Vertical profiles of Tl, Pb and Zn concentrations and Tl and Pb isotopic ratios in a contaminated peatland/fen (Wolbrom, Poland) were studied to address questions regarding (i) potential long-term immobility of Tl in a peat profile, and (ii) a possible link in Tl isotopic signatures between a Tl source and a peat sample. Both prerequisites are required for using peatlands as archives of atmospheric Tl deposition and Tl isotopic ratios as a source proxy. We demonstrate that Tl is an immobile element in peat with a conservative pattern synonymous to that of Pb, and in contrast to Zn. However, the peat Tl record was more affected by geogenic source(s), as inferred from the calculated element enrichments. The finding further implies that Tl was largely absent from the pre-industrial emissions (>~250 years BP). The measured variations in Tl isotopic ratios in respective peat samples suggest a consistency with anthropogenic Tl (ε²⁰⁵Tl between ~ -3 and −4), as well as with background Tl isotopic values in the study area (ε²⁰⁵Tl between ~0 and −1), in line with detected ²⁰⁶Pb/²⁰⁷Pb ratios (1.16–1.19). Therefore, we propose that peatlands can be used for monitoring trends in Tl deposition and that Tl isotopic ratios can serve to distinguish its origin(s). However, given that the studied fen has a particularly complicated geochemistry (attributed to significant environmental changes in its history), it seems that ombrotrophic peatlands could be better suited for this type of Tl research.

Frequency and intensity of wildfire occurrences are dramatically increasing worldwide due to global climate change, having a devastating effect on the entire ecosystem including plants. Moreover, distribution of fire-smoke can influence the natural environment over very long distances, i.e. hundreds of kilometres. Dry plant matter contains 0.1–0.9% (w/w) sulphur, which is mainly released during combustion into the atmosphere as sulphur dioxide (SO₂) resulting in local concentrations of up to 3000 nL L⁻¹. SO₂ is a highly hazardous gas, which enters plants mostly via the stomata. Toxic sulphite is formed inside the leaves due to conversion of SO₂. Plants as sessile organisms cannot escape from threats, why they evolved an impressive diversity of molecular defence mechanisms. In the present study, two recent wildfires in Germany were evaluated to analyse the effect of SO₂ released into the atmosphere on deciduous trees: the Meppen peat fire in 2018 and the forest fire close to Luebtheen in 2019. Collected leaf material from beech (Fagus sylvatica) and oak (Quercus robur) was examined with respect to detoxification of sulphur surplus due to the exposure to elevated SO₂. An induced stress reaction in both species was indicated by a 1.5-fold increase in oxidized glutathione. In beech leaves, the enzymatic activities of the sulphite detoxification enzymes sulphite oxidase and apoplastic peroxidases were increased 5-fold and a trend of sulphate accumulation was observed. In contrast, oaks did not regulate these enzymes during smoke exposure, however, the constitutive activity is 10-fold and 3-fold higher than in beech. These results show for the first time sulphite detoxification strategies of trees in situ after natural smoke exposure. Beech and oak trees survived short-term SO₂ fumigation due to exclusion of toxic gases and different oxidative detoxification strategies. Beeches use efficient upregulation of oxidative sulphite detoxification enzymes, while oaks hold a constitutively high enzyme-pool available.

