Increasing Arsenic Concentrations in Runoff from 12 Small Forested Catchments (Czech Republic, Central Europe): Patterns and Controls

The 40-year period of heavy industrialization in Central Europe (1950-1990) was accompanied by massive burning of arsenic-rich lignite in power plants. Absence of effective dust removal devices in power plants led to substantial accumulation of arsenic in ecosystems, mainly in forest soils. There are fears that retreating acidification in spruce die-back affected areas of southeastern Germany, northern Czech Republic and southern Poland (the Black Triangle) 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 area covering 75,000 km2 was characterized by a north-south gradient of decreasing pollution. Acidification has been retreating since the late 1980s. Between 1996 and 2003, maximum arsenic concentrations in stream water did not change, and were < 1 ppm in the rural south and < 2 ppm in the industrial north of the country. During the subsequent two years, 2004-2005, maximum arsenic concentrations in runoff increased in 11 of the 12 catchments, reaching 60% of the drinking water limit (10 ppm). Starting in 2006, another major change occurred. Maximum arsenic concentrations returned to lower values at most sites. We discuss three possible causes of the recent arsenic concentration maximum in streams. We rule out retreating acidification and a pulse of high industrial emission rates as possible controls. The pH of stream water 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. A wet year 2002 was followed by a dry year 2003 just before the high-arsenic period in runoff at 6 sites.JRC.E.5-Nuclear chemistr

The Fate of Atmospherically Derived Pb in Central European Catchments: Insights from Spatial and Temporal Pollution Gradients and Pb Isotope Ratios

Soils in polluted regions are generally regarded as a delayed, long-lasting source for Pb contamination of aquatic systems. Lead deposited on topsoil is slowly transported downward with particulate and colloidal organic matter, driven by infiltrating precipitation. Then, Pb is tightly retained in mineral soil. Lead export from catchments is extremely low and decoupled from the atmospheric input. We tested this hypothesis in 11 small catchments, differing in pollution levels. Input/ouput Pb fluxes were monitored for 14–15 years in an era of decreasing industrial Pb emission rates. Between 1996/1997 and 2010, Pb deposition fluxes decreased significantly, on average by 80%. At the beginning of the monitoring, Pb export constituted 2 to 58% of Pb input. At the end of the monitoring, Pb export constituted 2 to 95% of Pb input. Highly polluted sites in the northeast exported significantly more Pb than less polluted sites further south. The ²⁰⁶Pb/²⁰⁷Pb isotope ratios of runoff (1.16) were identical to those of topsoil and present-day deposition, and different from mineral soil and bedrock. Lead isotope systematics and between-site flux comparisons indicated that a portion of the incoming Pb had a relatively short residence time in the catchments, on the order of decades

Controls on δ26Mg variability in three Central European headwater catchments characterized by contrasting bedrock chemistry and contrasting inputs of atmospheric pollutants.

Magnesium isotope ratios (26Mg/24Mg) can provide insights into the origin of Mg pools and fluxes in catchments where Mg sources have distinct isotope compositions, and the direction and magnitude of Mg isotope fractionations are known. Variability in Mg isotope compositions was investigated in three small, spruce-forested catchments in the Czech Republic (Central Europe) situated along an industrial pollution gradient. The following combinations of catchment characteristics were selected for the study: low-Mg bedrock + low Mg deposition (site LYS, underlain by leucogranite); high-Mg bedrock + low Mg deposition (site PLB, underlain by serpentinite), and low-Mg bedrock + high Mg deposition (site UDL, underlain by orthogneiss). UDL, affected by spruce die-back due to acid rain, was the only investigated site where dolomite was applied to mitigate forest decline. The δ26Mg values of 10 catchment compartments were determined on pooled subsamples. At LYS, a wide range of δ26Mg values was observed across the compartments, from -3.38 ‰ (bedrock) to -2.88 ‰ (soil), -1.48% (open-area precipitation), -1.34 ‰ (throughfall), -1.19 ‰ (soil water), -0.99 ‰ (xylem), -0.95 ‰ (needles), -0.82 ‰ (bark), -0.76 ‰ (fine roots), and -0.76 ‰ (runoff). The δ26Mg values at UDL spanned 1.32 ‰ and were thus less variable, compared to LYS. Magnesium at PLB was isotopically relatively homogeneous. The δ26Mg systematics was consistent with geogenic control of runoff Mg at PLB. Mainly atmospheric/biological control of runoff Mg was indicated at UDL, and possibly also at LYS. Our sites did not exhibit the combination of low-δ26Mg runoff and high-δ26Mg weathering products (secondary clay minerals) reported from several previously studied sites. Six years after the end of liming at UDL, Mg derived from dolomite was isotopically undetectable in runoff

Mg, Ca and Sr isotope dynamics in a small forested catchment underlain by paragneiss: The role of geogenic, atmospheric, and biogenic sources of base cations

