Biogeochemical cycling of sulphur in karst and transfer into speleothem archives at Grotta di Ernesto, Italy

Trace amounts of sulphur in speleothems suggest that stalagmites may act as archives of sulphur deposition, thereby recording aspects of atmospheric variability in sulphur content. Accurate interpretation of this novel sulphur archive depends upon understanding how biogeochemical cycling in the soil and epikarst above the cave may modify the precursor atmospheric values of sulphur concentration and isotopic composition prior to incorporation into the speleothem record. Dual isotope analysis of δ³⁴S-SO₄ and δ¹⁸O-SO₄ is used to trace biogeochemical transformations of atmospheric sulphur through the cave system at Grotta di Ernesto in the Italian Alps and builds towards a framework for interpretation of speleothem sulphur archives which depends on overlying ecosystem dynamics and karst hydrological properties. A three component model of atmospheric sulphate signal modification is proposed to be driven by (1). vegetation and soil cycling, (2). the degree of groundwater mixing in the karst aquifer; and (3). redox status. The relative influence of each process is specific to individual drip flow sites and associated stalagmites, rendering each sulphur archive a unique signal of environmental conditions. Under conditions found in the soil and epikarst above Grotta di Ernesto, the dual isotope signatures of sulphate sulphur and oxygen incorporated into speleothem carbonate, closely reflect past conditions of industrial sulphur loading to the atmosphere and the extent of signal modification through biogeochemical cycling and aquifer mixing.     

Effects of ammonium sulphate application on the rhizosphere,fine-root and needle chemistry in aPicea abies (L.) Karst. stand

Rhizosphere, fine-root and needle chemistry were investigated in a 28 year old Norway spruce stand in SW Sweden. The uptake and allocation pattern of plant nutrients and aluminium in control plots (C) and plots repeatedly treated with ammonium sulphate (NS) were compared. Treatments started in 1988. Current year needles, one-year-old needles and cylindrical core samples of the LFH-layer and the mineral soil layers were sampled in 1988, 1989 and 1990. Compared to the control plots, pH decreased significantly in the rhizosphere soil in the NS plots in 1989 and 1990 while the SO₄-S concentration increased significantly. Aluminium concentration in the rhizosphere soil was generally higher in the NS plots in all soil layers, except at 0–10 cm depths, both in 1989 and 1990. Calcium, Mg and K concentrations also increased after treatment with ammonium sulphate. Ammonium ions may have replaced these elements in the soil organic matter. The NS treatment significantly reduced Mg concentrations in fine roots in all layers in 1990. A similar trend was found in the needles. Ca concentrations in fine roots were significantly lower in the NS plots in the LFH layer in 1990 and the same pattern was found in the current needles. The N and S concentrations of both fine roots and needles were significantly higher in the NS plots. It was suggested that NS treatment resulted in displacement of Mg, Ca and K from exchange sites in the LFH layer leading to leaching of these cations to the mineral soil. Further application of ammonium sulphate may damage the fine roots and consequently adversely affect the water and nutrient uptake of root systems.     

Measured and modelled differences in nutrient concentrations between rhizosphere and bulk soil in a Norway spruce stand

The gradient in soil characteristics from the bulk soil to the root surface is important to roots and to the organisms that live in the rhizosphere. Our ability to measure ion concentrations at the root surface is extremely limited, and models are largely untested. We used data from a well studied Norway spruce stand in SW Sweden to compare the measured difference in nutrient concentrations between rhizosphere and bulk soil with the difference predicted by a steady-state simulation model based on ecosystem budgets of nutrient uptake. The simulation model predicted depletion of NH₄, Ca, Mg, K in the rhizosphere, which shows that budgeted uptake rates were greater than the mass flow of bulk solution towards the root. In plots treated with ammonium sulphate, the model predicted an accumulation of S in the rhizosphere. In contrast, the observed rhizosphere concentrations were generally enriched in nutrients, relative to bulk soil. Collecting rhizosphere soil adhering to root surfaces may not be an appropriate method for describing the concentration gradient around the root. In addition, the simulation model omits some processes affecting conditions in the rhizosphere that are important to explaining nutrient uptake.     

