Carcinogenic effects of hexavalent chromium in waters are of concern in many countries worldwide. We explored Cr isotope systematics at 11 sites in the Czech Republic and Poland. Geogenic Cr pollution was associated with serpentinite bodies at former convergent plate margins, while anthropogenic Cr pollution resulted from electroplating, tanning, and the chemical industry. Cr(VI) concentration in geogenic waters was less than 40 ppb. Anthropogenic waters contained up to 127,000 ppb Cr(VI). At both geogenic and anthropogenic sites, where known, the source of pollution had a low δ53Cr (<1‰). δ53Cr of geogenic and anthropogenic waters was up to 3.9 and 5.8‰, respectively. At both serpentinite-dominated and industrial sites, δ53Cr(VI)aq was shifted toward higher values, compared to the pollution source. At the industrial sites, this positive δ53Cr shift was related to Cr(VI) reduction, a process known to fractionate Cr isotopes. At geogenic sites, the origin of high δ53Cr(VI)aq is tentatively ascribed to preferential release of 53Cr during oxidation of soil Cr(III) and its mobilization to water. δ53Cr(VI) of industrially contaminated waters was significantly higher (p<0.001) compared to δ53Cr of waters carrying geogenic Cr(VI), implying that either the effective fractionation factor or process extent was greater for Cr(VI) reduction than for Cr(III) oxidation.

Massive lignite burning in Central European power plants peaked in the 1980s. Dissolved arsenic in runoff from upland forest ecosystems is one of the ecotoxicological risks resulting from power plant emissions. Maxima in As concentrations in runoff from four forest catchments have increased 2-5 times between 1995 and 2006, and approach the drinking water limit (10 microg L(-1)). To assess the fate of anthropogenic As, we constructed input/output mass balances for three polluted and one relatively unpolluted forest catchment in the Czech Republic, and evaluated the pool size of soil As. The observation period was 11 years, and the sites spanned a 6-fold As pollution gradient. Two of the polluted sites exhibit large net As export via runoff solutes (mean of 4-5 g As ha(-1) yr(-1) for the 11-year period; up to 28 g As ha(-1) yr(-1) in 2005). This contrasts with previous studies which concluded that forest catchments are a net sink for atmogenic arsenic both at times of increasing and decreasing pollution. The amount of exported As is not correlated with the total As soil pool size, which is over 78% geogenic in origin, but correlates closely with water fluxes via runoff. Net arsenic release is caused by an interplay of hydrological conditions and retreating acidification which may mobilize arsenic by competitive ligand exchange. The effects of droughts and other aspects of climate change on subsequent As release from soil were not investigated. Between-site comparisons indicate that most pollutant As may be released from humus.

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Sulfate aerosols are harmful as respirable particles. They also play a role as cloud condensation nuclei and have radiative effects on global climate. A combination of delta18O-SO4 data with catchment sulfur mass balances was used to constrain processes affecting S cycling in the atmosphere and spruce forests of the Czech Republic. Extremely high S fluxes via spruce throughfall and runoff were measured at Jezeri (49 and 80 kg S ha(-1) yr(-1), respectively). The second catchment, Na Lizu, was 10 times less polluted. In both catchments, delta18O-SO4 decreased in the following order: open-area precipitation > throughfall > runoff. The delta18O-SO4 values of throughfall exhibited a seasonal pattern at both sites, with maxima in summer and minima in winter. This seasonal pattern paralleled delta18O-H2O values, which were offset by -18 per thousand. Sulfate in throughfall was predominantly formed by heterogeneous (aqueous) oxidation of SO2. Wet-deposited sulfate in an open area did not show systematic delta18O-SO4 trends, suggesting formation by homogeneous (gaseous) oxidation and/or transport from large distances. The percentage of incoming S that is organically cycled in soil was similar under the high and the low pollution. High-temperature 18O-rich sulfate was not detected, which contrasts with North American industrial sites.