate extractives were consistent in all samples collected. Spiking experiments of confirmed extractives revealed substantial losses following high-pressure liquid chromatographic fractionation and three different methods of fraction preparation. In an effort to propose chemical classes associated with biological activity, all unique condensate extractives in previously established bioactive and inactive fractions were classified based on their potential to depress testosterone in mummichog. Of 39 unique components in bioactive SPE extracts of condensates, six were associated with hormonal activity. Mass spectral interpretation indicated hydroxylated diterpenoids, sesquiterpenoids, and a lignin-derived stilbene as classes of chemicals associated with steroid depressions.

Perch (Perca fluviatilis L.) and roach (Rutilus rutilus L.) populations in a state of late vitellogenesis were studied downstream of two pulp and paper mills and at upstream references in southern Lake Saimaa, Finland. The mills used elemental chlorine-free bleaching and activated sludge effluent treatment technologies. The exposure of fish to pulp mill effluents, as measured by concentrations of chlorophenolics in the bile and liver ethoxyresorufin-O-deethylase (EROD) activity, was low and almost similar to the references. Nevertheless, bile resin acid concentrations in exposed perch and roach (260-320 micrograms/ml) and bile beta-sitosterol concentrations in exposed roach (1.5-3.5 micrograms/ml) were, respectively, 10 to 30 times and 2 to 5 times higher compared with the references. Reproductive parameters like plasma 17 beta-estradiol and testosterone levels were lower in exposed male and female perch but the same in roach. Vitellogenin concentrations in plasma and liver cytosol of roach were similar. Gonad weight and fecundity were lower in exposed female perch but similar in roach. The relative liver weight was higher in exposed roach but not in perch. The body condition and immunologic parameters in fish were the same. The growth and age at maturity of exposed perch and roach were similar to the references. The size and age distribution of perch in the recipient of one of the mills was shifted toward smaller and younger fish. Our results show that several reproductive variables were altered in late vitellogenic perch in the vicinity of the mills, but they were not altered in roach.