Assessing wild fish exposure to ligands for sex steroid receptors from pulp and paper mill effluents in the Biobio River Basin, Central Chile.

Bioactive substances in the Biobio River Basin in Chile were examined by deploying Semi Permeable Membrane Devices (SPMDs) upstream and downstream of 4 pulp mill effluent discharges. Androgenic and estrogenic activity of SPMD extracts were then evaluated using in vitro fish sex steroid receptor binding assays. The results indicated the occurrence of estrogenic type compounds associated with one of the mill discharges. A significant correlation among the presence of these compounds, an increase in gonadosomatic index GSI and induction of hepatic EROD activity of two native fish species was observed. However, no significant presence of mature oocytes in female gonads was detected. Although EROD induction was observed in sites impacted by mill effluents, an increase of its activity occurred towards the downstream areas, suggesting other non-mill sources. More research is needed to understand the environmental changes in context of the new technological improvements in treatment systems to MBBR (Moving Bed Biofilm Reactor) recently implemented by the pulp mill industries.

Study of persistent toxic pollutants in a river basin-ecotoxicological risk assessment.

This study presents a complementary approach for the evaluation of water quality in a river basin by employing active and passive sampling. Persistent toxic pollutants representing three classes: organochlorinated pesticides (OCPs), polychlorinated biphenyls (PCBs) and polycyclic aromatic hydrocarbons (PAHs), were studied in grab water samples, in passive samplers/SemiPermeable Membrane Devices (SPMDs) and in fish tissues collected along the Strymonas River, northern Greece at three sampling campaigns during the year 2013. Almost all the target compounds were detected in the study river of Strymonas, northern Greece at the periods of high rainfall intensity and/or low flow-rate. The most frequently detected compounds were 1,2-benzanthracene, benzo(a)pyrene, benzo(b)fluoranthene, endosulfan I, endosulfan II, endosulfan sulfate, endrin aldehyde, fluorene, methoxychlor, polychlorinated biphenyl PCB 28, PCB 180 and pyrene. The family of DDT compounds and aldrin were also occasionally detected. Agricultural run-off and waste effluents are the main sources of hydrophobic organic compounds in the river basin. The use of SPMDs allowed the detection of more micropollutants than active sampling (31 vs. 16, respectively). Results showed relatively low risk however the potential risk associated with micropollutants such as 1,2-benzanthracene, benzo(b)fluoranthene, p,p-dichlorodiphenyldichloroethane (DDD), endosulfan II, methoxychlor, PCB 180 and pyrene should not be neglected. Performing risk assessment based on passive sampling, more information was obtained about temporal and spatial variation. SPMDs could be applied as a pre-evaluation before chemical monitoring in biota.

Using wood frog (Lithobates sylvaticus) tadpoles and semipermeable membrane devices to monitor polycyclic aromatic compounds in boreal wetlands in the oil sands region of northern Alberta, Canada.

Several recent studies have reported evidence that surface mining operations of bitumen in northern Alberta's oil sands (OS) region contribute significantly to the atmospheric deposition of metals and polycyclic aromatic compounds (PACs) within the vicinity of OS development. The present study examines the accumulation of PACs in boreal wetlands at varying distance from OS industrial activities with the use of semipermeable membrane devices (SPMDs) and wood frog (Lithobates sylvaticus) tadpoles. SPMDs were deployed in shallow lentic waterbodies adjacent to wood frog egg masses and were retrieved, along with tadpoles, approximately 35-45 days later. The highest concentrations of PACs were detected in SPMDs deployed within a 25 km radius of surface mining activity, consistent with snow deposition studies of PACs in the region. In wetlands located within the vicinity of surface mining activity, PAC profiles of SPMDs and wood frog tadpoles were dominated by C1-C4 alkylated PACs, including alkylated dibenzothiophenes, which are strongly indicative of petrogenic sources. Contrary to differences seen in the SPMD PAC concentrations, there were no obvious differences in the ∑PACs in wood frog tissue between wetland study sites, although alkylated fluorenes were found to be higher in tadpoles collected from a wetland located within 10 km of two bitumen upgrading facilities. The use of SPMDs in tandem with wood frog tadpoles can help assess the potential exposure of aquatic organisms to PACs in boreal wetlands.

Contamination and risk implications of endocrine disrupting chemicals along the coastline of China: A systematic study using mussels and semipermeable membrane devices.

