Cadmium (Cd) concentration in wheat (<Emphasis Type="Italic">Triticum aestivum</Emphasis>) grown in Cd-spiked soil varies with the doses and biochar feedstock

Biochar is considered a promising amendment for the reduction of metal concentration in plants; however, the effects of biochar in terms of dose and feedstock on metal uptake by plants remain widely unclear. In the current study, three individual biochars were prepared at 450 °C from different feedstocks (wheat straw, sukh chain (Pongamia pinnata), and cotton sticks). The main aim was to evaluate their ability to remediate cadmium (Cd)-spiked soil in terms of growth response and Cd uptake by wheat (Triticum aestivum) tissues. Biochars were separately applied at 0, 1, and 2% (w/w) in Cd-spiked soil and wheat was grown until maturity in pots and then morphological and physiological parameters and Cd concentrations in grains, roots, and shoots were determined. The post-harvest soil was analyzed for extractable Cd concentrations. Plants grown in Cd-spiked soil treated with biochars had higher seed germination, lengths of roots, shoots, and spikes, grains per spike and leaf relative water contents, chlorophyll contents, and dry weight of roots, shoots, and grains as compared to the untreated control. Biochar treatments significantly decreased the Cd concentrations in shoots, roots, and grains as well as total Cd uptake by grains. Soil extractable Cd concentrations were significantly decreased with biochar treatments. The application of 2.0% wheat straw biochar was the most efficient treatment in increasing grain yield and decreasing Cd in grains as well as soil extractable Cd than the other two biochars and doses applied.     

Estimating long-term soil respiration rates from carbon isotopes occluded in gibbsite

Carbon occluded in the soil gibbsite crystal structure at the Panola Mountain Research Watershed, Georgia, U.S. is presumed to be in isotopic equilibrium with the CO₂ respired from soil organics by microbes and plant roots. Fitting of the stable carbon isotopic data to a Fickian diffusion-based depth function results in an estimate of 47 gC m⁻² y⁻¹ for the long-term soil respiration rate. A numerical model that includes depth-dependent production and diffusion terms results in estimates of 28-12 gC m⁻² y⁻¹. These values range from 15 to 50 times less than the average of modern values for mixed deciduous forests in wet temperate climates. This disparity has several implications for our understanding of the geologic record of climate change, which include: (1) evidence for a cooler and seasonally drier climate during the mid-Holocene in the southeastern U.S., or (2) fluxes of carbon from the soil pool as recorded by soil mineral proxies (i.e., long-term soil respiration rates) under estimate atmosphere annual carbon flux measurements (i.e., short-term measures), and (3) the need to refine soil respiration models used to relate paleosol stable carbon isotopic measurements to paleo-atmospheric estimates.     

A threshold in soil formation at Earth’s arid-hyperarid transition

The soils of the Atacama Desert in northern Chile have long been known to contain large quantities of unusual salts, yet the processes that form these soils are not yet fully understood. We examined the morphology and geochemistry of soils on post-Miocene fans and stream terraces along a south-to-north (27° to 24° S) rainfall transect that spans the arid to hyperarid transition (21 to ∼2 mm rain y⁻¹). Landform ages are ? 2 My based on cosmogenic radionuclide concentrations in surface boulders, and Ar isotopes in interbedded volcanic ash deposits near the driest site indicate a maximum age of 2.1 My. A chemical mass balance analysis that explicitly accounts for atmospheric additions was used to quantify net changes in mass and volume as a function of rainfall. In the arid (21 mm rain y⁻¹) soil, total mass loss to weathering of silicate alluvium and dust (−1030 kg m⁻²) is offset by net addition of salts (+170 kg m⁻²). The most hyperarid soil has accumulated 830 kg m⁻² of atmospheric salts (including 260 kg sulfate m⁻² and 90 kg chloride m⁻²), resulting in unusually high volumetric expansion (120%) for a soil of this age. The composition of both airborne particles and atmospheric deposition in passive traps indicates that the geochemistry of the driest soil reflects accumulated atmospheric influxes coupled with limited in-soil chemical transformation and loss. Long-term rates of atmospheric solute addition were derived from the ion inventories in the driest soil, divided by the landform age, and compared to measured contemporary rates. With decreasing rainfall, the soil salt inventories increase, and the retained salts are both more soluble and present at shallower depths. All soils generally exhibit vertical variation in their chemistry, suggesting slow and stochastic downward water movement, and greater climate variability over the past 2 My than is reflected in recent (∼100 y) rainfall averages. The geochemistry of these soils shows that the transition from arid to hyperarid rainfall levels marks a fundamental geochemical threshold: in wetter soils, the rate and character of chemical weathering results in net mass loss and associated volumetric collapse after 10⁵ to 10⁶ years, while continuous accumulation of atmospheric solutes in hyperarid soils over similar timescales results in dramatic volumetric expansion. The specific geochemistry of hyperarid soils is a function of atmospheric sources, and is expected to vary accordingly at other hyperarid sites. This work identifies key processes in hyperarid soil formation that are likely to be independent of location, and suggests that analogous processes may occur on Mars.     

