Effect of peat organic matter on sulfide weathering and thallium reactivity: Implications for organic environments.

Weathering of Tl-containing sulfides in a model (12-week) peat pot trial was studied to better understand their geochemical stability, dissolution kinetics, alteration products and the associated release and mobility of anthropogenic Tl in organic environments. We also present the effect of industrial acid rainwater on sulfide degradation and Tl migration in naturally acidic peat. Sphalerite (ZnS) was much less stable in peat than other Tl-containing sulfides (galena and pyrite), and thus acted as a major phase responsible for Tl mobilization. Furthermore, Tl incongruently leached out over Zn from ZnS, and accumulated considerably more in the peat solutions (≤5 µg Tl/L) and the peat samples (≤0.4 mg Tl/kg) that were subjected to acid rain watering compared to a deionized H2O regime. This finding was in good agreement with the absence of secondary Tl-containing phases, which could potentially control the Tl flux into the peat. The behavior of Tl was not as conservative as Pb throughout the trial, since a higher peat mobility and migration potential of Tl was observed compared to Pb. In conclusion, industrial acid precipitations can significantly affect the stability of ZnS even in acidic peat/organic environments, making it susceptible to enhanced weathering and Tl release in the long term.

The Admont Grassland Experiment: 70 years of fertilizer application and its effects on soil and vegetation properties in an alluvial meadow managed under a three-cut regime.

Fertilizer application is a widely used management technique for increasing forage production from agricultural grassland. Fertilization is also a key driver of changes in soil nutrient status and plant species composition of grassland as shown in many short-term studies. Results from long-term experiments can further improve understanding of plant-soil relationships and help with management recommendations for agricultural and environmental outcomes. We collected data from a long-term experiment on alluvial meadow (Admont Grassland Experiment, Austria; established 1946) with 24 fertilization treatments managed under a three-cut regime. Soil sampling in autumn 2015 and vegetation sampling in spring 2016 were conducted in seven selected treatments. Combinations of N (nitrogen 80 kg ha-1), P (phosphorus 35 kg ha-1) and K (potassium 100 kg ha-1) were applied annually and compared with a non-fertilized control. Treatments were: Control, N, P, K, NP, NK, PK and NPK fertilization. Long-term different fertilization affected soil pH and nutrient concentrations in the soil and plant species composition, but no significant effects on species richness were found. Short species (<0.5 m height) prevailed in all treatments regardless of nutrient application, probably as a result of the three-cut defoliation. The dry matter biomass (DMB) yield in the Control was limited by N and P and synergisticly co-limited by N, P and K, and DMB yields of more than 5 t ha-1 per year were achieved under nutrient combinations containing P (NP, PK, NPK) without loss of species richness. Results from the Admont Grassland Experiment show that the tested nutrient combinations significantly increased DMB yield and changed the species composition, but without significant effects on species richness. Long-term biomass yields of more than 5 t ha-1 DMB per year can be achieved with any nutrient combination containing P without loss species richness in an alluvial meadow managed under a three-cut regime.

Evaluation of thallium isotopic fractionation during the metallurgical processing of sulfides: An update.

In this study, we report combined Tl isotopic and Tl mineralogical and speciation data from a set of Tl-rich sulfide concentrates and technological wastes from hydrometallurgical Zn extraction. We also present the first evaluation of Tl isotopic ratios over a cycle of sulfide processing, from the ore flotation to pyro- and hydrometallurgical stages. The results demonstrate that the prevailing Tl form in all samples is Tl(I), without any preferential incorporation into sulfides or Tl-containing secondary phases, indicating an absence of Tl redox reactions. Although the Tl concentrations varied significantly in the studied samples (~9-280 mg/kg), the overall Tl isotopic variability was small, in the range of -3.1 to -4.4 ± 0.7 (2σ) ε205Tl units. By combining present ε205Tl results with the trends first found for a local roasting plant, it is possible to infer minimum Tl isotopic effects throughout the studied industrial process. As a result, the use of Tl isotopic ratios as a source proxy may be complicated or even impossible in areas with naturally high/extreme Tl background contents. On the other hand, areas with two or more isotopically contrasting Tl sources allow for relatively easy tracing, i.e., in compartments which do not suffer from post-depositional isotopic redistributions.

Restoration management of cattle resting place in mountain grassland.

