Effect of "black carbon" on antimony accumulation in traffic-loaded topsoil.

Traffic-loaded areas have been of increasing concern due to the potential risk of carcinogenic pollutants, including antimony (Sb), which accumulates mostly in atmospheric particles (PM) and can interact with soil organic matter (Corg). The stability of Sb in topsoils was studied via the adsorption mechanism using standard soils and Corg-reach vehicle-produced particles as the unique source of "traffic" Sb. The mixed adsorbents were prepared from loamy sand and clay standard soils, and braking abrasion dust and diesel engine soot as Sb sources in atmospheric PM. Whereas the black carbon (BC), as part of Corg, disposes of exceptional adsorption properties compared to the other Corg, all adsorption experiments were performed identically on the adsorbents prepared from the original standard soils and Sb source materials and on the adsorbents prepared from the same materials annealed at 375 °C to ensure only BC participation in adsorption processes. The concentration of the Sb model solution corresponded to the average Sb content in rainwater from traffic-loaded localities. In addition to Sb, the Corg and iron (Fe) were monitored. The sorbability of Sb on the loamy sand soil mixtures increased up to 90% compared with the pure soil due to new active surface sites for Sb binding created due to the Corg added with the source material. The clay soil mixture containing 10 times more Corg compared with the loamy sand soil accumulated the Corg from the source material, which resulted in blocking active sites and a decline in Sb sorbability by up to 20%. The processes performed identically with original and annealed materials showed the same trends and confirmed the key role of BC and soil quality in the accumulation and stability of Sb in traffic-loaded topsoils. The participation of Fe in Sb surface interactions was not observed.

Soil solution data from Bohemian headwater catchments record atmospheric metal deposition and legacy pollution.

Soil solution chemistry depends largely on mineralogy and organic matter properties of soil horizons with which they interact. Differing lithologies within a given catchment area can influence variability in soil cation exchange capacities and affect solute transport. Zero-tension and tension lysimeters were used to evaluate the fast transport of solutes in the topsoil vs. slow diffusional matrix flow at the subsoil of three contrasting lithology catchments in a mid-elevation mountain forest. Our aim was to test the feasibility of lysimeters' hydrochemical data as a gauge for legacy subsoil pollution. Due to contrasting lithologies, atmospheric legacy pollution prevailing at the soil-regolith interface is differently yet consistently reflected by beryllium, lead, and chromium soil solution concentrations of the three catchments. Geochemical (dis)equilibrium between the soil and soil matrix water governed the hydrochemistry of the soil solutions at the time of collection, potentially contributing to decreased dissolved concentrations with increased depths at sites with higher soil pH. A complementary isotopic δ18O runoff generation model constrained potential seasonal responses and pointed to sufficiently long water-regolith interactions as to permit important seasonal contributions of groundwater enriched in chemical species to the topsoil levels. Our study also reflects subsoil equilibration with atmospheric solutes deposited at the topsoil and thus provides guidance for evaluating legacy pollution in soil profiles derived from contrasting lithology.

Thermal stability of arsenic complexes in soils.

The release of soil arsenic (As) in an unsaturated zone under oxidative conditions and at two temperatures simulating the seasonal effect (15 °C and 23 °C) was studied in four cultivated soils from the Elbe River catchment (Czech Republic, Central Europe). The soils with a low geogenic As background contained from 10 to 50 µg.g-1 of As, mostly originating from atmospheric deposition in the past. The temperature effect on the stability of As in soils was studied in connection with the stability of hydrated iron (Fe) oxides and dissolved organic carbon (DOC), as essential binding partners of As in soils. The temperature impact on As release was related to the actual As binding in soil determined by the sequential leaching. With predominant As binding to amorphous and poorly crystalline Fe phases the higher temperature (23 °C) increased As release up to twice compare to 15 °C. In the soils with a low total Fe and the preferential As binding to well-crystallised Fe phases the temperature effect on As release was negligible. Unlike Fe, the release of DOC is strongly temperature dependent, therefore As mobilisation was controlled by the DOC concentration. A higher experimental temperature (23 °C) supported the formation of DOC and the consequent release of As and Fe into the soil solution.

Environmental interaction of antimony and arsenic near busy traffic nodes.

Antimony (Sb) and arsenic (As) are elements with similar chemistry, toxicity and binding properties, but different environmental risks and prevailing anthropogenic sources. A significant source of Sb contamination is associated with braking in extremely loaded traffic areas, where the produced abrasion dust contains up to 5% wt. of Sb2S3. In these same exposure areas, As still originates mostly from the combustion of fossil fuels. Heavily loaded crossroads from three different regions of the Czech Republic (Central Europe) were monitored for Sb content in road dusts, topsoils and reference soils during a two-year season (2016-2017). The same samples were also tested for As content to evaluate current contamination trends of both elements in exposed urban areas. The concentration of Sb varied from 5 to 70 µg g-1 in topsoils, and from 20 to 350 µg g-1 in road dusts with the preference for binding to the fine particle fraction (<0.1 mm). The average Sb concentration was up to 60 times the background value and decreased in the order: brake abrasion (103 µg g-1) > road dust (102 µg g-1)> topsoils (101 µg g-1) >> reference soils (<1 µg g-1). The concentration of As in road dust, topsoils and reference soils had about the same level, 101 µg g-1 indicating a more regional character of As pollution. Correlation factors for Sb/As versus iron (Fe)/organic matter (OM) indicated a more robust correlations in soils compared to road dusts and generally better correlations of Sb compared to As. While arsenic contamination has recently decreased thanks to a massive decline of arsenic emissions, antimony contamination indicates a dangerous trend due to growing automotive traffic.