Complexation of cadmium to sulfur and oxygen functional groups in an organic soil

Cadmium (Cd) is a toxic trace element and due to human activities soils and waters are contaminated by Cd both on a local and global scale. It is widely accepted that chemical interactions with functional groups of natural organic matter (NOM) is vital for the bioavailability and mobility of trace elements. In this study the binding strength of cadmium (Cd) to soil organic matter (SOM) was determined in an organic (49% organic C) soil as a function of reaction time, pH and Cd concentration. In experiments conducted at native Cd concentrations in soil (0.23 μg g⁻¹ dry soil), halides (Cl, Br) were used as competing ligands to functional groups in SOM. The concentration of Cd in the aqueous phase was determined by isotope-dilution (ID) inductively-coupled-plasma-mass-spectrometry (ICP-MS), and the activity of Cd²⁺ was calculated from the well-established Cd-halide constants. At higher Cd loading (500-54,000 μg g⁻¹), the Cd²⁺ activity was directly determined by an ion-selective electrode (ISE). On the basis of results from extended X-ray absorption fine structure (EXAFS) spectroscopy, a model with one thiolate group (RS⁻) was used to describe the complexation (Cd²⁺ + RS⁻ ? CdSR⁺; log K_CdSR) at native Cd concentrations. The concentration of thiols (RSH; 0.047 mol kg⁻¹ C) was independently determined by X-ray absorption near-edge structure (XANES) spectroscopy. Log K_CdSR values of 11.2-11.6 (pK_a for RSH = 9.96), determined in the pH range 3.1-4.6, compare favorably with stability constants for the association between Cd and well-defined thiolates like glutathione. In the concentration range 500-54,000 μg Cd g⁻¹, a model consisting of one thiolate and one carboxylate (RCOO⁻) gave the best fit to data, indicating an increasing role for RCOOH groups as RSH groups become saturated. The determined log K_CdOOCR of 3.2 (Cd²⁺ +  RCOO⁻ ? CdOOCR⁺; log K_CdOOCR; pK_a for RCOOH = 4.5) is in accordance with stability constants determined for the association between Cd and well-defined carboxylates. Given a concentration of reduced sulfur groups of 0.2% or higher in NOM, we conclude that the complexation to organic RSH groups may control the speciation of Cd in soils, and most likely also in surface waters, with a total concentration less than 5 mg Cd g⁻¹ organic C.     

In situ investigation of dissolution of heavy metal containing mineral particles in an acidic forest soil

We report the application of an in situ method to obtain field dissolution rates of fine mineral particles in soils. Samples with different metal-containing mineral and slag particles (lead oxide, copper concentrate and copper slag) from the mining and smelting industry were buried in the topsoil of an acidic forest soil for up to 18 months. In addition we studied the dissolution of these particles in samples of the same soil, in a sand matrix and in acid solution under constant temperature and moisture conditions in the laboratory. Under field conditions the PbO particles dissolved quite rapidly (2.4 ± 0.7 × 10⁻¹⁰ mol Pb m⁻² s⁻¹), whereas the copper concentrate (<1 × 10⁻¹¹ mol Cu m⁻² s⁻¹) and the copper slag particles (4.3 ± 0.8 × 10⁻¹¹ mol Cu m⁻² s⁻¹) proved to be more resistant to weathering. In addition to qualitative information on dissolution features (SEM), the method yielded quantitative data on in situ dissolution rates. The dissolution rates followed the order: sand with acid percolation (pH 3.5; lab) < soil (lab) < soil (field) < acid solution (pH 3.5; lab). Dissolution rates in soil were found to be lower under laboratory than under field conditions. The faster field rates may in part be attributed to the higher biological activity in the field soil compared to the same soil in the laboratory.     