This study investigated the effect of restoration management of a weed-infested area, previously used as cattle resting place, on herbage production and nutrient concentrations in the soil and herbage. The experiment was undertaken from 2004 to 2011 at the National Park of Nízké Tatry, Slovakia. Three treatments were applied: (i) cutting twice per year, (ii) herbicide application, followed after three weeks by reseeding with a mixture of vascular plant species and then cut twice per year, and (iii) unmanaged. Treatments had significant effect on biomass production and concentration of nutrients in the soil and in herbage. Nutrient concentrations in herbage and in soil declined progressively under the cutting treatments and reached optimum ranges for dairy cattle at the end of the experiment when herbage N was less than 15 g kg-1 and herbage P was 3.4 g kg-1. There was also a strong positive relationship under the cutting treatments between soil nutrient concentrations and herbage nutrient concentrations for N, P, K, Mg and Ca. Although the cutting management as well as the combination of herbicide application with cutting management reduced nutrient concentrations in the soil and in herbage, the nutrient concentrations remained relatively high. We can conclude that restoration of grassland covered with weedy species like Urtica dioica and Rumex obtusifolius, with excessive levels of soil nutrients, cannot be achieved just by cutting and herbicide application.

The effects of first defoliation and previous management intensity on forage quality of a semi-natural species-rich grassland.

Semi-natural grasslands occupy large parts of the European landscape but little information exists about seasonal variations in their nutritive value during the growing season. This paper presents results of novel data showing the effect of 13 years of previous contrasting management intensities on herbage nutritional value in relation to different dates of first defoliation (by grazing or haymaking). The treatments were: extensive management and intensive management from previous years (1998-2011). Both treatments were cut in June followed by intensive/extensive grazing for the rest of the grazing season (July-October). To evaluate forage quality in the first defoliation date, biomass sampling was performed in the year 2012 for 23 weeks from May to mid-October, and in 2013 for seven weeks from May to mid-June. Sampling was performed from plots that were not under management during the sampling year. Previous extensive management was associated with significantly reduced forage quality for in vitro organic matter digestibility (IVOMD), crude protein, neutral detergent fibre, acid detergent fibre and reduced divalent cations (Ca, Mg) and Na during the first seven weeks of the grazing season and the forage was suitable only for beef cattle. Due to low forage IVOMD, the forage is suitable only for cattle maintenance or for low quality hay when the start of grazing was postponed from seven weeks of vegetative growth to 13 weeks, regardless of the previous intensity. Herbage harvested after 13 weeks of the grazing season was of very low quality and was unsuitable as a forage for cattle when it was the only source of feed. Agri-environmental payments are necessary to help agricultural utilisation to maintain semi-natural grasslands by compensating for deterioration of forage quality, not only for the postponement of the first defoliation (either as cutting or grazing) after mid-June, but also when extensive management is required.

What is the effect of 19 years of restoration managements on soil and vegetation on formerly improved upland grassland?

Finding the best management strategies to restore grassland diversity and achieve a compromise between agricultural use and biodiversity protection is a global challenge. This paper reports novel data relating to the impacts of 19 years of restoration managements predicted to increase botanical diversity within reseeded upland temperate grassland common in less favoured areas in Europe. The treatments imposed were: continuous sheep grazing, with and without lime application; hay cutting only, with and without lime application; hay cutting followed by aftermath grazing, with and without lime application; and a control treatment continuing the previous site management (liming, NPK application and continuous sheep grazing). Defoliation type, irrespective of liming, was the key driver influencing plant species diversity (hay cutting followed by aftermath grazing > hay cutting > grazing). Grazing only managements supported grasses at the expense of forbs, and thus related plant species diversity significantly declined. Limed treatments had higher concentrations of Ca and Mg in the soil compared to those receiving no lime. However, no effects on species richness or plant species composition were found. Potassium was the only element whose plant-available concentration in the soil tended to decrease in response to cutting treatments with herbage removal. Postponing the first defoliation to the middle of the growing season enables forbs to reach seed production, and this was the most effective restoration management option for upland grassland (as hay cutting only, and as hay cut followed by aftermath grazing). Although continuous low-density sheep grazing is often adopted as a means of improving floristic biodiversity, deleterious effects of this on plant diversity mean that it cannot be recommended as a means of long-term maintenance or restoration management of European temperate grasslands.

Thallium isotopic fractionation in soil: the key controls.

We studied the key geochemical and mineralogical factors that could affect the fractionation of stable thallium (Tl) isotopes in soil. A set of grassland soil samples enriched in geogenic Tl in combination with selected Tl-containing mineral materials from the Czech Republic (Kluky) were investigated for this purpose. The results demonstrate significant incorporation of Tl in pedogenic (specific) Mn-oxide, which led to a large accumulation of the heavy 205Tl isotope (∼+14 ε205Tl units), presumably resulting from oxidative Tl sorption. Consequently, we concluded that the Mn-oxide-controlled Tl uptake is the primary cause of the observed 205Tl enrichment in the middle profile zone, at the A/B soil horizon interface, with up to +4 of ε205Tl. Furthermore, our results displayed a clear relationship between the Tl isotopic fractionation degree and the Mn-oxide soil concentration (R2 = 0.6), as derived from the oxalate-extractable data. A combination of soil and mineralogical considerations suggests that 205Tl enrichment in respective soil samples is also partly due to the Tl present in micaceous clay minerals, mainly illite, which is the predominant pedogenic Tl host phase. In line with our previous results, this Tl behavior can be inferred from systematic Mn-oxide degradation and the associated Tl (enriched in 205Tl) cycling in the studied soils and thus, presumably in the redoximorphic soils in general.