Distribution of sulphur forms in soils from beech and spruce forests of Mont Lozère (France)

From a quantitative inventory of sulphur forms and sulphur budget, the relation between the distribution of the various sulphur forms and the sulphate fluxes in three soil profiles has been addressed. These profiles are located in two forested watersheds at Mont Lozère. One has been sampled in a beech forest and the other two in a spruce forest and in a harvested plot of this spruce forest, respectively. The mean annual input-output budgets showed a sulphur immobilization in the soil cover of the three plots. In the preserved spruce forest plot, because of larger dry depositions, the sulphur immobilization is much greater than in other plots and occurs essentially in the B horizons. In the other two profiles, the dominant immobilization occurs in the parent material.The total sulphur content is very high in the forest floor reaching 2065 g S g^-1 in the litter of one of the soils under spruce. In the organo-mineral horizons of soils under spruce, the total sulphur content decreases with depth and ranges from 310 to 520 g S g^-1 in the A horizons to 100–200 g S g^-1 in the parent material. In the profile under beech, the total sulphur content is lower except in the parent material. In all cases, the organic sulphur is the major part of sulphur often representing more than 90% of total sulphur. In organo-mineral soil horizons of the spruce forest, the part of the sulphateesters is more important than in the soil of the beech forest, probably related to the different nature of the microbial activity in the spruce forest. In contrast, the humification processes are more efficient in the soil under beech, which can be due to the greater input of organic sulphur by litterfall. It appears that the dominant organic sulphur form varies as a function of microbial ecology and sulphate flux. The maximum of the inorganic sulphate is located at the base of the B horizons in the soil of the spruce forest and in the parent material of the soil under beech. In these horizons, the high content of inorganic sulphate can be related to the higher amounts of amorphous Fe and Al phases.     

Sulphate transformation to hydrogen sulphide in spruce seedlings

Summary Young Norway spruce seedlings irrigated with 5 per cent K₂SO₄ for 7 days exhale gaseous H₂S into the atmosphere. The share of the weight of H₂S per 1 kg of dry substance of needles for 1 h was 2.22 g during the 8th day. Where the K₂SO₄ solution was irrigated for 28 days, there began to appear on the needles a brown necrosis similar to those forming due to the effect of atmospheric sulphur dioxide. During the experiment, the exchange acidity of the soil pH/KCl did not change. The discussion discusses the mechanism of inhibition of metabolic processes in higher plants due to excessive amounts of SO₄-ion having been absorbed from the soil.     

Effects of liming and boron fertilization on boron uptake of Picea abies

The effects of liming on concentrations of boron and other elements in Norway spruce [Picea abies (L) Karst.] needles and in the mor humus layer were studied in long-term field experiments with and without B fertilizer on podzolic soils in Finland. Liming (2000+4000 kg ha^-1 last applied 12 years before sampling) decreased needle B concentrations in the four youngest needle age classes from 6–10 mg kg^-1 to 5 mg kg^-1. In boron fertilized plots the corresponding concentrations were 23–35 mg kg^-1 in control plots and 21–29 mg kg^-1 in limed plots. Both liming and B fertilizer decreased the Mn concentrations of needles. In the humus layer, total B concentration was increased by both lime and B fertilizer, and Ca and Mg concentrations and pH were still considerably higher in the limed plots than controls. Liming decreased the organic matter concentration in humus layer, whilst B fertilizer increased it.The results about B uptake were confirmed in a pot experiment, in which additionally the roles of increased soil pH and increased soil Ca concentration were separated by means of comparing the effects of CaCO₃ and CaSO₄. Two-year-old bare-rooted Norway spruce seedlings were grown in mor humus during the extension growth of the new shoot. The two doses of lime increased the pH of soil from 4.1 to 5.6 to 6.1, and correspondingly decreased the B concentrations in new needles from 22 to 12 to 9 mg kg^-1. However, CaSO₄ did not affect the pH of the soil or needle B concentrations. Hence the liming effect on boron availability in these soils appeared to be caused by the increased pH rather than increased calcium concentration.     