A systematic study has been carried out to assess the contamination of endocrine disrupting chemicals (EDCs) in five highly urbanized coastal cities spanning from temperate to subtropical environments along the coastline of China. In each of these cities, species of native mussels (Mytilus galloprovincialis, M. coruscus or Perna viridis) were deployed alongside with semipermeable membrane devices (SPMDs) for one month at a reference site and a polluted site. The level of 4-nonylphenol (4-NP), bisphenol A (BPA), 17ß-estradiol (E2) and 17α-ethynylestradiol (EE2) in SPMDs and transplanted mussels were determined and compared. The concentration of EDCs in mussels from polluted sites of Qingdao and Shenzhen ranged from 99.4±9.40 to 326.1±3.16ng/g dry wt. for 4-NP, Dalian and Shanghai from 170.3±4.00 to 437.2±36.8ng/g dry wt. for BPA, Dalian and Shenzhen from 82.9±3.03 to 315.6±6.50ng/g dry wt. for E2, and Shenzhen and Shanghai from 124.5±3.25 to 204.5±9.26ng/g dry wt. for EE2, respectively. These results demonstrate that concentrations of EDCs in mussels along the coastline of China are substantially higher than levels reported in mussels and seafood elsewhere. Despite high levels of EDCs and per capita seafood consumption in China, analysis indicated that 4-NP and BPA intake from mussels at polluted sites per se are still below the Tolerable Daily Intake (TDI). In contrast, the daily intake of E2 and EE2 (6.5 and 5.5µg/person/day, respectively) from mussel consumption exceeded the Acceptable Daily Intake (ADI) established by the WHO, USA and Australia by large margins, suggesting significant public health risks. A strong correlation was found between EDC concentrations in SPMDs and transplanted mussels, and the advantages of using mussels and SPMDs for monitoring EDCs in the aquatic environment are discussed.

Monitoring of organic pollutants in marine environment by semipermeable membrane devices and mussels: accumulation and biochemical responses.

This study involves the monitoring of organic pollutants using transplanted mussels (Mytilus galloprovincialis) as bioindicator organisms and semipermeable membrane devices (SPMDs) as passive samplers. Mussels and SPMDs were deployed to marinas, shipyards and shipbreaking yards on the coastal area of Turkey and retrieved after 60 days. Polycyclic aromatic hydrocarbons (PAH), polychlorinated biphenyls (PCB) and organochlorine pesticide (OCP) compounds were analysed with high-resolution GC-MS. Total PAH concentrations in SPMDs and mussels ranged from 200 to 4740 ng g sampler-1 and from 7.0 to 1130 ng g-1 in wet weight (ww). PCB and OCP concentrations in SPMDs changed between 0.04-200 and 4.0-26 ng g sampler-1, respectively. The highest PCB (190 ng g-1 ww) and OCP (200 ng g-1 ww) concentrations in mussels were measured at shipyard stations. A strong correlation was observed between the PAH and PCB concentrations in SPMDs and mussels. Enzyme assays (acetylcholinesterase, ethoxyresorufin-O-deethylase, glutathione S-transferase, glutathion reductase and carboxylesterase activities) were performed as biomarkers to reveal the effects of pollution on the mussels. There was no clear relationship found between the enzyme levels and the pollutant concentrations in mussels. Integrated biomarker responses were calculated to interpret the overall effect of pollutants.

Combined chemical and toxicological long-term monitoring for AhR agonists with SPMD-based virtual organisms in drinking water Danjiangkou Reservoir, China.

SPMD-based virtual organisms (VOs) were employed for time-integrating, long-term sampling combined biological and chemical analyses for exposure assessment of hydrophobic organic pollutants (HOPs) in a drinking water reservoir, China. The SPMDs were deployed at four and five sites in the Danjiangkou (DJK) reservoir over two periods of 26 and 31 d to sequester the hydrophobic contaminants in water. The chosen bioassay response for the extracts of the SPMDs, the induction of 7-ethoxyresorufin-o-deethylase (EROD) was assayed using a rat hepatoma cell line (H4IIE). The known aryl hydrocarbon receptor (AhR) agonists PAHs and PCBs were analyzed by HRGC/HRMS instrument. The cause-effect relationship between the observed AhR activities and chemical concentrations of detected AhR agonists was examined. The results show that the extracts from the SPMD samples could induce AhR activity significantly, whereas the chemically derived 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) equivalent (TEQcal) was not correlated with the bioassay-derived TCDD equivalent (TEQbio). The known AhR agonists could only account for 2-10% of the observed AhR responses among which the contribution of PCBs could almost be neglected. Unidentified AhR-active compounds represented a greater proportion of the TCDD equivalent (TCDD-EQ) in SPMD samples from DJK. Based on the first assessment, the VO followed by the combination of chemical and biological analyses emerges as a resource efficient water monitoring device in ecotoxicological assessment for toxicologically relevant compounds which are readily available for uptake by resident aquatic biota in drinking water resources.

Using SPMDs to monitor the seawater concentrations of PAHs and PCBs in marine protected areas (Western Mediterranean).

Aqueous concentrations of individual polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) were determined in coastal sites of two marine protected areas (MPAs), that is, Asinara and the La Maddalena Archipelago, in Sardinia (Western Mediterranean Sea). The use of semi-permeable membrane devices (SPMDs) enabled the detection of dissolved PAHs and PCBs, even in very low concentrations of (pgL(-1)), in seawater. The results reveal significant differences between the two sampling areas relative to the concentration of the individual PAHs, which provide information concerning the pollution sources affecting relatively pristine environments. The PCBs were generally observed at levels below the detection limits of the utilised method.