Scots pine (Pinus sylvestris L.) is a widespread tolerant forest tree-species; however, its adaptability to environmental change differs among sites with various buffering capacity. In this study, we compared the spatial effects of aridity index (AI) and nitrogen deposition (ND) on biomass density in natural and man-made pine stands of differing soil fertility using geographically weighted multiple lag regression. Soil fertility was defined using soil series as zonal trophic (27.9%), acidic (48.2%), gleyed (15.2%) and as azonal exposed (2.5%), maple (2.4%), ash (0.8%), wet (2.1%) and peat (0.9%) under pine stands in the Czech Republic (Central Europe; 4290.5 km²; 130–1298 m a.s.l.). Annual AI and ND in every pine stand were estimated by intersection between raster and vector from 1 × 1 km grid for years 2000, 2003, 2007 and 2010 of severe non-specific forest damage spread. Biomass density was obtained from a MODIS 250 × 250 m raster using the enhanced vegetation index (EVI) for years 2000–2015, with a decrease in EVI indicating non-specific damage. Environmental change was assessed by comparing predictor values at EVI time t and t+λ. Non-specific damage was registered over 51.9% of total forest area. Less than 8.8% of damaged stands were natural and the rest (91.2%) of damaged stands were man-made. Pure pine stands were more damaged than mixed. The ND effect prevailed up to 2007, while AI dominated later. Temporal increasing ND effect under AI effectiveness led to the most significant pine stand damage in 2008 and 2014. Predictors from 2000 to 2007 afflicted 58.5% of non-specifically damaged stands at R² 0.09–0.76 (median 0.38), but from 2000 to 2010 afflicted 57.1% of the stands at R² 0.16–0.75 (median 0.40). The most damaged stands occurred on acidic sites. Mixed forest and sustainable management on natural sites seem as effective remediation reducing damage by ND.

Mercury (Hg) is commonly extracted from solid phase samples using aqua regia for total Hg (tHg) analysis. However, uncertainties exist regarding the complete extraction of Hg by aqua regia, especially from carbonaceous materials. To investigate whether aqua regia can completely extract Hg from biochars, batch-style experiments were carried out to evaluate extraction efficiency of aqua regia with respect to Hg-loaded biochar and to characterize the residual Hg speciation and spatial distribution. Different types of biochars (raw, FeCl₃-modified, and FeSO₄-modified, prepared at different temperatures) were reacted with Hg-spiked solution before the digestion experiments. Adsorption analyses indicate the biochars were successfully loaded with Hg and that the Hg content was higher in biochars pyrolyzed at higher temperature (900 versus 300 or 600 °C). The results of digestion experiments indicate Hg could not be completely extracted from the biochars tested, with a greater percentage of residual Hg in biochars pyrolyzed at 600 (60 ± 15%) and 900 (75 ± 22%) than 300 °C (7 ± 2%). Furthermore, the fraction of residual Hg in FeSO₄-modified biochars after aqua regia digestion was significantly lower than in FeCl₃-modified and unmodified biochars. Confocal micro-X-ray fluorescence imaging (CMXRFI) showed residual Hg in biochars is concentrated on surfaces prior to digestion, but more homogeneously distributed after digestion, which indicates Hg on biochar surface is more easily digested. Hg extended X-ray absorption fine structure (EXAFS) spectra modelling showed residual Hg in biochars mainly exists as Hg(II)–Cl. These results indicate extra caution should be paid for tHg determinations using aqua regia digestion method in soil (especially in forest), sediment, and peat samples containing black carbon, activated carbon, or biochar.

Bitumen recovery from oil sands in northeastern Alberta, Canada produces large volumes of tailings, which are deposited in mining areas that must be reclaimed upon mine closure. A new technology of non-segregated tailings (NST) developed by Canadian Natural Resources Limited (CNRL) was designed to accelerate the process of oil sands fine tailings consolidation. However, effects of these novel tailings on plants used for the reclamation of oil sands mining areas remain to be determined. In the present study, we investigated the effects of NST on seedlings of three species of plants commonly planted in oil sands reclamation sites including paper birch (Betula papyrifera), white spruce (Picea glauca) and green alder (Alnus viridis). In the controlled-environment study, we grew seedlings directly in NST and in the two types of reclamation soils with and without added NST and we measured seedling growth, gas exchange parameters, as well as tissue concentrations of selected elements and foliar chlorophyll. White spruce seedlings suffered from severe mortality when grown directly in NST and their needles contained high concentrations of Na. The growth and physiological processes were also inhibited by NST in green alder and paper birch. However, the addition of top soil and peat mineral soil mix to NST significantly improved the growth of plants, possibly due to a more balanced nutrient uptake. It appears that NST may offer some advantages in terms of site revegetation compared with the traditional oil sands tailings that were used in the past. The results also suggest that, white spruce may be less suitable for planting at reclamation sites containing NST compared with the two studied deciduous tree species.