Stable carbon isotope discrimination in rice field soil during acetate turnover by syntrophic acetate oxidation or acetoclastic methanogenesis

Rice fields are an important source for the greenhouse gas methane. In Italian rice field soil CH₄ is produced either by hydrogenotrophic and acetoclastic methanogenesis, or by hydrogenotrophic methanogenesis and syntrophic acetate oxidation when temperatures are below and above about 40-45 °C, respectively. In order to see whether these acetate consumption pathways differently discriminate the stable carbon isotopes of acetate, we measured the δ¹³C of total acetate and acetate-methyl as well as the δ¹³C of CO₂ and CH₄ in rice field soil that had been pre-incubated at 45 °C and then shifted to different temperatures between 25 and 50 °C. Acetate transiently accumulated to about 6 mM, which is about one-third of the amount of CH₄ produced, irrespective of the incubation temperature and the CH₄ production pathway involved. However, the patterns of δ¹³C of the CH₄ and CO₂ produced were different at low (25, 30, 35 °C) versus high (40, 45, 50 °C) temperatures. These patterns were consistent with CH₄ being exclusively formed by hydrogenotrophic methanogenesis at high temperatures, and by a combination of acetoclastic and hydrogenotrophic methanogenesis at low temperatures. The patterns of δ¹³C of total acetate and acetate-methyl were also different at high versus low temperatures, indicating the involvement of different pathways of production and consumption of acetate at the two temperature regimes. Isotope fractionation during consumption of the methyl group of acetate was more pronounced at low (α = 1.010-1.025) than at high (α = 1.0-1.01) temperatures indicating that acetoclastic methanogenesis exhibits a stronger isotope effect than syntrophic acetate oxidation. Small amounts of propionate also transiently accumulated and were analyzed for δ¹³C. The δ¹³C values slightly increased (by about 10‰) during production and consumption of propionate, but were not affected by incubation temperature. Collectively, our results showed distinct isotope discrimination for different paths of acetate (and propionate) production and consumption, albeit differences were only small, and discrimination between methanogenic and syntrophic acetate consumption in nature may be difficult to detect.     

Degradation of grass-derived pyrogenic organic material, transport of the residues within a soil column and distribution in soil organic matter fractions during a 28 month microcosm experiment

The microbial recalcitrance of char accumulated after vegetation fires and its transport within a soil column were studied in microcosms using ¹³C- and ¹⁵N-enriched pyrogenic organic material (PyOM). The PyOM from rye grass (Lolium perenne L.) was produced by charring at 350 °C under oxic conditions for 1 and 4 min to examine the impact of the charring degree. After 28 months, ¹³C recovery decreased to values between 62% and 65%, confirming that this material can be attacked by microorganisms and that the degradation occurs rapidly after accumulation of PyOM at the soil surface. The respective ¹⁵N recovery followed the same trend but tended to be higher (between 67% and 80%). Most of the added PyOM isotopic labels were recovered in the particulate organic matter (POM) fraction, containing between 84% and 65% of the added ¹³C and ¹⁵N after the first 2 months, being reduced by half at the end of the experiment. After 1 month, up to 13.8% of the ¹³C label and 12.4% of the ¹⁵N label were detected in the POM-free mineral fractions. This fast association of PyOM with the mineral phase indicates that physical soil properties have to be considered for the elucidation of PyOM stability. Addition of fresh unlabelled grass material as co-substrate resulted in comparable trends as for the pure PyOM but the total recovery of the isotopic labels clearly increased with respect to the amount of mineral-associated PyOM. Between 73% and 82% of the mineral-associated PyOM occurred in the clay separates (<2 μm) for which the highest values were obtained for the experiment with the more intensively charred PyOM and co-substrate addition.In summary, the study demonstrates the degradability of grass-derived PyOM. The addition of fresh plant material as an easily degradable co-substrate promoted the formation of partially decomposed PyOM and subsequently its association with the mineral phase, but did not increase the respective mineralisation rates. Detection of ¹³C and ¹⁵N content at different depths of the microcosm column demonstrated an additional loss of PyOM from top soil by way of mobilisation and transport to deeper horizons. All these processes have to be taken into account in order to obtain a more realistic view about the behaviour of PyOM in environmental systems and for estimation of the C and N sequestration potential.     

Spatial distribution of lead and lead isotopes in soil B-horizon, forest-floor humus, grass (Avenella flexuosa) and spruce (Picea abies) needles across the Czech Republic