Thallium stable isotope fractionation in white mustard: Implications for metal transfers and incorporation in plants.

We studied thallium (Tl) isotope fractionation in white mustard grown hydroponically at different Tl doses. Thallium isotope signatures in plants indicated preferential incorporation of the light 203Tl isotope during Tl uptake from the nutrient solution. Negative isotope fractionation was even more pronounced in dependence on how much the available Tl pool decreased. This finding corresponds to the concept of isotope overprinting related to a high contamination level in the growing media (solution or soil). Regarding Tl translocation in plants, we observed a large Tl isotope shift with an enrichment in the heavy 205Tl isotope in the shoots relative to the roots in treatments with low/moderate solution Tl concentrations (0.01/0.05 mg Tl/L), with the corresponding α205/203Tl fractionation factors of ˜1.007 and 1.003, respectively. This finding is probably a consequence of specific (plant) reactions of Tl replacing K in its cycle. The formation of the S-coordinated Tl(I) complexes, potentially affecting both Tl accumulation and Tl isotope fractionation in plants, however, was not proven in our plants, since we did not have indication for that on the basis of X-ray absorption spectroscopy, suggesting that Tl was mainly present as free/hydrated Tl+ ion or chemically bound to O-containing functional groups.

Thallium contamination of desert soil in Namibia: Chemical, mineralogical and isotopic insights.

We studied arid desert soils from Namibia (Rosh Pinah) that were contaminated with up to 7 mg kg-1 of thallium (Tl) via dust emitted from a local flotation tailing dam. Chemical extractions of waste and soil materials indicated that most of the Tl is strongly bound, in accordance with X-ray diffraction and X-ray absorption spectroscopy data that point to the predominant association of Tl with metal sulfides and phyllosilicates. The isotope fractionation factor ε205Tl of the soil samples (from -0.4 to +3.8) shows a positive linear relationship (R2 = 0.62) with 1/Tl, indicative for the mixing of two major Tl pools, presumably anthropogenic Tl and geogenic Tl. The ε205Tl value for the topmost soil samples (∼+3) closely matches the ε205Tl value for post-flotation waste particles with a diameter of <0.05 mm, whereas the bulk flotation waste exhibits a significantly larger ε205Tl value (∼+6). These variations are in accordance with predominant atmospheric transfer of Tl from the tailings to the adjacent soils via fine (dust) particles. The identified minimal Tl alteration in soils indicates that only a small part of the Tl could be potentially released and passively enter the vegetation, local population and/or food chain in the long term. From this viewpoint, Tl does not represent such an important environmental concern as other (abundant) contaminants at the locality. Furthermore, there could be a relevance for other alkaline desert soils, including those where Tl pollution plays a major role.

Thallium isotopes in metallurgical wastes/contaminated soils: A novel tool to trace metal source and behavior.

Thallium (Tl) concentration and isotope data have been recorded for contaminated soils and a set of industrial wastes that were produced within different stages of Zn ore mining and metallurgical processing of Zn-rich materials. Despite large differences in Tl levels of the waste materials (1-500mgkg-1), generally small changes in ε205Tl values have been observed. However, isotopically lighter Tl was recorded in fly ash (ε205Tl∼-4.1) than in slag (ε205Tl∼-3.3), implying partial isotope fractionation during material processing. Thallium isotope compositions in the studied soils reflected the Tl contamination (ε205Tl∼-3.8), despite the fact that the major pollution period ended more than 30 years ago. Therefore, we assume that former industrial Tl inputs into soils, if significant, can potentially be traced using the isotope tracing method. We also suggest that the isotope redistributions occurred in some soil (subsurface) horizons, with Tl being isotopically heavier than the pollution source, due to specific sorption and/or precipitation processes, which complicates the discrimination of primary Tl. Thallium isotope analysis proved to be a promising tool to aid our understanding of Tl behavior within the smelting process, as well as its post-depositional dynamics in the environmental systems (soils).

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.

Thallium contamination of soils/vegetation as affected by sphalerite weathering: a model rhizospheric experiment.

