An Innovative Method to Generate Bromine Monochloride for Trace Hg Analysis.

This work presents a new method for generating a BrCl solution, starting from the commercially available dibromodimethylhydantoin (DBDMH). This method is notable due to the straightforward, safe and clean performance, being based on a simple addition of DBDMH into aqueous HCl. The whole procedure is finished in about 20 min. An advantage of the proposed method is avoiding of tedious reagents pre-cleaning by prolonged thermal treatment, spontaneous overheating and excessive vapor evolution. The resulting BrCl stabilization reagent is low enough in mercury content to be directly used in trace mercury analysis. A thorough study of the BrCl solutions prepared by this method showed that they conform in all respects to US EPA 1631e/2002 requirements.

Metal(loid)s remobilization and mineralogical transformations in smelter-polluted savanna soils under simulated wildfire conditions.

The surroundings of mines and smelters may be exposed to wildfires, especially in semi-arid areas. The temperature-dependent releases of metal(loid)s (As, Cd, Cu, Pb, Zn) from biomass-rich savanna soils collected near a Cu smelter in Namibia have been studied under simulated wildfire conditions. Laboratory single-step combustion experiments (250-850 °C) and experiments with a continuous temperature increase (25-750 °C) were coupled with mineralogical investigations of the soils, ashes, and aerosols. Metals (Cd, Cu, Pb, Zn) were released at >550-600 °C, mostly at the highest temperatures, where complex aerosol particles, predominantly composed of slag-like aggregates, formed. In contrast, As exhibited several emission peaks at ~275 °C, ~370-410 °C, and ~580 °C, reflecting its complex speciation in the solid phase and indicating its remobilization, even during wildfires with moderate soil heating. At <500 °C, As was successively released via the transformation of As-bearing hydrous ferric oxides, arsenolite (As2O3) grains attached to the organic matter fragments, metal arsenates, and/or As-bearing apatite, followed by the thermal decomposition of enargite (Cu3AsS4) at >500 °C. The results indicate that the active and abandoned mining and smelting sites, especially those highly enriched in As, should be protected against wildfires, which can be responsible for substantial As re-emissions.

Chronic exposure of soybean plants to nanomolar cadmium reveals specific additional high-affinity targets of cadmium toxicity.

Solving the global environmental and agricultural problem of chronic low-level cadmium (Cd) exposure requires better mechanistic understanding. Here, soybean (Glycine max) plants were exposed to Cd concentrations ranging from 0.5 nM (background concentration, control) to 3 µM. Plants were cultivated hydroponically under non-nodulating conditions for 10 weeks. Toxicity symptoms, net photosynthetic oxygen production and photosynthesis biophysics (chlorophyll fluorescence: Kautsky and OJIP) were measured in young mature leaves. Cd binding to proteins [metalloproteomics by HPLC-inductively coupled plasma (ICP)-MS] and Cd ligands in light-harvesting complex II (LHCII) [X-ray absorption near edge structure (XANES)], and accumulation of elements, chloropyll, and metabolites were determined in leaves after harvest. A distinct threshold concentration of toxicity onset (140 nM) was apparent in strongly decreased growth, the switch-like pattern for nutrient uptake and metal accumulation, and photosynthetic fluorescence parameters such as Φ RE10 (OJIP) and saturation of the net photosynthetic oxygen release rate. XANES analyses of isolated LHCII revealed that Cd was bound to nitrogen or oxygen (and not sulfur) atoms. Nutrient deficiencies caused by inhibited uptake could be due to transporter blockage by Cd ions. The changes in specific fluorescence kinetic parameters indicate electrons not being transferred from PSII to PSI. Inhibition of photosynthesis combined with inhibition of root function could explain why amino acid and carbohydrate metabolism decreased in favour of molecules involved in Cd stress tolerance (e.g. antioxidative system and detoxifying ligands).

Estimation of Hg(II) in Soil Samples by Bioluminescent Bacterial Bioreporter E. coli ARL1, and the Effect of Humic Acids and Metal Ions on the Biosensor Performance.

