Cu-Zn isotope constraints on the provenance of air pollution in Central Europe: Using soluble and insoluble particles in snow and rime.

Copper (Cu) and zinc (Zn) isotope ratios can be used to fingerprint sources and dispersion pathways of pollutants in the environment. Little is known, however, about the potential of δ65Cu and δ66Zn values in liquid and solid forms of atmospheric deposition to distinguish between geogenic, industrial, local and remote sources of these potentially toxic base metals. Here we present Cu-Zn deposition fluxes at 10 mountain-top sites in the Czech Republic, a region affected by extremely high industrial emission rates 25 years ago. Additionally, we monitored isotope composition of Cu and Zn in vertical and horizontal atmospheric deposition at two sites. We compared δ65Cu and δ66Zn values in snow and rime, extracted by diluted HNO3 and concentrated HF. Cu and Zn isotope signatures of industrial pollution sources were also determined. Cu and Zn deposition fluxes at all study sites were minute. The mean δ65Cu value of atmospheric deposition (-0.07‰) was higher than the mean δ65Cu value of pollution sources (-1.17‰). The variability in δ65Cu values of atmospheric deposition was lower, compared to the pollution sources. The mean δ66Zn value of atmospheric deposition (-0.09‰) was slightly higher than the mean δ66Zn value of pollution sources (-0.23‰). The variability in δ66Zn values of atmospheric deposition was indistinguishable from that of pollution sources. The largest isotope differences (0.35‰) were observed between the insoluble and soluble fractions of atmospheric deposition. These differences may result from different sources of Cu/Zn for each fraction. The difference in isotope composition of soluble and insoluble particles appears to be a promising tool for pollution provenance studies in Central Europe.

Common occurrence of a positive δ53Cr shift in Central European waters contaminated by geogenic/industrial chromium relative to source values.

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.

Atmospheric deposition of beryllium in Central Europe: comparison of soluble and insoluble fractions in rime and snow across a pollution gradient.

Little is known about atmospheric input of beryllium (Be) into ecosystems, despite its highly toxic behavior. For three consecutive winters (2009-2011), we measured Be concentrations in horizontal deposition (rime) and vertical deposition (snow) at 10 remote mountain-top locations in the Czech Republic, Central Europe. Beryllium was determined both in filtered waters, and in HF digests of insoluble particles. Across the sites, soluble Be concentrations in rime were 7 times higher, compared to snow (6.1 vs. 0.9ng·L(-1)). Rime scavenged the pollution-rich lower segments of clouds. The lowest Be concentrations were detected in the soluble fraction of snow. Across the sites, 34% of total Be deposition occurred in the form of soluble (bioavailable) Be, the rest were insoluble particles. Beryllium fluxes decreased in the order: vertical dry deposition insoluble>vertical dry deposition soluble>horizontal deposition soluble>vertical wet deposition insoluble>vertical wet deposition soluble>horizontal deposition insoluble. The average contributions of these Be forms to total deposition were 56, 21, 8, 7, 5 and 3%, respectively. Sites in the northeast were more Be-polluted than the rest of the country with sources of pollution in industrial Silesia.

Using S and Pb isotope ratios to trace leaching of toxic substances from an acid-impacted industrial-waste landfill (Pozdatky, Czech Republic).

Slightly elevated concentrations of toxic species in waters sampled in the surroundings of a leaky landfill may be both a sign of an approaching contaminant plume, or a result of water-rock interaction. Isotopes can be instrumental in distinguishing between anthropogenic and geogenic species in groundwater. We studied sulfur and lead isotope ratios at an abandoned industrial-waste landfill, located in a densely populated part of Central Europe. Stable isotope variability in space and time was used to follow the movement of a groundwater plume, contaminated with toxic metals (Cd, Cr, Be), in fractured granitoids. Toxic metals had been mobilized from industrial waste by a strong pulse of sulfuric acid, also deposited in the landfill. Both tracers exhibited a wide range of values (δ(34)S between +2.6 and +18.9‰; (206)Pb/(207)Pb between 1.16 and 1.39), which facilitated identification of mixing end-members, and made it possible to assess the sources of the studied species. In situ fractionations did not hinder source apportionment. Influx of contaminated groundwater was observed neither in irrigation wells in a nearby village, nor at distances greater than 300 m from the landfill. Combination of stable isotope tracers can be used as part of an early-warning system in landscapes affected by landfills.

Behaviour of arsenic in forested catchments following a high-pollution period.

Due to high availability of adsorption sites, forested catchments could be net sinks for pollutant arsenic both during the period of increasing and decreasing pollution. We tested this hypothesis along a north-south pollution gradient in spruce die-back affected areas of Central Europe. For two water years (2007-2008), we monitored As fluxes via spruce-canopy throughfall, open-area precipitation, and runoff in four headwater catchments (Czech Republic). Since 1980, atmospheric As inputs decreased 26 times in the north, and 13 times in the south. Arsenic export by runoff was similar to atmospheric inputs at three sites, resulting in a near-zero As mass balance. One site exhibited a net export of As (2.2 g ha(-1) yr(-1)). In contrast, the preceding period (1995-2006) showed much higher As fluxes, and higher As export. Czech catchments do not serve as net sinks of atmospheric As. A considerable proportion of old industrial arsenic is flushed out of the soil.