Lead concentrations were determined in samples of soil B-horizon (N = 258), forest-floor humus (O-horizon, N = 259), grass (Avenella flexuosa, N = 251) and spruce (Picea abies, N = 253) needles (2nd year) collected at the same locations evenly spread over the territory of the Czech Republic at an average density of 1 site/300 km². Median Pb concentrations differ widely in the four materials: soil B-horizon: 27 mg/kg (3.3-220 mg/kg), humus: 78 mg/kg (19-1863 mg/kg), grass: 0.37 mg/kg (0.08-8 mg/kg) and spruce needles: 0.23 mg/kg (0.07-3 mg/kg). In the Pb distribution maps for humus, grass and spruce a number of well-known Pb-contamination sources are indicated by unusually high concentrations (e.g., the Pb smelter at Pribram, the metallurgical industry in the NE of the Czech Republic and along the Polish border, as well as the metallurgical industry in Upper Silesia and Europe’s largest coal-fired power plant at Bogatynia, Poland). The ratio ²⁰⁶Pb/²⁰⁷Pb was determined in all four materials. The median value of the ²⁰⁶Pb/²⁰⁷Pb isotope ratio in the soil B-horizon is 1.184 (variation: 1.145-1.337). In both humus and grass the median value for the ²⁰⁶Pb/²⁰⁷Pb isotope ratio is 1.162 (variation: 1.130-1.182), in spruce needles the median ratio is 1.159 (variation: 1.116-1.186). In humus, grass and spruce needles the known contamination sources are all marked by higher ²⁰⁶Pb/²⁰⁷Pb isotope ratios in the maps. Furthermore, the soil B-horizon, humus, grass and spruce needles show distinctly different spatial distribution patterns of the ²⁰⁶Pb/²⁰⁷Pb isotope ratios. The B-horizon does not provide a viable background value for metal concentrations in the O-horizon or plant materials. None of the maps provides evidence for the importance of traffic-related emissions for the observed isotope ratios at the scale of the Czech Republic.     

Arsenic speciation and turnover in intact organic soil mesocosms during experimental drought and rewetting

Wetlands are significant sources and sinks for arsenic (As), yet the geochemical conditions and processes causing a release of dissolved arsenic and its association with the solid phase of wetland soils are poorly known. Here we present experiments in which arsenic speciation was determined in peatland mesocosms in high spatiotemporal resolution over 10 months. The experiment included a drought/rewetting treatment, a permanently wet, and a defoliated treatment. Soil water content was determined by the TDR technique, and arsenic, iron and sulfate turnover from mass balancing stocks and fluxes in the peat, and solid phase contents by sequential extractions. Arsenic content ranged from 5 to 25 mg kg⁻¹ and dissolved concentrations from 10 to 300 μg L⁻¹, mainly in form of As(III), and secondarily of As(V) and dimethylated arsenic (DMA). Total arsenic was mainly associated with amorphous iron hydroxides (R² > 0.95, α < 0.01) and deeper into the peat with an unidentified residual fraction. Arsenic release was linked to ferrous iron release and primarily occurred in the intensely rooted uppermost soil. Volumetric air contents of 2-13 % during drought eliminated DMA from the porewater and suppressed its release after rewetting for >30 d. Dissolved As(III) was oxidized and immobilized as As(V) at rates of up to 0.015 mmol m⁻³ d⁻¹. Rewetting mobilized As(III) at rates of up to 0.018 mmol m⁻³ d⁻¹ within days. Concurrently, Fe(II) was released at depth integrated rates of up 20 mmol m⁻³ d⁻¹. The redox half systems of arsenic, iron, and sulfur were in persistent disequilibrium, with H₂S being a thermodynamically viable reductant for As(V) to As(III). The study suggests that rewetting can lead to a rapid release of arsenic in iron-rich peatlands and that methylation is of lesser importance than co-release with iron reduction, which was largely driven by root activity.     

Mineralogical impact on organic nitrogen across a long-term soil chronosequence (0.3-4100 kyr)