The oxygen isotopic signature of soil‐ and plant‐derived sulphate is controlled by fertilizer type and water source

The oxygen isotope signature of sulphate (δ¹⁸O_sulphate) is increasingly used to study nutritional fluxes and sulphur transformation processes in a variety of natural environments. However, mechanisms controlling the δ¹⁸O_sulphate signature in soil–plant systems are largely unknown. The objective of this study was to determine key factors, which affect δ¹⁸O_sulphate values in soil and plants. The impact of an ¹⁸O‐water isotopic gradient and different types of fertilizers was investigated in a soil incubation study and a radish (Raphanus sativus L.) greenhouse growth experiment. Water provided 31–64% of oxygen atoms in soil sulphate formed via mineralization of organic residues (green and chicken manures) while 49% of oxygen atoms were derived from water during oxidation of elemental sulphur. In contrast, δ¹⁸O_sulphate values of synthetic fertilizer were not affected by soil water. Correlations between soil and plant δ¹⁸O_sulphate values were controlled by water δ¹⁸O values and fertilizer treatments. Additionally, plant δ³⁴S data showed that the sulphate isotopic composition of plants is a function of S assimilation. This study documents the potential of using compound‐specific isotope ratio analysis for investigating and tracing fertilization strategies in agricultural and environmental studies.     

The effects of SO2 and O3 on the foliar nutrition of Scots pine, Norway spruce and Sitka spruce in the Liphook open-air fumigation experiment

Foliar elements were analysed in Scots pine, Sitka spruce and Norway spruce over a 6 year period before and during continuous exposure to SO₂ and O₃ in an open-air fumigation experiment. Sulphur dioxide treatment elevated foliar sulphur concentration in all species, and there were increases in foliar nitrogen in the two spruce species but not in pine. The concentrations of cations were frequently increased by SO₂ treatment, but there was no correlation between the sulphur concentration of needles and their total cation charge. SO₂-related elevations of foliar magnesium were correlated with the concentration of this element in soil solution, but the mechanism by which other cations were enhanced remains unclear. The only consistent effects on nutrient ratios were for SO₂ treatments to increase sulphur/cation ratios.     

Deposition and soil leaching in stands of Norway spruce and European Beech: Results from the Höglwald research in comparison with other European case studies

Stands of Norway spruce (Picea abies K.) and European beech (Fagus sylvatica L.) were investigated at the Höglwald research area, Southern Germany from 1985–1988 and from 1994–1997 in order to determine the effects of tree species on deposition and soil solution fluxes. The results were compared to 15 European case studies representing different deposition levels and site conditions. At the Höglwald site, which is characterised by a high nitrogen and a moderate sulphur load, throughfall deposition of nitrogen and sulphur compounds was about two-fold higher in spruce stands compared to beech stands. The differences in elemental input were clearly reflected in soil solution chemistry with a higher leaching of nitrate and sulphate in the spruce stands. The turnover of sulphur and nitrogen compounds induced a strong soil internal production of protons especially in the spruce stands. These results are in accordance with the other European case studies. Throughfall deposition and soil leaching of nitrogen and sulphur compounds was generally higher for spruce stands compared to beech stands. The species-related differences were mainly caused by dry deposition and were relatively small in remote areas. The consequences for the forest ecosystem itself and for the hydrosphere are discussed.     

Chemolithoautotrophic Nitrifiers in the Phyllosphere of a Spruce Ecosystem Receiving High Atmospheric Nitrogen Input

Evidence is presented for the first time that chemolithoautotrophic ammonia oxidizers (CAO) and chemolithoautotrophic nitrite oxidizers (CNO) colonize in appreciable cell numbers the phyllosphere of spruce trees in a forest ecosystem exposed for decades to high levels of atmospheric nitrogen (The Höglwald Forest, Bavaria, Germany). The results strongly indicate that both, CAO and CNO are predominantely located inside the spruce needles, most likely within the stomatal cavity. These results are further supported by field experiments of NH₃ uptake into twigs on intact spruce trees in the presence and absence of 10 Pa acetylene, an inhibitor of the ammonia monooxygenase of CAO. It is clearly demonstrated for the first time that in situ uptake of NH₃ from the atmosphere into spruce needles exposed to high levels of atmospheric N is not catalyzed exclusively by the tree, but is the result of combined activities of both, the spruce trees and the chemolithoautotrophic nitrifiers colonizing the needles.     