Mercury is a ubiquitous environmental pollutant of dominantly anthropogenic origin. A critical concern for human health is the introduction of mercury to the food chain; therefore, monitoring of mercury levels in agricultural soil is essential. Unfortunately, the total mercury content is not sufficiently informative as mercury can be present in different forms with variable bioavailability. Since 1990, the use of bioreporters has been investigated for assessment of the bioavailability of pollutants; however, real contaminated soils have rarely been used in these studies. In this work, a bioassay with whole-cell bacterial bioreporter Escherichia coli ARL1 was used for estimation of bioavailable concentration of mercury in 11 soil samples. The bioreporter emits bioluminescence in the presence of Hg(II). Four different pretreatments of soil samples prior to the bioassay were tested. Among them, laccase mediated extraction was found to be the most suitable over water extraction, alkaline extraction, and direct use of water-soil suspensions. Nevertheless, effect of the matrix on bioreporter signal was found to be severe and not possible to be completely eliminated by the method of standard addition. In order to elucidate the matrix role, influences of humic acid and selected metal ions present in soil on the bioreporter signal were tested separately in laboratory solutions. Humic acids were found to have a positive effect on the bioreporter growth, but a negative effect on the measured bioluminescence, likely due to shading and Hg binding resulting in decreased bioavailability. Each of the tested metal ions solutions affected the bioluminescence signal differently; cobalt (II) positively, iron (III) negatively, and the effects of iron (II) and nickel (II) were dependent on their concentrations. In conclusion, the information on bioavailable mercury estimated by bioreporter E. coli ARL1 is valuable, but the results must be interpreted with caution. The route to functional bioavailability bioassay remains long.

Larch Tree Rings as a Tool for Reconstructing 20th Century Central European Atmospheric Mercury Trends.

We propose the tree rings of European Larch ( Larix decidua) as a widely available and reliable geochemical archive of local and regional changes in atmospheric mercury (Hg). Mean Hg concentrations in larch tree rings from 8 background sites across the Czech Republic ranged from 2.2 to 4.8 µg kg-1; the maximum concentrations occurred in the period 1951-1970. At 3 sites impacted by Hg-emission sources [gold amalgamation processing, caustic soda production, and lead (Pb) ore smelting] mean larch tree ring Hg concentrations were significantly elevated relative to background sites. Changes in larch tree ring Hg concentrations were temporally coherent with known activities at the sites that would alter Hg emissions; the nearly simultaneous response in tree rings indicated little or no translocation of Hg within the larch bole. Based on the present-day atmospheric Hg concentration of 1.63 ng m-3 at the intensively monitored Czech Global Mercury Observation System site and the most recent mean tree ring Hg concentration of 2.8 µg kg-1 in co-located larch trees, we developed a simple distribution model of Hg between the atmosphere and larch tree rings. We applied the model using observed changes of Hg in larch tree rings from the countrywide background sites to reconstruct past atmospheric Hg concentrations in central Europe. Modeled Hg concentrations were in agreement with annual means from the European Monitoring and Evaluation Programme observatories.

Bioaccessibility of As, Cu, Pb, and Zn in mine waste, urban soil, and road dust in the historical mining village of Kank, Czech Republic.

Historical mining activities in the village of Kank (in the northern part of the Kutná Hora ore district, Czech Republic) produced large amounts of mine wastes which contain significant amounts of metal(loid) contaminants such as As, Cu, Pb, and Zn. Given the proximity of residential communities to these mining residues, we investigated samples of mine waste (n = 5), urban soil (n = 6), and road dust (n = 5) with a special focus on the solid speciation of As, Cu, Pb, and Zn using a combination of methods (XRD, SEM/EDS, oxalate extractions), as well as on in vitro bioaccessibility in simulated gastric and lung fluids to assess the potential exposure risks for humans. Bulk chemical analyses indicated that As is the most important contaminant in the mine wastes (~1.15 wt%), urban soils (~2900 mg/kg) and road dusts (~440 mg/kg). Bioaccessible fractions of As were quite low (4-13%) in both the simulated gastric and lung fluids, while the bioaccessibility of metals ranged between <0.01% (Pb) and 68% (Zn). The bioaccessibilities of the metal(loid)s were dependent on the mineralogy and different adsorption properties of the metal(loid)s. Based on our results, a potential health risk, especially for children, was recognized from the ingestion of mine waste materials and highly contaminated urban soil. Based on the risk assessment, arsenic was found to be the element posing the greatest risk.