Large portions of organic N (ON) in soil exist tightly associated with minerals. Mineral effects on the type of interactions, chemical composition, and stability of ON, however, are poorly understood. We investigated mineral-associated ON along a Hawaiian soil chronosequence (0.3-4100 kyr) formed in basaltic tephra under comparable climatic, topographic, and vegetation conditions. Mineral-organic associations were separated according to density (ρ > 1.6 g/cm³), characterized by X-ray photoelectron spectroscopy (XPS), X-ray absorption near edge fine structure (NEXAFS) and analyzed for amino acid enantiomers and amino sugars. The ¹⁴C activity of mineral-bound OC was estimated by accelerator mass spectrometry. The close OC-ON relationship (r = 0.96) and XPS results suggest that ON exists incorporated in bulk mineral-bound OM and likely becomes associated with minerals as part of sorbing OM. The youngest site (0.3 kyr), with soils mainly composed of primary minerals (olivine, pyroxene, feldspar) and with little ON, contained the largest proportion of hydrolyzable amino sugars and amino acids but with a small share of acidic amino acids (aspartic acid, glutamic acid). In soils of the intermediate weathering stage (20-400 kyr), where poorly crystalline minerals and metal(hydroxide)-organic precipitates prevail, more mineral-associated ON was present, containing a smaller proportion of hydrolyzable amino sugars and amino acids due to the preferential accumulation of other OM components such as lignin-derived phenols. Acidic amino acids were more abundant, reflecting the strong association of acidic organic components with metal(hydroxide)-organic precipitates and variable-charge minerals. In the final weathering stage (1400-4100 kyr) with well-crystalline secondary Fe and Al (hydr)oxides and kaolin minerals, mineral-organic associations held less ON and were, relative to lignin phenols, depleted in hydrolyzable amino sugars and amino acids, particularly in acidic amino acids. XPS and NEXAFS analyses showed that the majority (59-78%) of the mineral-associated ON is peptide N while 18-34% was aromatic N. Amino sugar ratios and d-alanine suggest that mineral-associated ON comprises a significant portion of bacterial residues, particularly in the subsoil. With increasing ¹⁴C age, a larger portion of peptide N was non-hydrolyzable, suggesting the accumulation of refractory compounds with time. The constant d/l ratios of lysine in topsoils indicate fresh proteinous material, likely due to continuous sorption of or exchange with fresh N-containing compounds. The ¹⁴C and the d/l signature revealed a longer turnover of proteinous components strongly bound to minerals (not NaOH-NaF-extractable). This study provides evidence that interactions with minerals are important in the transformation and stabilization of soil ON. Mineral-associated ON in topsoils seems actively involved in the N cycling of the study ecosystems, accentuating N limitation at the 0.3-kyr site but increasing N availability at older sites.     

Coupled mobilization of dissolved organic matter and metals (Cu and Zn) in soil columns

Dissolved organic carbon (DOC) is a key component involved in metal displacement in soils. In this study, we investigated the concentration profiles of soil-borne DOC, Cu and Zn at various irrigation rates with synthetic rain water under quasi steady-state conditions, using repacked soil columns with a metal-polluted topsoil and two unpolluted subsoils. Soil solution was collected using suction cups installed at centimeter intervals over depth. In the topsoil the concentrations of DOC, dissolved metals (Zn and Cu), major cations (Ca²⁺ and Mg²⁺) and anions ( and ) increased with depth. In the subsoil, the Cu and Zn concentrations dropped to background levels within 2 cm. All compounds were much faster mobilized in the first 4 cm than in the rest of the topsoil. DOC and Cu concentrations were higher at higher flow rates for a given depth, whereas the concentrations of the other ions decreased with increasing flow rate. The decomposition of soil organic matter resulted in the formation of DOC, , and and was the main driver of the system. Regression analysis indicated that Cu mobilization was governed by DOC, whereas Zn mobilization was primarily determined by Ca and to a lesser extent by DOC. Labile Zn and Cu²⁺ concentrations were well predicted by the NICA-Donnan model. The results highlight the value of high-resolution in-situ measurements of DOC and metal mobilization in soil profiles.     

Climatic dependence of stable carbon and oxygen isotope signals recorded in speleothems: From soil water to speleothem calcite

Understanding the relationship between stable isotope signals recorded in speleothems (δ¹³C and δ¹⁸O) and the isotopic composition of the carbonate species in the soil water is of great importance for their interpretation in terms of past climate variability. Here the evolution of the carbon isotope composition of soil water on its way down to the cave during dissolution of limestone is studied for both closed and open-closed conditions with respect to CO₂.The water entering the cave flows as a thin film towards the drip site. CO₂ degasses from this film within approx. 10 s by molecular diffusion. Subsequently, chemical and isotopic equilibrium is established on a time scale of several 10-100 s. The δ¹³C value of the drip water is mainly determined by the isotopic composition of soil CO₂. The evolution of the δ¹⁸O value of the carbonate species is determined by the long exchange time T_ex, between oxygen in carbonate and water of several 10,000 s. Even if the oxygen of the CO₂ in soil water is in isotopic equilibrium with that of the water, dissolution of limestone delivers oxygen with a different isotopic composition changing the δ¹⁸O value of the carbonate species. Consequently, the δ¹⁸O value of the rainwater will only be reflected in the drip water if it has stayed in the rock for a sufficiently long time.After the water has entered the cave, the carbon and oxygen isotope composition of the drip water may be altered by CO₂-exchange with the cave air. Exchange times, , of about 3000 s are derived. Thus, only drip water, which drips in less than 3000 s onto the stalagmite surface, is suitable to imprint climatic signals into speleothem calcite deposited from it.Precipitation of calcite proceeds with time constants, τ_p, of several 100 s. Different rate constants and equilibrium concentrations for the heavy and light isotopes, respectively, result in isotope fractionation during calcite precipitation. Since T_ex ? τ_p, exchange with the oxygen in the water can be neglected, and the isotopic evolution of carbon and oxygen proceed analogously. For drip intervals T_d < 0.1τ_p the isotopic compositions of both carbon and oxygen in the solution evolve linearly in time. The calcite precipitated at the apex of the stalagmite reflects the isotopic signal of the drip water.For long drip intervals, when calcite is deposited from a stagnant water film, long drip intervals may have a significant effect on the isotopic composition of the DIC. In this case, the isotopic composition of the calcite deposited at the apex must be determined by averaging over the drip interval. Such processes must be considered when speleothems are used as proxies of past climate variability.     

