A high-resolution soil sampling has been applied to two forest podzols (ACB-I and ACB-II) from SW Europe in order to investigate the soil components and processes influencing the content, accumulation and vertical distribution of Hg. Total Hg contents (THg) were 28.0 and 23.6 μg kg⁻¹ in A horizons of ACB-I and ACB-II, then they strongly decreased in the E horizons and peaked in the Bhs horizons of both soils (55.3 and 63.0 μg kg⁻¹). THg decreased again in BwC horizons to 17.0 and 39.8 μg kg⁻¹. The Bhs horizons accounted for 46 and 38% of the total Hg stored (ACB-I and ACB-II, respectively). Principal component analysis (PCA) and principal components regression (PCR), i.e. using the extracted components as predictors, allowed to distinguish the soil components that accounted for Hg accumulation in each horizon. The obtained model accurately predicted accumulated Hg (R² = 0.845) through four principal components (PCs). In A horizons, Hg distribution was controlled by fresh soil organic matter (PC4), whereas in E horizons the negative values of all PCs were consistent with the absence of components able to retain Hg and the corresponding very low THg concentrations. Maximum THg contents in Bhs horizons coincided with the highest peaks of reactive Fe and Al compounds (PC1 and PC2) and secondary crystalline minerals (PC3) in both soils. The THg distribution in the deepest horizons (Bw and BwC) seemed to be influenced by other pedogenetic processes than those operating in the upper part of the profile (A, E and Bhs horizons). Our findings confirm the importance of soils in the global Hg cycling, as they exhibit significant Hg pools in horizons below the uppermost O and A horizons, preventing its mobilization to other environmental compartments.

Even though the Amazon region is widely studied, there is still a gap regarding Cr exposure and its risk to human health. The objectives of this study were to 1) determine Cr concentrations in seven chemical fractions and 6 particle sizes in Amazon soils, 2) quantify hexavalent Cr (CrVI) concentrations using an alkaline extraction, 3) determine the oral and lung bioaccessible Cr, and 4) assess Cr exposure risks based on total and bioaccessible Cr in soils. The total Cr in both A (0–20 cm) and B (80–100 cm) horizons was high at 2346 and 1864 mg kg⁻¹. However, sequential extraction indicated that available Cr fraction was low compared to total Cr, with Cr in the residual fraction being the highest (74–76%). There was little difference in total Cr concentrations among particle sizes. Hexavalent Cr concentration was also low, averaging 0.72 and 2.05 mg kg⁻¹ in A and B horizon. In addition, both gastrointestinal (21–22 mg kg⁻¹) and lung (0.95–1.25 mg kg⁻¹) bioaccessible Cr were low (<1.2%). The low bioavailability of soil Cr and its uniform distribution in different particle sizes indicated that Cr was probably of geogenic origin. Exposure based on total Cr resulted in daily intake > the oral reference dose for children, but not when using CrVI or bioaccessible Cr. The data indicated that it is important to consider both Cr speciation and bioaccessibility when evaluating risk from Cr in Amazon soils.

The discharge of acidic mine drainage waters onto a hillslope in Dalarna, central Sweden, has lead to the contamination of the podzol soils with Cu, Fe, Ni, Pb, Zn and sulfate. Samples from contaminated and reference soils have been collected for chemical and mineralogical analyses. Jarosite is identified by x-ray diffraction analysis as a precipitate in the upper horizons (A, E, B) of the contaminated soils, where the soil acidity (pHKCₗ ∼ 2.6) promotes jarosite stability. The sequential chemical extraction of soil samples indicates that, in the reference A horizon, Cu, Pb, Ni and Zn are bound primarily to cation exchange sites and organic matter. In the A horizon of the contaminated soils closest to the rock dump, metal partitioning is dominated by the Fe oxide fractions, despite the high organic matter content; Pb is almost completely bound to crystalline Fe oxides, possibly adsorbed to Fe oxides or occuring in a jarosite solid solution. In the reference B and C horizons, Cu, Ni and Zn are primarily adsorbed/coprecipitated in the Fe oxide fractions, while Pb remains with a large fraction bound to organic matter. In the Fe-rich B horizon of the contaminated soils, the partitioning of the metals in cation exchange sites and to organic matter has greatly increased relative to the reference soils, resulting from the mobilization of organo-metal complexes down the profile.