Knowledge of the origin of magnesium (Mg) and calcium (Ca) in soil solutions and catchment runoff helps to predict forest ecosystems’ vulnerability to deficiencies in essential nutrients in an era of climate change, environmental pollution and bark-beetle calamities. Here we discuss isotope aspects of Mg, Ca and strontium (Sr) cycling in a spruce-forested headwater catchment in a relatively unpolluted part of Central Europe. We investigated to what extent Mg and Ca isotope signatures of runoff reflect the isotope compositions of specific Mg- and Ca-rich minerals that easily dissolve during the weathering of paragneiss, and compared the isotope variability of Mg and Ca in fresh bedrock minerals, soils and other ecosystem reservoirs. We also compared conclusions from Mg and Ca isotope systematics with inferences from catchment input–output mass budgets. Long-term input–output monitoring in the studied catchment situated near the Czech–German border (Central Europe) revealed 3.5–7 times higher outputs of Mg, Ca, and Sr via surface runoff relative to their present-day atmospheric inputs. It follows that hydrological exports of recent atmospheric Mg, Ca and Sr are minor. Release of geogenic base cations into the runoff results from the interplay between mineral abundances, concentrations of the studied elements in the minerals, and their dissolution rates. Chemical depletion fractions for the studied elements from bedrock to the soil were 50–70 %, and the losses of dominant soluble minerals in the soil were 30–80 %. Exports of residual Mg, Ca and Sr following partial incorporation of these elements into secondary phyllosilicates are probably low because newly-formed clay minerals are not abundant in the soil. Residual Ca following preferential incorporation of isotopically light Ca into growing tree biomass may contribute to the isotopically heavy runoff Ca. Isotope ratios of base cations were obtained for six minerals (plagioclase, orthoclase, biotite, muscovite, apatite, and ilmenite). Mineral fractions differ greatly in δ26Mg and δ44Ca values and 87Sr/86Sr ratios. 80–97 % of each of the three studied base cations are present in the bedrock in a single relatively easily dissolvable mineral: Mg in biotite, and Ca and Sr in plagioclase. The isotope composition of Mg in biotite was similar to the isotope composition of Mg in runoff. The isotope compositions of Ca and Sr in plagioclase were also similar to Ca and Sr isotope compositions in runoff. Thus, the dominant geogenic source of each of the studied elements (Mg, Ca and Sr) in the investigated paragneiss catchment can be represented by one relatively soluble mineral

Mg, Ca and Sr isotope dynamics in a small forested catchment underlain by paragneiss: The role of geogenic, atmospheric, and biogenic sources of base cations

Knowledge of the origin of magnesium (Mg) and calcium (Ca) in soil solutions and catchment runoff helps to predict forest ecosystems’ vulnerability to deficiencies in essential nutrients in an era of climate change, environmental pollution and bark-beetle calamities. Here we discuss isotope aspects of Mg, Ca and strontium (Sr) cycling in a spruce-forested headwater catchment in a relatively unpolluted part of Central Europe. We investigated to what extent Mg and Ca isotope signatures of runoff reflect the isotope compositions of specific Mg- and Ca-rich minerals that easily dissolve during the weathering of paragneiss, and compared the isotope variability of Mg and Ca in fresh bedrock minerals, soils and other ecosystem reservoirs. We also compared conclusions from Mg and Ca isotope systematics with inferences from catchment input–output mass budgets. Long-term input–output monitoring in the studied catchment situated near the Czech–German border (Central Europe) revealed 3.5–7 times higher outputs of Mg, Ca, and Sr via surface runoff relative to their present-day atmospheric inputs. It follows that hydrological exports of recent atmospheric Mg, Ca and Sr are minor. Release of geogenic base cations into the runoff results from the interplay between mineral abundances, concentrations of the studied elements in the minerals, and their dissolution rates. Chemical depletion fractions for the studied elements from bedrock to the soil were 50–70 %, and the losses of dominant soluble minerals in the soil were 30–80 %. Exports of residual Mg, Ca and Sr following partial incorporation of these elements into secondary phyllosilicates are probably low because newly-formed clay minerals are not abundant in the soil. Residual Ca following preferential incorporation of isotopically light Ca into growing tree biomass may contribute to the isotopically heavy runoff Ca. Isotope ratios of base cations were obtained for six minerals (plagioclase, orthoclase, biotite, muscovite, apatite, and ilmenite). Mineral fractions differ greatly in δ²⁶Mg and δ⁴⁴Ca values and ⁸⁷Sr/⁸⁶Sr ratios. 80–97 % of each of the three studied base cations are present in the bedrock in a single relatively easily dissolvable mineral: Mg in biotite, and Ca and Sr in plagioclase. The isotope composition of Mg in biotite was similar to the isotope composition of Mg in runoff. The isotope compositions of Ca and Sr in plagioclase were also similar to Ca and Sr isotope compositions in runoff. Thus, the dominant geogenic source of each of the studied elements (Mg, Ca and Sr) in the investigated paragneiss catchment can be represented by one relatively soluble mineral.ISSN:0016-7061ISSN:1872-625