Retraction Statement: Comparison of nitrogen inputs and accumulation in 210 Pb-dated peat cores: Evidence for biological N2 -fixation in Central European peatlands despite decades of atmospheric N pollution.

"Comparison of nitrogen inputs and accumulation in 210 Pb-dated peat cores: Evidence for biological N2 -fixation in Central European peatlands despite decades of atmospheric N pollution" https://doi.org/10.1111/gcb.14505, by Martin Novak, Melanie A. Vile, Jan Curik, Bohuslava Cejkova, Jiri Barta, Marketa Stepanova, Ivana Jackova, Frantisek Buzek, Leona Bohdalkova, Eva Prechova, Frantisek Veselovsky, Marie Adamova, Ivana Valkova and Arnost Komarek. The above article, first published online in Wiley Online Library (wileyonlinelibrary.com) in Global Change Biology, has been retracted by agreement between the authors, the journal Editor-in-Chief, Stephen P. Long, and John Wiley & Sons Ltd. Since publication of the above article, it was brought to the attention of the authors that the peat accretion rates violate reasonable ranges of peatland C/N/P stoichiometry, placing the quantitative conclusions of the article in serious error. The authors apologize for any inconvenience the publication of this work may have caused our readers. REFERENCE Novak, M., Vile, M. A., Cejkova, B., Barta, J., Stepanova, M., Jackova, I., Buzek, F., Bohdalkova, L., Prechova, E., Veselovsky, F., Adamova, M., Valkova, I., & Komarek, A. (2018). Comparison of nitrogen inputs and accumulation in 210 Pb-dated peat cores: Evidence for biological N2 -fixation in Central European peatlands despite decades of atmospheric N pollution. Global Change Biology.. https://doi.org/10.1111/gcb.14505.

Leaching effect on arsenic mobility in agricultural soils.

The stability of soil arsenic during long-term leaching was studied in four soils from an agricultural area. Two identical columns simulating soil profiles of three layers were leached with As-free natural rainwater (<3.10(-3)mgL(-1) As) to test As mobility and the same rainwater enriched with As(V) (2.5mgL(-1) As) for the study of As accumulation. The relative As flow (µgg(-1)day(-1)) showed a comparable run for all soils, with the peak corresponding to maximum As release in the first leaching stage, and then with a tendency to equilibrate. The amount of released As was controlled by the saturated hydraulic conductivity Ksat and free Fe oxides, and the kinetics of the leaching process correlated with the content of organic matter (OM). An overall stability and accumulation of soil arsenic were mostly affected by soil properties (Ksat, particle size, clay fraction), while the chemical composition (Fe, OM content) and surface properties (specific surface area SBET, theoretical adsorption capacity Qt) were of marginal significance. The distribution of As forms was performed by sequential extraction (SEP), which indicated negligible transformation (<12%) of As species in upper soil layers.

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.

Adsorption behavior of arsenic relating to different natural solids: soils, stream sediments and peats.

The sorption of anthropogenically derived arsenic to natural solids plays an important role in the mobility and fate of this toxic metalloid in the environment. The adsorption affinity of dissolved As(V) and As(III) to contrasting natural solids was investigated using model solutions of As(V)/As(III) and homogenized samples of soils, stream sediments and peat cores. The adsorption of As(III) and As(V) on investigated sorbents ran mostly according to the Langmuir model, with high correlation factors (>0.7). Sorption capacities varied from 3.5×10(-3) to 2.0×10(-1) mmol/g of As, whereas As(III) achieved a higher adsorption affinity due to the presence of Fe ions in the model solution. The lower horizons of soils and the intact peat, characterized by high enrichment factors of As content (R>1), represented a more stable system with decreased adsorption/desorption dynamics of As transport. A higher surface activity of solids associated with R<1, and an increased As mobility in the solid-water interface, prevailed in upper horizons of the soil and intact peat, where the contact with atmospheric deposition was expected. Stream sediments proved to be a well-balanced system with R≈1. A strong As-Fe correlation in the natural solids confirmed As affinity to Fe particles.

Application of two-component model of drainage discharge to nitrate contamination.

A conceptual two-component model of drainage discharge based on delta(18)O, nitrate content and delta(15)N data was constructed. It comprises the infiltrated precipitation and the local groundwater, both discharging into the drainage system. The movement of the water via the unsaturated zone is described as a piston-like flow with a varying amount contributing to the total drainage. Two tile drainage systems were studied for nitrate loss. The transit time between the rainfall infiltration and the drainage into the tile system is estimated to be approximately one year. This process is strongly dependent on the duration of the infiltration and its magnitude, and thus on the discharge dynamics in general. The local groundwater contribution to the system formed a significant part of the drainage discharge (varying as 65-98% of the whole drained amount). Nitrate content and delta(15)N data were used for the specification of the nitrate flux and nitrate origin in the drainage discharge.

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.