The weathering release rate of base cations (BCw) from soil minerals is fundamentally important for terrestrial ecosystem growth, function, and sensitivity to acid deposition. Understanding BCw is necessary to reduce or prevent damage to acid-sensitive natural systems, in that this information is needed to both evaluate the effectiveness of existing policies, and guide establishment of further policies in the event they are required. Yet BCw is challenging to estimate. In this study, major sources of uncertainty associated with a process-based model (PROFILE) commonly used to estimate weathering rates were quantified in the context of efforts to quantify BCw for upland forest sites across the continental USA. These include uncertainty associated with parameterization of mineral content where horizon data are not available, stoichiometry of individual minerals, and specific surface area of soil and individual soil minerals. Mineral stoichiometry was not an important influence on BCw estimates (uncertainty < 1%). Characterizing B horizon mineralogy by averaging A and C horizons was found to be a minor (< 5%) contributor to uncertainty in some areas, but where mineralogy is known to vary with depth the uncertainty can be large. Estimating mineral-specific surface areas had a strong influence on estimated BCw, with rates increasing by as much as 250%. The greatest uncertainty in BCw estimates, however, was attributed to the particle size class-based method used to estimate the total specific surface area upon which weathering reactions can take place. The resulting uncertainty in BCw spanned multiple orders of magnitude at individual sites, highlighting this as the greatest challenge to ongoing efforts to produce robust BCw estimates across large spatial scales in the USA. Recommendations for improving estimates of BCw to support robust decision making for protection against terrestrial acidification are provided.

The potential for sulfate retention is an important soil feature for buffering of atmospheric acid deposition. We studied the effects of increasing additions of different neutral salts and acids on mobilization and retention of SO₄ ²- in acid forest soils. Soils containing up to 11 mmol SO₄ ²- kg⁻¹ were equilibrated with H₂O, NaCl, MgCl₂, and HCl. Release of SO₄ ²- was highest with H₂O and NaCl additions and lowest when HCl was used. Increasing the ionic strength of the added solutions caused decreasing SO₄ ²- concentrations in equilibrium solution. Decreasing pH in equilibrium solution was found to be the reason for the decrease in release. Even when the pH was < 4, the SO₄ ²- release decreased. We assume that this finding resulted from the fact that in the soils studied the SO₄ ²- sorption was controlled by the high contents of Fe oxides/hydroxides.Experiments with Na₂SO₄, MgSO₄, and H₂SO₄ demonstrated that the B horizons already containing high amounts of SO₄ ²- were still able to retain SO₄ ²-. Sulfate retention increased in the order Na₂SO₄ < MgSO₄ < H₂SO₄, which corresponds to increasing H⁺ availability. The higher SO₄ ²- retention along with MgSO₄ compared to Na₂SO₄ may be caused by higher potential of Mg to mobilize soil acidity compared to Na.

Microbial removal of C and N in soil-based wastewater treatment involves emission of CO₂, CH₄, N₂O, and N₂ to the atmosphere. Water-filled pore space (WFPS) can exert an important control on microbial production and consumption of these gases. We examined the impact of WFPS on emissions of CO₂, CH₄, N₂O, and N₂ in soil microcosms receiving septic tank effluent (STE) or effluent from a single-pass sand filter (SFE), with deionized-distilled (DW) water as a control. Incubation of B and C horizon soil for 1 h (the residence time of wastewater in 1 cm of soil) with DW produced the lowest greenhouse gas (GHG) emissions, which varied little with WFPS. In B and C horizon soil amended with SFE emissions of N₂O increased linearly with increasing WFPS. Emissions of CO₂ from soil amended with STE peaked at WFPS of 0.5–0.8, depending on the soil horizon, whereas in soil amended with SFE, the CO₂ flux was detectable only in B horizon soil, where it increased with increasing WFPS. Methane emissions were detectable only for STE, with flux increasing linearly with WFPS in C horizon soil, but no clear pattern was observed with WFPS for B horizon soil. Emissions of GHG from soil were not constrained by the lack of organic C availability in SFE, or by the absence of NO₃ availability in STE, and addition of acetate or NO₃ resulted in lower emissions in a number of instances. Emission of ¹⁵N₂ and ¹⁵N₂O from ¹⁵NH₄ took place within an hour of contact with soil, and production of ¹⁵N₂ was much higher than ¹⁵N₂O. ¹⁵N₂ emissions were greatest at the lowest WFPS value and diminished markedly as WFPS increased, regardless of water type and soil texture. Our results suggest that the fluxes of CO₂, CH₄, N₂O, and N₂ respond differently to WFPS, depending on water type and soil texture.

The nitrite reductase (nirS and nirK) and nitrous oxide reductase-encoding (nosZ) genes of denitrifying populations present in an agricultural grassland soil were quantified using real-time polymerase chain reaction (PCR) assays. Samples from three separate pedological depths at the chosen site were investigated: horizon A (0–10 cm), horizon B (45–55 cm), and horizon C (120–130 cm). The effect of carbon addition (treatment 1, control; treatment 2, glucose-C; treatment 3, dissolved organic carbon (DOC)) on denitrifier gene abundance and N₂O and N₂ fluxes was determined. In general, denitrifier abundance correlated well with flux measurements; nirS was positively correlated with N₂O, and nosZ was positively correlated with N₂ (P < 0.03). Denitrifier gene copy concentrations per gram of soil (GCC) varied in response to carbon type amendment (P < 0.01). Denitrifier GCCs were high (ca. 10⁷) and the bac:nirK, bac:nirS, bac:nir ᵀ , and bac:nosZ ratios were low (ca. 10⁻¹/10) in horizon A in all three respective treatments. Glucose-C amendment favored partial denitrification, resulting in higher nir abundance and higher N₂O fluxes compared to the control. DOC amendment, by contrast, resulted in relatively higher nosZ abundance and N₂ emissions, thus favoring complete denitrification. We also noted soil depth directly affected bacterial, archaeal, and denitrifier abundance, possibly due to changes in soil carbon availability with depth.