The environmental stability of Tl-rich sphalerite in two contrasting soils was studied. Rhizospheric conditions were simulated to assess the risk associated with sulfide microparticles entering agricultural (top)soils. The data presented here clearly demonstrate a significant effect of 500 µM citric acid, a model rhizospheric solution, on ZnS alteration followed by enhanced Tl and Zn release. The relative ZnS mass loss after 28 days of citrate incubation reached 0.05 and 0.03 wt.% in Cambisol and Leptosol samples respectively, and was up to 4 times higher, compared to H2O treatments. Incongruent (i.e., substantially increased) mobilization of Tl from ZnS was observed during the incubation time. Generally higher (long-term) stability of ZnS with lower Tl release is predicted for soils enriched in carbonates. Furthermore, the important role of silicates (mainly illite) in the stabilization of mobilized Tl, linked with structural (inter)layer Tl-K exchange, is suggested. Thallium was highly bioavailable, as indicated by its uptake by white mustard; maximum Tl amounts were detected in biomass grown on the acidic Cambisol. Despite the fact that sulfides are thought as relatively stable phases in soil environments, enhanced sulfide dissolution and Tl/trace element release (and bioaccumulation) can be assumed in rhizosphere systems.

Assessment of soil aluminium pools along three mountainous elevation gradients.

Anthropogenic soil acidification in mountain forests and consequent Al release still present a significant problem in many regions. The effect of deposition may differ according to stand conditions, including altitude. This contribution is focused on three elevation transects, two in the Jizera Mountains strongly influenced by acid deposition, one in the less affected Novohradske Mountains. Quantification of pools of different Al forms and related soil characteristics (organic carbon, exchangeable hydrogen cations, sorption characteristics, etc.) is evaluated. In the Novohradske Mountains, the pool of both organically bound and water-soluble Al increases with increasing altitudes. In the Jizera Mountains, the distribution is more complicated; it is strongly affected by different forest type (beech vs. spruce), deforestation, and other local differences. Higher amounts of Al are bound in the mineral horizons compared to the surface organic horizons, even in the case of organically bound Al pools. Further differences between different altitudes and between soil horizons in Al distribution were revealed by detailed Al speciation using HPLC/IC method.

Comparison of Al speciation and other soil characteristics between meadow, young forest and old forest stands.

The aim of this paper is to describe the influence of spruce (Picea abies) afforestation on soil chemical properties, especially on soil acidity and aluminium (Al) mobilization and speciation in soil. For our study we used a unique set of three adjacent plots, including a meadow and two spruce forest stands of different age, in otherwise comparable conditions. The plots were located in the region of Giant Mountains, north-eastern Czech Republic. In general, pH values decreased and Al concentrations increased significantly after afforestation. Speciation of KCl-extractable and water-soluble Al in soil samples was done by means of HPLC/IC method. The concentrations of Al(X)(1+) and Al(Y)(2+) forms (in both extracts) are higher in humic and organically enriched (Bhs) horizons. The highest concentration of Al(3+) in both extracts is in the B horizons of old forest. Generally, in all studied stands majority of Al in aqueous extract is in the Al(X)(1+) form, which indicates that a large amount of mobile Al is bound in organic complexes. It suggests that actual toxicity is rather low. On the other hand, we have proved that majority of KCl-extractable Al exists in Al(3+) form. Thus we can conclude that disturbance of existing equilibrium may cause massive release of highly toxic Al(3+) from soil sorption complex to the soil solution, and consequently it can endanger the whole ecosystem. Moreover, continuous soil acidification accelerated by anthropogenic factors leading to Al mobilization represents a chemical time bomb.

Grass cover on forest clear-cut areas ameliorates some soil chemical properties.

Clear-cut areas formed after forest decline due to acid deposition, pest attacks, or wind-breaks in temperate mountainous regions are often populated by grass (mainly Calamagrostis villosa). This study focused on the changes of soil chemical characteristics under the grass cover replacing the forest, focusing mainly on aluminium (Al) speciation. Clear-cut area due to strong acid deposition in the Jizera Mountains (Northern Bohemia) was studied. The soils under grass cover exhibit higher pH values and lower exchangeable Al content compared to adjacent surviving forest. Mobile Al species under the grass have larger proportion of non-toxic organic complexes. The content of exchangeable base cations is slightly higher under the grass. The positive effect of grass on soil chemistry was enhanced by liming. The temporary grass cover can therefore improve soil chemical quality for following reforestation. However, the differences are generally limited to surface organic horizons. Similar results were found also on a bark-beetle clear-cut area in the Bohemian Forest (Southern Bohemia) with smaller acid deposition; nevertheless, most differences were not significant there.