Accumulation patterns of Cu and Ni for Indigofera melanadenia and Tephrosia longipes plant species growing in Cu–Ni mining area in Botswana

Indigofera melanadenia and Tephrosia longipes plant species, collected from Cu–Ni mining area, were evaluated for accumulation of Cu and Ni. The total and bioavailable concentrations of Cu and Ni in the host soils were also determined. Flame Atomic Absorption Spectrometry was used for all metal determinations. The total and bioavailable concentrations of Cu in the soils were in the range 900–9000 μg/g and 200–2000 μg/g respectively. For Ni, the total and bioavailable concentrations were in the range 900–2000 μg/g and ∼ 40–100 μg/g respectively. The concentrations of Cu and Ni in the leaves of I. melanadenia were higher than in the roots with a range 80–130 μg/g in the leaves and 20–80 μg/g in the roots for Cu and a range of 150–200 μg/g in the leaves and 20–60 μg/g in the roots for Ni. Concentration of Cu in T. longipes was in the range of 37–240 μg/g and 150–200 μg/g in the leaves and roots respectively while the concentration of Ni was 80–140 μg/g in the leaves and 25–100 μg/g in the roots. Results indicate that both species have a potential for accumulating Cu and Ni. Translocation factor, a ratio of shoots to roots metal concentration, was used to evaluate the translocation properties of the plants from roots to shoots. Translocation factors of the plants were ≥ 1 suggesting efficient translocation of metals from roots to shoots.     

Soils at the hyperarid margin: The isotopic composition of soil carbonate from the Atacama Desert, Northern Chile

We evaluate the impact of exceptionally sparse plant cover (0-20%) and rainfall (2-114 mm/yr) on the stable carbon and oxygen composition of soil carbonate along elevation transects in what is among the driest places on the planet, the Atacama Desert in northern Chile. δ¹³C and δ¹⁸O values of carbonates from the Atacama are the highest of any desert in the world. δ¹³C (VPDB) values from soil carbonate range from −8.2‰ at the wettest sites to +7.9‰ at the driest. We measured plant composition and modeled respiration rates required to form these carbonate isotopic values using a modified version of the soil diffusion model of [Cerling (1984) Earth Planet. Sci. Lett.71, 229-240], in which we assumed an exponential form of the soil CO₂ production function, and relatively shallow (20-30 cm) average production depths. Overall, we find that respiration rates are the main predictor of the δ¹³C value of soil carbonate in the Atacama, whereas the fraction C₃ to C₄ biomass at individual sites has a subordinate influence. The high average δ¹³C value (+4.1‰) of carbonate from the driest study sites indicates it formed—perhaps abiotically—in the presence of pure atmospheric CO₂.δ¹⁸O (VPDB) values from soil carbonate range from −5.9‰ at the wettest sites to +7.3‰ at the driest and show much less regular variation with elevation change than δ¹³C values. δ¹⁸O values for soil carbonate predicted from local temperature and δ¹⁸O values of rainfall values suggest that extreme (>80% in some cases) soil dewatering by evaporation occurs at most sites prior to carbonate formation. The effects of evaporation compromise the use of δ¹⁸O values from ancient soil carbonate to reconstruct paleoelevation in such arid settings.     