Long-distance Transport of Reduced Sulphur in Spruce (Picea abies L.)

Individual needles of 4-year-old spruce trees (Picea abies L.)were exposed to ³⁵S-GSH via the cut surface of the needle tipfor 2–3 h at different times during the growing season.From the previous year's source needle, ³⁵S-GSH was exportedinto the twig and translocated predominantly towards the twigapex. Independent from the growing season, transport towardsthe stem did not exceed 20% of the radioactivity recovered fromthe tissue samples. In July, the new needles appeared to bemetabolic sinks for reduced sulphur as indicated by the higherpercentages of both soluble and insoluble ³⁵S in this twig section,as compared to the previous years' needles. In October, thenew needles were no longer found to be a preferential sink forreduced sulphur. Estimates of the rate of GSH export from thesource needle in the light (2.5–11.3 nmol GSH g     

Studies of ‘Available’ and isotopically exchangeable sulphur in some North Queensland soils

Summary Using ³⁵S-sulphate, the specific activity of various sulphur fractions in some diverse North Queensland soils has been followed for up to 185 days in a glasshouse experiment. The sulphur extracted with 0.01 M calcium phosphate was from the same pool as that used by the test plants, and since near full recovery of added ³⁵SO₄ was obtained initially, this fraction is comparable to the L-value. On the other hand, 0.5 M NaHCO₃ removed some soil sulphur that was not available to the plants.Liming caused an initial increase in the phosphate extractable fraction, the sulphur seemingly being released from the NaHCO₃ extractable fraction, but decreased sulphate sorption also contributed to the increase in S uptake by the plants upon liming. re]19750507     

SO2-dependent cation competition and compartmentalization in Norway spruce needles

Ion contents in needles from Norway spruce trees [Picea abies (L.) Karst.] growing in Würzburg and in the SO₂-polluted Erzgebirge mountains were analysed to quantify cations which accumulate together with sulphate. In Würzburg there was a positive correlation of potassium (0.680 ± 0.300 Eq Eq^?1 SO₄^?2), magnesium (0.415 ± 0.111 Eq Eq^?1 SO₄^?2) and zinc (0.059 ± 0.006 Eq Eq^?1 SO₄^2?). In the Erzgebirge, potassium was also the stoichiometrically most important cation (0–887 ± 0–180 Eq K⁺ Eq^?1 SO₄^2?). All other correlations examined were weak or statistically non-significant. At both sites the calcium content of spruce needles did not depend on the sulphate content. The lack of a role for Ca²⁺ in neutralizing sulphate is a consequence of the presence of free oxalic acid in needles. Soluble oxalic acid precipitates Ca²⁺, which thereby becomes unavailable as a counterion for SO₄^2?. The activity coefficients of Ca²⁺ and oxalate^2?, and the solubility product of Ca-oxalate, were determined from in vivo data. It is concluded that the chronic accumulation of atmospheric sulphate in spruce needle vacuoles depletes available potassium and thereby strongly interferes with spruce growth and canopy turnover. This leads to impaired spruce vitality, even at sites where acute SO₂ disease symptoms are absent.     

Influence of nitrogen and sulphur form on manganese acquisition by barley (<Emphasis Type="Italic">shape Hordeum vulgare</Emphasis>)

The influence of various nitrogen (N) and sulphur (S) forms on the uptake of manganese (Mn) in young spring barley (Hordeum vulgare L cv Golf) plants was examined in both a hydroponic system and in a soil-based system. The soil was a typical Danish Mn-deficient soil viz. a sandy loam soil developed on old marine sediments. Plants growing in solution culture with NO₃^– as the only N source had a higher Mn uptake than plants receiving mixtures of NO₃^– and NH₄⁺. These findings were opposite to the results obtained in the soil-based experiments, where plants fertilized with NO₃^– as the only N source accumulated much less Mn than plants fertilized with NH₄⁺. Combining the results of these experiments confirmed that NH₄⁺ acted as a powerful antagonist to Mn²⁺ during uptake but that this antagonistic effect was more than compensated for by the influence of NH₄⁺ in reducing plant-unavailable Mn(IV) to plant-available Mn(II) in the soil. Furthermore the soil experiments showed that fertilizers containing sulphur in the form of reduced S (thiosulphate) had a strong mobilizing effect on Mn, and enabled the plants to accumulate large amounts of Mn in the biomass compared with oxidized S (sulphate). Thus, fertilization with thiosulphate may be very effective in alleviating Mn-deficiency in soils developed on old marine sediments where Mn availability is limiting plant growth.     