Isotopic Tracing of Thallium Contamination in Soils Affected by Emissions from Coal-Fired Power Plants.

Here, for the first time, we report the thallium (Tl) isotope record in moderately contaminated soils with contrasting land management (forest and meadow soils), which have been affected by emissions from coal-fired power plants. Our findings clearly demonstrate that Tl of anthropogenic (high-temperature) origin with light isotope composition was deposited onto the studied soils, where heavier Tl (ε(205)Tl ∼ -1) naturally occurs. The results show a positive linear relationship (R(2) = 0.71) between 1/Tl and the isotope record, as determined for all the soils and bedrocks, also indicative of binary Tl mixing between two dominant reservoirs. We also identified significant Tl isotope variations within the products from coal combustion and thermo-desorption experiments with local Tl-rich coal pyrite. Bottom ash exhibited the heaviest Tl isotope composition (ε(205)Tl ∼ 0), followed by fly ash (ε(205)Tl between -2.5 and -2.8) and volatile Tl fractions (ε(205)Tl between -6.2 and -10.3), suggesting partial Tl isotope fractionations. Despite the evident role of soil processes in the isotope redistributions, we demonstrate that Tl contamination can be traced in soils and propose that the isotope data represent a possible tool to aid our understanding of postdepositional Tl dynamics in surface environments for the future.

Preconcentration and detection of mercury with bioluminescent bioreporter E. coli ARL1.

Cell wall envelopes treated with sodium hydroxide and spray-dried were used as mercury sorbents. The sorbent having sorption capacity 17.7 ± 0.1 µmol/g determined was employed for preconcentration of mercury containing 1-10 ng/L. After preconcentration, bioavailable mercury was detected in samples of soil, stream, and tap water via induction of bioluminescence of E. coli ARL1. Iron and manganese at concentrations of tenth microgram per liter interfered bioluminescence detection of mercury. In tap water was detected semiquantitatively 0.127 ± 0.1 nmol/L by the induction of bioluminescence of E. coli ARL1 in medium with tryptone after preconcentration using a method of standard addition.

The influence of sample drying procedures on mercury concentrations analyzed in soils.

Methods commonly used for soil sample preparation may be unsuitable for measuring Hg concentrations due to the possible loss of volatile Hg species when drying at higher temperatures. Here, the effects of freeze-drying, air drying at 25°C and oven-drying at 105°C on Hg concentrations in two soil types and three standard reference materials were tested. Two soils with different levels of Hg contamination and three reference materials were examined. A systematic decrease of Hg concentrations was observed in air-dried (24 %) and oven-dried (3 %) contaminated upland soils in comparison to freeze-dried control samples. The 105°C oven drying also led to loss of Hg from reference materials (5 %-8 % in comparison with the certified Hg concentration). Different results from the drying of sterilized reference materials and natural soils were probably related to the extent of microbiological activity, demonstrating the importance of this parameter in sample preparation for Hg analysis.

Quarter century of mercury litterfall at a coniferous forest responding to climate change, Central Europe.

