STUDY REGION Hokusetsu Region in Osaka, Japan. STUDY FOCUS The As contamination was investigated through the geochemical mapping and analysis of river waters and bed sediments over an area of 440km2. Sulfur from sulfides in rocks and dissolved sulfates in water were compared via isotopic analysis to assess their origin and the subsequently released As. The fate of As (transport, binding on settling particles) was evaluated through the total and dissolved fractions of As and trace metals Fe, Mn and Al in river waters. NEW HYDROLOGICAL INSIGHTS FOR THE REGION The geochemical mapping showed that As in river water exceeded the maximum limit concentration of 10ppb in several places. The highest As levels (waters and sediments) correlated well with the surface geologies, concentrating in a halo around granitic intrusion and nearby faults. The isotopic analysis of sulfur revealed the occurrence of two kinds of sulfide mineralizations responsible for As contamination: one from Late Paleozoic submarine volcanism in sedimentary rocks, and one from Late Cretaceous igneous activities in contact-metamorphosed rocks disseminated with sulfides. The transport of As along river courses occurred mainly as a dissolved species rather than absorbed on Fe/Mn/Al particles, signifying the least role of iron oxy-hydroxides in As adsorption.

Speleothem-like deposits that develop underground in urban areas are an archive of the environmental impact of anthropic activities that has been little studied so far. In this paper, the sulfate content in shallow groundwater from northern Paris (France) is compared with the sulfur content in two 300-year-old urban carbonate deposits that grew in a historical underground aqueduct. The present-day waters of the aqueduct have very high sulfur and calcium contents, suggesting pollution from gypsum dissolution. However, geological gypsum levels are located below the water table. Sulfur content was measured by micro-X-ray fluorescence in these very S-rich carbonate deposits (0.5 to 1% of S). A twofold S increase during the second half of the 1800s was found in both samples. These dates correspond to two major periods of urbanization above the site. We discus three possible S sources: anthropic sources (industries, fertilizers…), volcanic eruptions and input within the water through gypsum brought for urbanization above the studied site (backfill with quarry waste) since the middle of the 19th century. For the younger second half of the studied section, S input from gypsum brought during urbanization was confirmed by the study of isotopic sulfur composition (δ34S=+15.2‰ at the top). For the oldest part, several sulfur peaks could be related to early industrial activity in Paris, that caused high local air pollution, as reported in historical archives but also to historical gypsum extraction. This study provides information on the origin and timing of the very high SO42− levels measured nowadays within the shallow groundwater, thus demonstrating the interest in using carbonate deposits in urban areas as a proxy for the history of urbanization or human activities and their impact on water bodies.

A particular river-whiting phenomenon occurred in the early 2000s in the Xiaoche River and since then it has been reoccurring from June to November each year. Residents were surprised by this phenomenon and worried about it. This study was designed to reveal the forming mechanism of the river-whiting phenomenon. A comparison of T, EC, ORP, DO, TDS and δ34S in the culvert water and discharge pipe water with that in the water column of Aha Reservoir strongly indicated that the culvert water and discharge pipe water derived primarily from the hypolimnetic reservoir water. When the hypolimnetic water enriched in SO42- and H2S, through seepage from the penstock, flows into the Xiaoche River, the water's supersaturation degree with respect to CaSO4 is increased as a result of increased temperature and DO, thus colloid CaSO4 can be formed. This is the essential cause of the river-whiting phenomenon. The sources of high concentrations of SO42- and H2S in hypolimnetic water include not only direct SO42- and H2S input of acid mine drainage as a result of irrational coal mining in the watershed, but also the sulfur-enriched surface sediments which may release H2S through the sulfate reduction processes. The contaminated sediment has acted as an important contamination source for sulfur to the overlying water in Aha Reservoir. There are more than 50,000 large dams in the world until now. With the increase of reservoir age and the persistent accumulation of pollutants within the reservoir system, discharged hypolimnetic water may contain high levels of pollutants and lead to unpredicted disasters. More investigations are needed to illuminate the water quality condition of discharge water from reservoirs and estimate its impacts on the downstream eco-environment.

Very little is known on the exposure of high trophic level species to current-use brominated (BFRs) and phosphorus flame retardants (PFRs), although observations on their persistence, bioaccumulation potential, and toxicity have been made. We investigated the accumulation of BFRs and PFRs, and their associations with dietary proxies (δ(13)C, δ(15)N and δ(34)S), in plasma and feathers of White-tailed Eagle Haliaeetus albicilla nestlings from Trøndelag, Norway. In addition to accumulation of a wide range of polybrominated diphenyl ether (PBDE) congeners in both plasma and feathers, all non-PBDE BFRs and PFRs could be measured in feathers, while in plasma only two of six PFRs, i.e. tris-(2-chloroisopropyl) phosphate (TCIPP) and tris-(2,3-dichloropropyl) phosphate (TDCPP) were detected. PFR concentrations in feathers (0.95-3,000 ng g(-1)) were much higher than selected organochlorines (OCs), such as polychlorinated biphenyl 153 (CB 153; 2.3-15 ng g(-1)) and dichlorodiphenyldichloroethylene (p,p'-DDE; 2.3-21 ng g(-1)), PBDEs (0.03-2.3 ng g(-1)) and non-PBDE BFRs (0.03-1.5 ng g(-1)). Non-significant associations of PFR concentrations in feathers with those in plasma (P ≥ 0.74), and their similarity to reported atmospheric PFR concentrations, may suggest atmospheric PFR deposition on feathers. Most OCs and PBDEs, as well as tris(chloroethyl) phosphate (TCEP), tris(phenyl) phosphate (TPHP) and tri-(2-butoxyethyl) phosphate (TBOEP) were associated to δ(15)N and/or δ(13)C (all P ≤ 0.02). Besides δ(15)N enrichment, δ(34)S was depleted in nestlings from fjords, inherently close to an urbanised centre. As such, both may have been a spatial proxy for anthropogenic disturbance, possible confounding their use as dietary proxy.