Increasing arsenic concentrations in runoff from 12 small forested catchments (Czech Republic, Central Europe): patterns and controls.

The 40-year long period of heavy industrialization in Central Europe (1950-1990) was accompanied by burning of arsenic-rich lignite in thermal power plants, and accumulation of anthropogenic arsenic in forest soils. There are fears that retreating acidification may lead to arsenic mobilization into drinking water, caused by competitive ligand exchange. We present monthly arsenic concentrations in surface runoff from 12 headwater catchments in the Czech Republic for a period of 13 years (1996-2008). The studied area was characterized by a north-south gradient of decreasing pollution. Acidification, caused mainly by SOx and NOx emissions from power plants, has been retreating since 1987. Between 1996 and 2003, maximum arsenic concentrations in runoff did not change, and were < 1 ppb in the rural south and < 2 ppb in the industrial north. During the subsequent two years, 2004-2005, maximum arsenic concentrations in runoff increased, reaching 60% of the drinking water limit (10 ppb). Starting in 2006, maximum arsenic concentrations returned to lower values at most sites. We discuss three possible causes of the recent arsenic concentration maximum in runoff. We rule out retreating acidification and a pulse of high industrial emission rates as possible controls. The pH of runoff has not changed since 1996, and is still too low (<6.5) at most sites for an As-OH(-) ligand exchange to become significant. Elevated arsenic concentrations in runoff in 2004-2005 may reflect climate change through changing hydrological conditions at some, but not all sites. Dry conditions may result in elevated production of DOC and sulfur oxidation in the soil. Subsequent wet conditions may be accompanied by acidification leading to faster dissolution of arsenic-bearing sulfides, dissolution of arsenic-bearing Fe-oxyhydroxides, and elevated transport of arsenic sorbed on organic matter. Anaerobic domains exist in normally well-aerated upland soils for hours-to-days following precipitation events.

Export of arsenic from forested catchments under easing atmospheric pollution.

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.

Accumulation of organic carbon over the past 150 years in five freshwater peatlands in western and central Europe.

Under predicted scenarios of global climate change, peatlands may become a net source of greenhouse gases which will accelerate warming of the atmosphere. Comparative studies of peat bogs along present climatic gradients may provide an insight into the future response of boreal and subarctic peatlands to changing temperature and moisture. Three maritime peat bogs in the British Isles, and two high-elevation peatlands in the Czech Republic were studied. All sites were relatively wet, the mean annual temperatures were higher by up to 6 degrees C at the British/Irish sites than at the Czech sites. Cumulative carbon content in (210)Pb-dated Sphagnum-dominated vertical peat cores increased from the warmer to the colder sites when evaluated for the most recent decades (since ca. 1950). That would correspond to formation of thinner, more highly decomposed peat deposits over the long-term in warmer conditions, and deeper peat bogs in colder conditions. However, when cumulative carbon content was evaluated for the last ca. 150 years, no relationship was found between mean annual temperature and the carbon pool size. Even along broad present-day climatic gradients, site-specific factors controlled organic carbon preservation in peat. Pollen analysis was instrumental in corroborating the (210)Pb dates, identifying wet and dry periods in the past, and it also provided evidence for increasing nitrogen loads in wetland areas.

Arsenic in atmospheric deposition at the Czech-Polish border: two sampling campaigns 20 years apart.

Arsenic (As) occurs in atmospheric deposition both in soluble and insoluble forms, mainly bound to fine aerosol particles (less than 2.5 microm). Interception deposition (i.e. fog, dew and ice accretion) represents a specific type of atmospheric deposition, which has been much more contaminated with As than bulk deposition. This study compares the As amount and its binding forms in bulk and interception deposition in the winters of 1984-1986 and 2003-2005 in the Orlické hory mountains (Adlergebirge) near the Czech-Polish border; sampled and analysed by the same methodology. The As concentrations in ice accretions decreased 16 times over the twenty year period (from 50 microg L(-1) to 3 microg L(-1)), while the pH values increased by 0.8 units. As concentrations in snow decreased from 15 microg L(-1) in 1984-1986 to <2 microg L(-1) in 2003-2005. This decline mirrored the considerable decrease in industrial emissions in Central Europe. Higher acidity of interception deposition (about 1 pH unit) in comparison with the bulk deposition was observed in both sampling periods. The quantity of bulk deposition (snowfall) also influenced the As concentration in interception deposition. Dry periods resulted in higher As-amounts in interception deposition due to limited washing of atmospheric aerosol particles by wet deposition. The As concentration and stability in atmospheric deposition are important for the study of subsequent As-migration and/or accumulation in soil -- groundwater -- surface water.

Processes affecting oxygen isotope ratios of atmospheric and ecosystem sulfate in two contrasting forest catchments in Central Europe.

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.