This work evaluated the 25-year-long trends (1994-2018) in mercury (Hg) concentrations and fluxes in spruce litterfall at a forest research plot Nacetín (NAC) recovering from acidic deposition in the Ore Mountains, Czech Republic. The mean litterfall Hg deposition averaged 51 ± 18 µg m-2 year-1, which has been the highest litterfall Hg deposition reported up to date on the European continent. In contrast, the wet deposition (2017-2019) was an order of magnitude lower averaging at 2.5 ± 1.5 µg m-2 year-1. All the spruce litterfall components bark, twigs, needles, cones, and a mixture of unidentified fragments had elevated mean Hg concentrations relative to background sites averaging 256 ± 77, 234 ± 62, 119 ± 23, 95 ± 14, and 44 ± 15 µg kg-1, respectively. Elevated litterfall Hg deposition and concentrations were attributed to the nearby local Hg emission source-coal-fired power plants. Temporally, the decrease of Czech Hg emissions since the 1990s was reflected by the decreasing trend of Hg concentrations in litterfall bark, cones, and twigs, while in needles and other material, Hg increased but insignificantly. Total litterfall ratios of Hg/C, Hg/N, and Hg/S were lower than those in soil O horizons averaging at 0.23 ± 0.04, 9.5 ± 2.0, and 170 ± 37 µg g-1, respectively. Since the beginning of monitoring, total litterfall Hg/C exhibited no trend, Hg/N decreased, and Hg/S increased. The litterfall biomass deposition averaging at 469 ± 176 g m-2 year-1 increased through time resulting in an increased Hg litterfall deposition at NAC by 1.1 µg m-2 year-1 despite the decreases in Czech Hg emissions. Peaks of annual litterfall Hg deposition up to 96 µg m-2 year-1 at NAC during the 25 years of monitoring resulted from weather extremes such as rime-snow accumulation, wind gusts, droughts, and insect infestation, which all significantly affected the annual biomass deposition. Based on our observations, further increases in biomass and litterfall Hg deposition rates can be expected due to the onset of bark beetle infestation and the increasing number of droughts caused by climate change.

Climate-forced Hg-remobilization associated with fern mutagenesis in the aftermath of the end-Triassic extinction.

The long-term effects of the Central Atlantic Magmatic Province, a large igneous province connected to the end-Triassic mass-extinction (201.5 Ma), remain largely elusive. Here, we document the persistence of volcanic-induced mercury (Hg) pollution and its effects on the biosphere for ~1.3 million years after the extinction event. In sediments recovered in Germany (Schandelah-1 core), we record not only high abundances of malformed fern spores at the Triassic-Jurassic boundary, but also during the lower Jurassic Hettangian, indicating repeated vegetation disturbance and stress that was eccentricity-forced. Crucially, these abundances correspond to increases in sedimentary Hg-concentrations. Hg-isotope ratios (δ202Hg, Δ199Hg) suggest a volcanic source of Hg-enrichment at the Triassic-Jurassic boundary but a terrestrial source for the early Jurassic peaks. We conclude that volcanically injected Hg across the extinction was repeatedly remobilized from coastal wetlands and hinterland areas during eccentricity-forced phases of severe hydrological upheaval and erosion, focusing Hg-pollution in the Central European Basin.

Mobilization of aluminum by the acid percolates within unsaturated zone of sandstones.

The area of the Black Triangle has been exposed to extreme levels of acid deposition in the twentieth century. The chemical weathering of sandstones found within the Black Triangle became well-known phenomenon. Infiltration of acid rain solutions into the sandstone represents the main input of salt components into the sandstone. The infiltrated solutions--sandstone percolates--react with sandstone matrix and previously deposited materials such as salt efflorescence. Acidic sandstone percolates pH 3.2-4.8 found at ten sites within the National Park Bohemian Switzerland contained high Al-tot (0.8-10 mg L(-1)) concentrations and high concentrations of anions SO4 (5-66 mg L(-1)) and NO3 (2-42 mg L(-1)). A high proportion (50-98 %) of Al-tot concentration in acid percolates was represented by toxic reactive Al(n+). Chemical equilibrium modeling indicated as the most abundant Al species Al(3+), AlSO4 (+), and AlF(2+). The remaining 2-50 % of Al-tot concentration was present in the form of complexes with dissolved organic matter Al-org. Mobilization and transport of Al from the upper zones of sandstone causes chemical weathering and sandstone structure deterioration. The most acidic percolates contained the highest concentrations of dissolved organic material (estimated up to 42 mg L(-1)) suggesting the contribution of vegetation on sandstone weathering processes. Very low concentrations of Al-tot in springs at BSNP suggest that Al mobilized in unsaturated zone is transported deeper into the sandstone. This process of mobilization could represent a threat for the water quality small-perched aquifers.