Effects of anthropopressure and soil properties on the accumulation of polycyclic aromatic hydrocarbons in the upper layer of soils in selected regions of Poland

Fifty soil samples collected from agricultural land in four regions of Poland with different anthropopressure were analysed for their content of 16PAHs by GC/MS. The regions correspond to Polish administrative units (voievodeships): Podlaskie and Lubelskie are situated in the rural East part of the country and more industrialised Slaskie and Dolnoslaskie voievodeships – in the South-West part. Basic physicochemical properties as well as the content of selected potentially harmful metals (Pb and Zn) were included in the soil analysis. Overall accumulation of Σ16PAHs in the upper soil layer was within the range 73–1800 μg kg⁻¹ with a geometric mean (GM) of 252 μg kg⁻¹, while the mean benzo(a)pyrene (BaP) load was 20 μg kg⁻¹. This corresponds with data for other European countries. Carcinogenic compounds contributed nearly in 50% to the total PAHs loads. In uncontaminated rural regions the mean Σ16PAHs and BaP contents were 113–159 μg kg⁻¹ and 11–13 μg kg⁻¹, respectively. Regional conditions strongly influenced the accumulation of PAHs ?4-rings, which were highly dependent (over 95%) on local anthropopressure expressed as dust and 4PAHs emission indexes. Soil acidity was the main soil parameter related to the accumulation of higher molecular weight PAHs in soils. In more contaminated regions a significant link between soil OM and PAH loads was noted. The same regions were characterised by associations between PAHs and potentially harmful metals implying common sources of pollution. Those relationships were not observed in the uncontaminated part of the country. The lower molecular weight PAHs contributed to a smaller extent (about 20%) to the total PAHs content in soils, and were less affected by anthropogenic factors.     

Use of GEMAS data for risk assessment of cadmium in European agricultural and grazing land soil under the REACH Regulation

Over 4000 soil samples were collected for the “Geochemical Mapping of Agricultural and Grazing Land Soil of Europe” (GEMAS) project carried out by the EuroGeoSurveys Geochemistry Expert Group. Cadmium concentrations are reported for the <2 mm fraction of soil samples from regularly ploughed fields (agricultural soil, Ap, 0–20 cm, N = 2218) and grazing land soil (Gr, 0–10 cm, N = 2127). The samples were collected in 33 European countries, covering 5.6 million km² at a sample density of 1 sample each per 2500 km² and were analysed in an aqua regia extraction followed by an ICP-MS finish. The median Cd value is 0.181 mg/kg for the Ap and 0.202 mg/kg for the Gr soil samples. The data allow a directly comparable country-specific regional exposure and risk characterisation for all EU countries covered. Direct risks of Cd for terrestrial organisms are only predicted for a few isolated sample sites: 2.3% of the Ap and 4.5% of the Gr sites, respectively.     

Stable Cu and Zn isotope ratios as tracers of sources and transport of Cu and Zn in contaminated soil

Copper and Zn metals are produced in large quantities for different applications. During Cu production, large amounts of Cu and Zn can be released to the environment. Therefore, the surroundings of Cu smelters are frequently metal-polluted. We determined Cu and Zn concentrations and Cu and Zn stable isotope ratios (δ⁶⁵Cu, δ⁶⁶Zn) in three soils at distances of 1.1, 3.8, and 5.3 km from a Slovak Cu smelter and in smelter wastes (slag, sludge, ash) to trace sources and transport of Cu and Zn in soils. Stable isotope ratios were measured by multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS) in total digests. Soils were heavily contaminated with concentrations up to 8087 μg g⁻¹ Cu and 2084 μg g⁻¹ Zn in the organic horizons. The δ⁶⁵Cu values varied little (−0.12‰ to 0.36‰) in soils and most wastes and therefore no source identification was possible. In soils, Cu became isotopically lighter with increasing depth down to 0.4 m, likely because of equilibrium reactions between dissolved and adsorbed Cu species during transport of smelter-derived Cu through the soil. The δ⁶⁶Zn_IRMM values were isotopically lighter in ash (−0.41‰) and organic horizons (−0.85‰ to −0.47‰) than in bedrock (−0.28‰) and slag (0.18‰) likely mainly because of kinetic fractionation during evaporation and thus allowed for separation of smelter-Zn from native Zn in soil. In particular in the organic horizons large variations in δ⁶⁶Zn values occur, probably caused by biogeochemical fractionation in the soil-plant system. In the mineral horizons, Zn isotopes showed only minor shifts to heavier δ⁶⁶Zn values with depth mainly because of the mixing of smelter-derived Zn and native Zn in the soils. In contrast to Cu, Zn isotope fractionation between dissolved and adsorbed species was probably only a minor driver in producing the observed variations in δ⁶⁶Zn values. Our results demonstrate that metal stable isotope ratios may serve as tracer of sources, vertical dislocation, and biogeochemical behavior in contaminated soil.     