The Uptake and Metabolism of Sulphate in Scenedesmus as Influenced by Citrate, Carbon Dioxide, and Metabolic Inhibitors

The incorporation of sulphur from external sulphate into different fractions was studied in cells with a P content of 0.6 to 1 mg/g fresh weight as against 3 to 5 mg/g fresh weight in normal cells. — There is a flat and broad optimum for the action of pH in the region between 5.7 and 7. — In most cases, citrate inhibits the uptake of sulphur. — Five per cent CO₂ in the air enhances the incorporation of S. It is suggested that the effects of CO₂ may well be exerted by way of the carboxylation and decarboxylation mechanisms in the cells. — Selenate inhibits the formation of DNA-S and protein S more than that of lipid S, but the main effect in both cases seems to be in an early step of the assimilation of sulphate. In the absence of external phosphate, the inhibition is counteracted by CO₂, especially in darkness. Phosphate enhances the action of selenate on the organic S fractions, and in its presence CO₂ and darkness make the inhibition more pronounced. — Without P in the medium, the effects of selenate on uptake into the inorganic sulphate fraction are smaller than when the organic fractions are concerned. In the presence of CO₂ even stimulations due to selenate have been observed. External phosphate brings the inhibition of uptake into cellular SO₄^2- to the same level as found in the case of organic S. More than one pathway for the uptake as SO₄^2-seem possible. — Anaerobiosis and menadione affect the organic S fractions more than the sulphate; 2,4-dinitrophenol has a more uniform action all over the field.     

Plant Community Composition as a Predictor of Regional Soil Carbon Storage in Alaskan Boreal Black Spruce Ecosystems

The boreal forest is the largest terrestrial biome in North America and holds a large portion of the world’s reactive soil carbon. Therefore, understanding soil carbon accumulation on a landscape or regional scale across the boreal forest is useful for predicting future soil carbon storage. Here, we examined the relationship between floristic composition and ecosystem parameters, such as soil carbon pools, the carbon-to-nitrogen (C/N) ratio of live black spruce needles, and normalized basal area increment (NBAI) of trees in black spruce communities, the most widespread forest type in the boreal forest of Alaska. Variability in ecosystem properties among black spruce stands was as large as that which had previously been documented among all forest types in the central interior of Alaska; we found an eightfold range in NBAI and fivefold range in mineral soil carbon and nitrogen pools. Acidic black spruce communities had significantly more carbon in the organic soil horizon than did nonacidic black spruce communities, but did not differ in any other measured ecosystem parameter. We explained 48% of the variation in total soil carbon with a combination of plant community indices and abiotic and biotic factors. Plant community composition was at least as effective as any single environmental factor or stand characteristic in predicting soil C pools in Alaskan black spruce ecosystems. We conclude that among the community properties analyzed, the presence of key groups of species, overall species composition, and diversity of certain functional types, especially Sphagnum moss species, are important predictors of soil carbon sequestration in the black spruce forest type.     

The effect of air-borne ammonium sulphate onPinus nigra var.maritima in the Netherlands

Summary As a result of air pollution, considerable deposition of ammonium sulphate occurs on vegetation and soil in the vicinity of chicken farms and fields dressed with animal slurry. A clear relation exists between this ammonium sulphate deposition and the distance to certain agricultural activities. Field investigations and ecophysiological experiments both show that the needles ofPinus nigra var.maritima (Ait.) Melville take up ammonium and excrete potassium, magnesium and calcium. This often results in potassium and/or magnesium deficiencies and may lead to premature shedding of needles. The high levels of nitrogen in the needles are strongly correlated to fungal diseases.Whether the observed cation leaching will result in disturbed nutrient budgets depends mainly on soil conditions. Leaching of K, Mg and Ca from the soil, caused by ammonium sulphate, may further inhibit nutrient uptake.Field investigations show a clear correlation between increased ratios of NH₄ to K, Mg and Ca in the soil solution and the damage to pine forests.     