Atmospheric mercury and its deposition during the phasing out of an amalgam electrolysis plant: temporal, seasonal, and spatial patterns.

Large amounts of mercury (Hg) were consumed and emitted into the atmosphere during the process of amalgam electrolysis used to produce chlorine and caustic soda since the nineteenth century. In Europe, amalgam electrolysis has been gradually replaced by advanced Hg-free technologies. In this work, we describe changes in atmospheric Hg and bulk Hg wet deposition during the phasing out of an amalgam electrolytic production line of a chlor-alkali plant in Neratovice, Czech Republic, central Europe. Bulk wet deposition Hg near the chlor-alkali plant was low at 3.6 ± 0.8 µg m-2 year-1 due in part to low annual precipitation amounts (486 ± 97 mm) in the period 2015-2021. Nevertheless, Hg deposition was elevated relative to a nearby reference site both before and after decommissioning of the electrolytic line. Switching off the amalgam electrolytic line did not notably affect bulk wet deposition Hg near the chlor-alkali plant. Levels of gaseous elemental Hg (GEM) and particle-bound Hg (PBM) monitored seasonally four times per year over 24-h time periods indicated rapid declines in four nearby settlements set in cardinal directions from the Hg emission source. Mean atmospheric GEM and PBM concentrations decreased rapidly from 9.0 ± 2.1 ng m-3 and 243 ± 255 pg m-3 in the period 2013-2017 when amalgam electrolysis was operating to 3.3 ± 0.4 ng m-3 and 32 ± 6 pg m-3 in the period 2018-2021 after its decommissioning in November 2017. Seasonal changes of GEM coincided with changes in temperature with the highest concentrations in summer, while PBM air levels were lowest in summer due to the highest seasonal precipitation amount. GEM concentrations at the four monitored settlements at Neratovice remained elevated at 2.8 ng m-3 with respect to regional background, but PBM levels decreased to background levels.

Mobilisation of Cd, Mn, and Zn in floodplains by action of plants and its consequences for spreading historical contamination and fluvial geochemistry.

Cadmium, Mn, and Zn are mobilised by plants commonly growing in floodplains, most notably willows (Salix) and alder (Alnus). These plants accumulate unwanted elements (Cd) or excessive element concentrations (Mn, Zn) in their foliage, thus introducing them into the food web and enriching them in floodplain surface by litterfall. In floodplain of the Litavka River in Czechia, contaminated by historical mining activities, up to 100 mg kg-1 Cd and up to several thousand mg kg-1 Mn and Zn are present in willow leaves in autumn, probably close maxima for sustainable plant growth. Willows and alders show seasonal growth of their foliar Mn and Zn. The willow leaves showed Cd/Zn larger than contaminated fluvisol of the Litavka River. Senesced willow leaves thus contribute to spread of risk elements from historically contaminated floodplains back to river water even without the bank erosion. Alders and willows alter geochemical cycles of Cd, Mn, and Zn in fluvial systems and increase Cd/Zn and Mn/Fe concentration ratios and Cd and Mn concentrations in fluvially transported particles relative to global geochemical averages as well as relative to floodplain sediments. Willows, in particular Salix fragilis L., S. aurita L, and S. cinerea L are particularly important "plant pumps". Other common floodplain plants, such as bird cherry (Prunus padus L.) and herbaceous plants (common nettle, Urtica dioica L. and grasses, Poaceae) do not contribute to those phenomena.

Reconstructing atmospheric Hg levels near the oldest chemical factory in central Europe using a tree ring archive.