We investigated the influence of sulfate (SO₄²⁻) deposition and concentrations on the net formation and solubility of methylmercury (MeHg) in peat soils. We used data from a natural sulfate deposition gradient running 300 km across southern Sweden to test the hypothesis posed by results from an experimental field study in northern Sweden: that increased loading of SO₄²⁻ both increases net MeHg formation and redistributes methylmercury (MeHg) from the peat soil to its porewater. Sulfur concentrations in peat soils correlated positively with MeHg concentrations in peat porewater, along the deposition gradient similar to the response to added SO₄²⁻ in the experimental field study. The combined results from the experimental field study and deposition gradient accentuate the multiple, distinct and interacting roles of SO₄²⁻ deposition in the formation and redistribution of MeHg in the environment.

Hematite nanoparticles (NPs) exist naturally and ubiquitously in soil, and they are always associated with soil organic matter by forming organic-inorganic complexes. In this work, hematite NPs coated with peat humic acid (HAₚₑₐₜ) and soil humic acid (HAₛₒᵢₗ) were chosen as sorbents for hydrophobic organic contaminants (HOCs) to simulate the sorption processes in soil. Ionizable pentachlorophenol (PCP) and non-ionizable phenanthrene (PHE) were selected as representative HOCs. Compared with sorption isotherms of uncoated hematite NPs, the coating of HA onto the surface of hematite NPs substantially increased its sorption affinity for PCP and PHE by about 1-2 orders of magnitude, and the increasing degree was positively correlated to the HA content. These phenomena emphasized the dominant role of HA in the sorption process. The reduced polarity and the introduction of functional groups contributed to the enhanced sorption of HOCs on HA-coated hematite NPs. Furthermore, HAₚₑₐₜ-hematite NPs showed higher sorption affinity for both PCP and PHE than HAₛₒᵢₗ-hematite NPs, which was mainly due to the lower polarity and higher hydrophobicity of HAₚₑₐₜ-hematite NPs. The sorption of PCP and PHE on HA-coated hematite NPs was inhibited obviously with increasing pH values and the pH effect on PCP sorption was more significant than that of PHE, due to the deprotonation of functional groups within adsorbed HA, the loose structure of adsorbed HA and the dissociation of PCP. Our findings elucidated the mechanisms involved in HOCs sorption processes by HA-hematite NPs and provided a theoretical basis for environmental remediation with natural NPs (e.g., hematite NPs).

Dissolved organic carbon (DOC) has a major influence upon sorption/desorption and transport of hydrophobic organic contaminants (HOCs) in soil environments. However, the molecular mechanisms of DOC sorption and its effects on aged HOC desorption in contaminated soils still remain largely unclear. Here, effects of three different DOC (one from commercial peat and two from biochars produced at 300 °C and 500 °C pyrolysis temperatures, respectively) and oxalate (as a reference) on abiotic desorption behavior of aged phenanthrene from three agricultural soils were investigated. Results showed that desorption of aged phenanthrene from soils was predominantly dependent on soil organic carbon content. The presence of DOC and oxalate resulted in higher desorption of phenanthrene compared to water alone, and the effects were positively related to soil organic carbon content and DOC/oxalate concentration. The facilitating effects of DOC were further increased during the second consecutive desorption, whereas oxalate had no such effect. Ultra-high-resolution Fourier transform-ion cyclotron resonance-mass spectrometry confirmed the molecular fractionation of DOC at the soil-water interface during DOC sorption. Specifically, the DOC molecules with O-rich moieties were preferentially adsorbed, whereas the molecules with phenolic and aromatic structures were selectively retained in the soil solutions through competitive displacement and co-sorption reactions during sorption. The enriched phenyl structures in the retained DOC facilitated its association with phenanthrene in the solutions and thus the release of phenanthrene from the soils. In contrast, oxalate replaced some organic carbon from the soils and thus released the associated phenanthrene into the solutions. Our findings highlight the importance of the molecular composition and structure of DOC for the desorption of phenanthrene in soil-water environments, which may help improve our understanding of the release and transport of organic compounds in the environments.