The aim of this study was to evaluate the use of various indicators in the assessment of environmental pollution and to determine the response of pine to changes of pollution levels. Mezaparks is a part of Riga that has been subject to various long-term effects of atmospheric pollution and, in particular, historically from a large superphosphate factory. To determine the spatial distribution of pollution, moss, pine bark and soil O and B horizons were used as sorbents in this study, as well as the additional annual increment of pine trees. The current spatial distribution of pollution is best shown by heavy metal accumulation in mosses and the long-term accumulation of P₂O₅ pollution by the soil O horizon. The methodological problems of using these sorbents were explored in the study. Environmental pollution and its changes could be associated with the tree growth ring annual additional increment of Mezaparks pine forest stands. The additional increment increased after the closing of the Riga superphosphate factory.

Background, aim and scope Chlormequat (Cq) is a plant growth regulator used throughout the world. Despite indications of possible effects of Cq on mammalian health and fertility, little is known about its fate and transport in subsurface environments. The aim of this study was to determine the fate of Cq in three Danish subsurface environments, in particular with respect to retardation of Cq in the A and B horizons and the risk of leaching to the aquatic environment. The study combines laboratory fate studies of Cq sorption and dissipation with field scale monitoring of the concentration of Cq in the subsurface environment, including artificial drains. Materials and methods For the laboratory studies, soil was sampled from the A and B horizons at three Danish field research stations—two clayey till sites and one coarse sandy site. Adsorption and desorption were described by means of the distribution coefficient (K d) and the Freundlich adsorption coefficient (K F,ads). The dissipation rate was estimated using soil sampled from the A horizon at the three sites. Half life (DT₅₀) was calculated by approximation to first-order kinetics. A total of 282 water samples were collected at the sites under the field monitoring study— groundwater from shallow monitoring screens located 1.5-4.5 m b.g.s. at all three sites as well as drainage water from the two clayey sites and porewater from suction cups at the sandy site, in both cases from 1 m b.g.s. The samples were analysed using LC-MS/MS. The field monitoring study was supported by hydrological modelling, which provided an overall water balance and a description of soil water dynamics in the vadose zone. Results The DT₅₀ of Cq from the A horizon ranged from 21 to 61 days. The Cq concentration-dependant distribution coefficient (K d) ranged from 2 to 566 cm³/g (median 18 cm³/g), and was lowest in the sandy soil (both the A and B horizons). The K F,ads ranged from 3 to 23 (µg¹ ⁻ ¹/n (cm³)¹/n g⁻¹) with the exponent (1/n) ranging from 0.44 to 0.87, and was lowest in the soil from the sandy site. Desorption of Cq was very low for the soil types investigated (<10%w). Cq in concentrations exceeding the detection limit (0.01 µg/L) was only found in two of the 282 water samples, the highest concentration being 0.017 µg/L. Discussion That sorption was highest in the clayey till soils is attributable to the composition of the soil, the soil clay and iron content being the main determinant of Cq sorption in both the A and B horizons of the subsurface environment. Cq was not detected in concentrations exceeding the detection limit in either the groundwater or the porewater at the sandy site. The only two samples in which Cq was detected were drainage water samples from the two clayey till sites. The presence of Cq here was probably attributable to the hydrogeological setting as water flow at the two clayey till sites is dominated by macropore flow and less by the flow in the low permeability matrix. In contrast, water flow at the sandy site is dominated by matrix flow in the high permeability matrix, with negligible macropore flow. Given the characteristics of these field sites, Cq adsorption and desorption can be expected to be controlled by the clay composition and content and the iron content. Combining these observations with the findings of the sorption and dissipation studies indicates that the key determinant of Cq retardation and fate in the soil is sorption characteristics and bioavailability. Conclusions The leaching risk of Cq was negligible at the clayey till and sandy sites investigated. The adsorption and desorption experiments indicated that absorption of Cq was high at all three sites, in particular at the clayey till sites, and that desorption was generally very limited. The study indicates that leaching of Cq to the groundwater is hindered by sorption and dissipation. The detection of Cq in drainage water at the clayey till sites and the evidence for rapid transport through macropores indicate that heavy precipitation events may cause pulses of Cq. Recommendations and perspectives The present study is the first to indicate that the risk of Cq leaching to the groundwater and surface water is low. Prior to any generalisation of the present results, the fate of Cq needs to be studied in other soil types, application regimes and climatic conditions to determine the Cq retardation capacity of the soils. The study identifies bioavailability and heavy precipitation events as important factors when assessing the risk of Cq contamination of the aquatic environment. The possible effects of future climate change need to be considered when assessing whether or not Cq poses an environmental risk.