The Chemical Factory in Marktredwitz (CFM) is known as the oldest chemical factory in Germany (1778-1985), and from the beginning of the 20th century focused primarily on the production of mercury (Hg) compounds. Due to extensive pollution, together with employee health issues, the CFM was shut in 1985 by a government order and remediation works proceeded from 1986 to 1993. In this study, tree ring archives of European Larch (Larix decidua Mill.) were used to reconstruct changes of air Hg levels near the CFM. Mercury concentrations in larch boles decreased from 80.6 µg kg-1 at a distance of 0.34 km-3.4 µg kg-1 at a distance of 16 km. The temporal trend of atmospheric Hg emissions from the CFM reconstructed from the tree ring archives showed two main peaks. The first was in the 1920s, with a maximum tree ring Hg concentration 249.1 ± 43.9 µg kg-1 coinciding with when the factory had a worldwide monopoly on the production of Hg-based seed dressing fungicide. The second peak in the 1970s, with a maximum tree ring Hg concentration of 116.4 ± 6.3 µg kg-1, was associated with a peak in the general usage and production of Hg chemicals and goods. We used the tree ring record to reconstruct past atmospheric Hg levels using a simple model of Hg distribution between the larch tree rings and atmosphere. The precision of the tree ring model was checked against the results of air Hg measurements during the CFM remediation 30 years ago. According to the tree ring archives, the highest air Hg concentrations in the 1920s in Marktredwitz were over 70 ng m-3. Current air Hg levels of 1.18 ng m-3, assessed in the city of Marktredwitz, indicate the lowest air Hg in the past 150 years, underscoring the effective remediation of the CFM premises 30 years ago.

Uranium, thorium and rare earth elements in macrofungi: what are the genuine concentrations?

Concentrations of uranium, thorium and rare earth elements (REE) in 36 species of ectomycorrhizal (26 samples) and saprobic (25 samples) macrofungi from unpolluted sites with differing bedrock geochemistry were analyzed by inductively coupled plasma mass spectrometry (ICP-MS). Analytical results are supported by use of certified reference materials (BCR-670, BCR-667, NIST-1575a) and the reliability of the determination of uranium was verified by epithermal neutron activation analysis (ENAA). It appears that data recently published on these elements are erroneous, in part because of use of an inappropriate analytical method; and in part because of apparent contamination by soil particles resulting in elevated levels of thorium and REE. Macrofungi from unpolluted areas, in general, did not accumulate high levels of the investigated metals. Concentrations of uranium and thorium were generally below 30 and 125 µg kg(-1) (dry weight), respectively. Concentrations of REE in macrofungi did not exceed 360 µg kg(-1) (dry weight) and their distribution more or less followed the trend observed in post-Archean shales and loess.

Spring snowmelt and mercury export from a forested catchment in the Czech Republic, Central Europe.

The annual output of filtered mercury (Hg) from Lesni potok catchment, a forested ecosystem in central Europe, was estimated at 0.87 µg m⁻². More than 70% of the annual mercury output flux occurred during the spring snowmelt period. The snowmelt period is the most important part of the hydrological year in central European forested ecosystems. Average filtered concentrations of mercury (17.8 ng L⁻¹) and DOC (10.5 mg L⁻¹) in the stream water during snowmelt were greater than average values for the rest of the hydrological year. Omitting frequent daily or bi-daily filtered mercury analysis during the snowmelt caused underestimation of the annual mercury output flux (0.79 µg m⁻²) and decreased the accuracy of flux calculations.

Contrasting tree ring Hg records in two conifer species: Multi-site evidence of species-specific radial translocation effects in Scots pine versus European larch.