Background concentrations of elements in surface soils and their changes as affected by agriculture use in the desert-oasis ecotone in the middle of Heihe River Basin,North-west China

The concentrations of twenty four chemical elements in the surface layer of natural desert soils and the cultivated farmland soils were measured at a desert-oasis ecotone in the middle of Heihe river basin, north-west China. Background values were estimated for (a) major elements (Si 335.3 g kg^− 1, Al 49.4 g kg^− 1, Fe 19.1 g kg^− 1, Ca 29.4 g kg^− 1, Mg 8.9 g kg^− 1, K 20.1 g kg^− 1, Na 17.5 g kg^− 1 and P 0.338 g kg^− 1), (b) heavy metals and non-metals (Cr 55.8 mg kg^− 1, Mn 404.8 mg kg^− 1, Ni 17.7 mg kg^− 1, Cu 5.1 mg kg^− 1, Zn 33.7 mg kg^− 1, Pb 15.5 mg kg^− 1 and As 5.2 mg kg^− 1) and (c) other trace elements (Ti 2.0 mg kg^− 1, V 55.3 mg kg^− 1, Co 5.7 mg kg^− 1, Rb 82.4 mg kg^− 1, Sr 232.9 mg kg^− 1, Y 14.7 mg kg^− 1, Zr 194.9 mg kg^− 1, Nb 7.8 mg kg^− 1 and Ba 720.6 mg kg^− 1). After natural desert soil was cultivated for agricultural use, significant changes in element concentrations occurred under tillage, irrigation and fertilisation management. Compared to natural soil, the for the levels of Si, K, Na, Sr, Zr and Ba decreased, and no changes were observed for Rb, while the values of the other 17 elements increase in agricultural soil from 1.2 to 3.5 times. However, their absolute concentrations are still low, suggesting that the arable soil in this region remains comparatively a clean soil. The increased silt, clay and organic carbon content, under long-term irrigation, enriched the fine-grained materials, and application of fertilisers and manure contributed to the accumulation of most elements in arable soil. The accumulation of elements in agricultural soil increased with increasing cultivation years and extent of soil development.     

Transfer of litter-derived N to soil mineral-organic associations: Evidence from decadal N tracer experiments

Mineral-organic associations act as mediators of litter-derived N flow to the mineral soil, but the time scales and pathways involved are not well known. To close that gap, we took advantage of decade old ¹⁵N litter labeling experiments conducted in two European forests. We fractionated surface soils by density with limited disaggregating treatment and investigated organic matter (OM) characteristics using δ¹³C, δ¹⁵N and the C/N ratio. Mineral properties were studied by X-ray diffraction and selective dissolution of pedogenic oxides.Three types of associations were isolated: plant debris with few trapped minerals (<1.65 g/cm³), aggregates dominated by phyllosilicates (1.65-2.4 g/cm³), and single mineral grains and pedogenic oxides with little OM (>2.4 g/cm³). A small proportion of ¹⁵N tracer was rapidly attached to single mineral grains, while most of it moved from plant debris to aggregates of low density and progressively to aggregates of higher density that contain a more microbially processed OM. After a decade, 60% of the ¹⁵N tracer found in the investigated horizon was retained in aggregates, while plant debris still contained 40% of the tracer.We present a conceptual model of OM and N flow through soil mineral-organic associations, which accounts for changes in density, dynamics and chemistry of the isolated structures. It suggests that microbial reworking of OM entrapped within aggregates (1.65-2.4 g/cm³) causes the gradient of aggregate packing and, further on, controls the flow of litter-derived N through aggregates. For associations with denser material (>2.4 g/cm³), mineralogy determines the density of the association, the type of patchy OM attached to mineral surfaces and controls the extent of litter-derived N incorporation.     

Incorporation of lead into calcium carbonate granules secreted by earthworms living in lead contaminated soils

The influence of soil organisms on metal mobility and bioavailability in soils is not currently fully understood. We conducted experiments to determine whether calcium carbonate granules secreted by the earthworm Lumbricus terrestris could incorporate and immobilise lead in lead- and calcium-amended artificial soils. Soil lead concentrations were up to 2000 mg kg⁻¹ and lead:calcium ratios by mass were 0.5-8. Average granule production rates of 0.39 ± 0.04 mg_calcite earthworm⁻¹ day⁻¹ did not vary with soil lead concentration. The lead:calcium ratio in granules increased significantly with that of the soil (r² = 0.81, p = 0.015) with lead concentrations in granules reaching 1577 mg kg⁻¹. X-ray diffraction detected calcite and aragonite in the granules with indications that lead was incorporated into the calcite at the surface of the granules. In addition to the presence of calcite and aragonite X-ray absorption spectroscopy indicated that lead was present in the granules mainly as complexes sorbed to the surface but with traces of lead-bearing calcite and cerussite. The impact that lead-incorporation into earthworm calcite granules has on lead mobility at lead-contaminated sites will depend on the fraction of total soil lead that would be otherwise mobile.