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).

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.

Cadmium toxicity investigated at the physiological and biophysical levels under environmentally relevant conditions using the aquatic model plant Ceratophyllum demersum.

Cadmium (Cd) is an important environmental pollutant and is poisonous to most organisms. We aimed to unravel the mechanisms of Cd toxicity in the model water plant Ceratophyllum demersum exposed to low (nM) concentrations of Cd as are present in nature. Experiments were conducted under environmentally relevant conditions, including nature-like light and temperature cycles, and a low biomass to water ratio. We measured chlorophyll (Chl) fluorescence kinetics, oxygen exchange, the concentrations of reactive oxygen species and pigments, metal binding to proteins, and the accumulation of starch and metals. The inhibition threshold concentration for most parameters was 20 nM. Below this concentration, hardly any stress symptoms were observed. The first site of inhibition was photosynthetic light reactions (the maximal quantum yield of photosystem II (PSII) reaction centre measured as Fv /Fm , light-acclimated PSII activity ΦPSII , and total Chl). Trimers of the PSII light-harvesting complexes (LHCIIs) decreased more than LHC monomers and detection of Cd in the monomers suggested replacement of magnesium (Mg) by Cd in the Chl molecules. As a consequence of dysfunctional photosynthesis and energy dissipation, reactive oxygen species (superoxide and hydrogen peroxide) appeared. Cadmium had negative effects on macrophytes at much lower concentrations than reported previously, emphasizing the importance of studies applying environmentally relevant conditions. A chain of inhibition events could be established.

Responses of diatom composition and teratological forms to environmental pollution in a post-mining lake (SW Poland).

Various types of environmental stressors, such as heavy metals, lignite residues, or extremely low water pH, cause the formation of teratological forms of diatoms during the reproductive cycle. The damage mainly includes an abnormal diatom valve outline, changes in the striation pattern, anomalies in the raphe line/sternum, reduction in the cell size, metabolism alterations, or combined deformities. Diatom remains with such morphological deformities occur in the sediments of post-mining lake LK-46 (SW Poland). This lake was formed by excavation after the end of lignite exploitation in the mid-1960s. The percentage of teratological valves in the studied lake ranged from 12 to 33% of the relative abundance. The majority of abnormal diatoms have been observed in species of Eunotia. The reconstruction of the diatom-inferred pH (DI-pH), together with the concentration of heavy metals in the sediments and contemporary measurements of the water pH, indicates that the lake was contaminated to varying degrees and was acidic from the beginning of lake creation until today. The lake is located in an area of acid mine drainage (AMD), and in its vicinity, there are overburden heaps containing lignite residues, which are eroded and supplied to the lake, constantly acidifying the water. In the youngest sediments, the concentration of heavy metals increased, while the percentage of abnormal diatoms decreased. Determining which factor, i.e., extremely low water pH and the presence of lignite or heavy metals, was responsible for the formation or reduction of teratogenic forms of diatoms is very difficult.

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.

Effects of a point source of phosphorus on the arsenic mobility and transport in a small fluvial system.

One of the leading causes of As release from streambed sediments into freshwater systems is competition with phosphate. Among important sources of P to the fluvial ecosystems are wastewater treatment plants (WWTP), estimated to account for 25-45% of all P in surface waters. In this paper, long-term effects of discharged phosphorus from a small WWTP on the arsenic mobility were studied in an As-enriched fluvial system (approx. 240 mg/kg) in central Czech Republic. After 7 years of elevated P (≤7.7 mg/L) in the stream water, the total As decreased by 25% and the total P increased by 40% in the sediments downstream (at a distance of 66 m). The results of the chemical extractions and mineralogical analyses indicated that the changes in the concentration were mostly due to the sorption processes in the Fe (oxyhydr)oxides (goethite and hematite). In the downstream samples, the As in these phases decreased two-fold, and P was significantly enriched by 45-140%. Phosphorus was also found precipitated as newly formed Ca phosphates. The stream water monitoring indicated that the discharged P was either sequestered when the levels of dissolved P were high (>2.3 mg/L) or released from the downstream sediments when these levels were low (<∼1.5 mg/L). Meanwhile, As was continuously mobilized from the downstream sediments likely due to (i) the ongoing As desorption from the exterior parts of the Fe (oxyhydr)oxides at high aqueous P levels and (ii) the dissolution of As-bearing Ca phosphates at low dissolved P levels. These findings clearly demonstrate that point sources of P to streams and rivers, such as WWTP, may result in the permanent and long-term release of As from contaminated streambed sediments.

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.

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.

Interaction Between Zn Deficiency, Toxicity and Turnip Yellow Mosaic Virus Infection in Noccaea ochroleucum.

Zinc is essential for the functioning of numerous proteins in plants. To investigate how Zn homeostasis interacts with virus infection, Zn-tolerant Noccaea ochroleucum plants exposed to deficient (Zn'0'), optimal (Zn10), and excess Zn (Zn100) concentrations, as well as Cd amendment, were infected with Turnip yellow mosaic virus (TYMV). Imaging analysis of fluorescence kinetics from the µs (OJIP) to the minutes (Kautsky effect, quenching analysis) time domain revealed strong patchiness of systemic virus-induced photosystem II (PSII) inhibition. That was more pronounced in Zn-deficient plants, while Zn excess acted synergistically with TYMV, in both cases resulting in reduced PSII reaction centers. Infected Cd-treated plants, already severely stressed, showed inhibited non-photochemical quenching and PSII activity. Quantitative in situ hybridization at the cellular level showed increased gene expression of ZNT5 and downregulation of HMA4 in infected Zn-deficient leaves. In Zn10 and Zn100 infected leaves, vacuolar sequestration of Zn increased by activation of HMA3 (mesophyll) and MTP1 (epidermis). This correlated with Zn accumulation in the mesophyll and formation of biomineralization dots in the cell wall (Zn100) visible by micro X-ray fluorescence tomography. The study reveals the importance of adequate Zn supply and distribution in the maintenance of photosynthesis under TYMV infection, achieved by tissue-targeted activation of metal transporter gene expression.

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.