Tree ring records are increasingly being used as a geochemical archive of past atmospheric mercury (Hg) pollution. However, it is not clear whether all tree species can be used reliably for this purpose. We compared tree-ring Hg records of two coniferous species - widely used Scots pine (Pinus sylvestris) and less frequently used European larch (Larix decidua) at 6 study sites across the Czech Republic. Site-specific mean Hg concentrations in tree-ring segments of larch ranged from 2.1 to 5.2 µg kg-1, whereas pine had higher mean Hg concentrations (3.6-8.3 µg kg-1). Temporal records of Hg concentrations in tree rings of larch and pine differed significantly. Comparisons with previously documented peat Hg records showed that larch tree-ring Hg records more closely agreed with peat archive records. For pines, which had a large, tree-age dependent number of sapwood rings (62 ± 17, 1SD), we found a strong relationship between the year of peak Hg and the number of sapwood tree rings (p = 0.012, r2 = 0.35), as well as between peak Hg year and the sapwood-heartwood boundary year (p < 0.001, r2 = 0.65), rather than with temporal changes in atmospheric Hg levels. The much greater number of pine sapwood tree rings appears to promote radial Hg translocation, resulting in the shift of Hg peaks backward in time through the tree-ring record. In contrast, Larch consistently had a low number of sapwood tree rings (19 ± 6, 1SD), and more closely agreed with peat Hg records. This study suggests that European larch, a tree species characterized by a relatively low and consistent number of sapwood tree rings, records changes in atmospheric Hg concentrations more reliably than does Scots pine, a species with a relatively high and variable number of sapwood tree rings.

Uptake of Cd, Pb, U, and Zn by plants in floodplain pollution hotspots contributes to secondary contamination.

Willows, woody plants of genus Salix common in floodplains of temperate regions, act as plant pumps and translocate the Cd and Zn in the soil profiles of uncontaminated and weakly contaminated floodplains from the sediment bulk to the top strata. We suggest this process occurs because the Cd and Zn concentrations in willow leaves exceed those in the sediments. Senescing foliage of plant species common in floodplains can increase the Cd and Zn ratios as compared to other elements (Pb and common 'lithogenic elements' such as Al) in the top strata of all floodplains, including those that have been severely contaminated. The top enrichment is caused by the root uptake of specific elements by growing plants, which is followed by foliage deposition. Neither the shallow groundwater nor the plant foliage shows that Cd, Zn, and Pb concentrations are related to those in the sediments, but they clearly reflect the shallow groundwater pH, with the risk element mobilised by the acidity that is typical for the subsurface sediments in floodplains. The effect that plants have on the Pb in floodplains is significantly lower than that observed for Cd and Zn, while U can be considered even less mobile than Pb. Groundwater and plant leaves can contribute to secondary contamination with Cd and Zn from floodplain pollution hotspots, meaning that plants can accumulate these elements on the floodplain surface or even return them back to the fluvial transport, even if bank erosion would not occur. For Pb and U at the sites studied, these risks were negligible.

The potential wildfire effects on mercury remobilization from topsoils and biomass in a smelter-polluted semi-arid area.

Wildfires can be responsible for significant mercury (Hg) emissions especially in contaminated areas. Here, we investigated the Hg distribution in topsoils and vegetation samples and temperature-dependent Hg mobilization from biomass-rich topsoils collected near a copper (Cu) smelter in Tsumeb (semi-arid Namibia), where Hg-rich Cu concentrates are processed. The thermo-desorption (TD) experiments conducted on representative biomass-rich topsoils (3.9-7.7 mg Hg/kg) indicated that more than 91% of the Hg was released at ∼340 °C, which corresponds to the predominant grassland-fire conditions. The mineralogical investigation indicated that the Hg comes mainly from the deposited smelter emissions because no distinct Hg-rich microparticles corresponding to the windblown dust from the nearby disposal sites of the technological materials (concentrates, slags, tailings) were found. A comparison with the TD curves of the Hg reference compounds confirmed that the Hg in the biomass-rich topsoils occurs as a mixture of Hg bound to the organic matter and metacinnabar (black HgS), which exhibits similarities with the TD pattern of smelter flue dust residue. Despite the installation of a sulfuric acid plant in the smelter in 2015 and a calculated drop in the estimated Hg emissions (from 1301 ± 457 kg/y for the period 2004-2015 to 67 ± 5 kg/y after 2015), the Hg legacy pool in the smelter surroundings can potentially be re-emitted back to the atmosphere by wildfire. Using the Hg spatial distribution data in the area (184 km2), the estimates indicate that up to 303 kg and 1.3 kg can be remobilized from the topsoils and vegetation, respectively.