Interaction effect of sulphur and phosphorus on growth and nutrient content of moong (Phaseolus aureus L.)

Summary Sulphur-phosphorus interaction has been studied in a greenhouse experiment on a soil, deficient both in S and P with moong (Phaseolus aureus) as the test crop. The treatments were in the factorial combination of five levels of S and P (0, 5, 10, 20 and 40 ppm) applied as CaSO₄. 2H₂O and Ca(H₂PO₄)₂. H₂O respectively. A uniform treatment of N and K was made. The yield of vegetative tissues and grains increased with the application of S and P individually but decreased when S and P were applied in different combinations. Sulphur application increased S content but decreased P content in straw as well as in grains. Total P content increased with applied P and decreased with S application. Applied sulphur increased and phosphorus decreased the protein content in moong grains. Changes in N:S ratio in interaction was found to exist between S and P on the yield, grain quality, concentration and total removal of sulphur and phosphorus by Moong crop The antagonistic effect of sulphur and phosphorus fertilizer on the uptake and utilization of each other was more conspicuous when they were applied together. re]19760106     

Temporal changes and fluxes of sulphur and calcium in wet and dry deposition, internal circulation as well as in run-off and soil in a forest at Gårdsjön, Sweden

Sulphur dioxide in air as well as dry deposition of sulphur dioxide to a forest has decreased by a factor of 20 during the last two decades. It was earlier found that the internal circulation of calcium in Norway spruce follows the dry deposition of sulphur dioxide. The sulphur and calcium fluxes from 1992 were calculated from wet deposition, throughfall and a surrogate surface. Earlier fluxes from 1981 to 1991 were calculated using assumptions of the dry deposition of non-marine sulphate and calcium. The new estimates confirm the earlier studies that the internal circulation of calcium in a coniferous forest is directly related to the dry deposition of sulphur dioxide to the canopies and that the internal circulation of calcium decreases at the same rate as the deposition of sulphur decreased during the last two decades. The deposition fluxes were also compared to run-off and uptake of calcium in the forest as well as on modelled weathering rates from severely acidified forested catchments near the coast and inland and the soil pool. A reconstruction of changes in the soil pool of calcium over the last 100 years indicate that the soil pool has decreased by ca. 70% in catchments with complete harvest of the forest and ca. 40% if branches and needles are left on the ground. In a natural forest without acid deposition the soil pool of calcium would have increased by 6%. Estimates for the 21st century show that harvesting of stems+branches and needles may almost empty the soil pool of calcium in the next 100 years. Increased nitrogen deposition has increased forest growth, which indirectly increased uptake of calcium by the trees and indirectly caused a further decrease of the soil pool of calcium.     

Molybdate toxicity in Chinese cabbage is not the direct consequence of changes in sulphur metabolism

• In polluted areas, plants may be exposed to supra‐optimal levels of the micronutrient molybdenum. The physiological basis of molybdenum phytotoxicity is poorly understood. Plants take up molybdenum as molybdate, which is a structural analogue of sulphate. Therefore, it is presumed that elevated molybdate concentrations may hamper the uptake and subsequent metabolism of sulphate, which may induce sulphur deficiency.
• In the current research, Chinese cabbage (Brassica pekinensis) seedlings were exposed to 50, 100, 150 and 200 μm Na₂MoO₄ for 9 days.
• Leaf chlorosis and a decreased plant growth occurred at concentrations ≥100 μm . Root growth was more affected than shoot growth. At ≥100 μm Na₂MoO₄, the sulphate uptake rate and capacity were increased, although only when expressed on a root fresh weight basis. When expressed on a whole plant fresh weight basis, which corrects for the impact of molybdate on the shoot‐to‐root ratio, the sulphate uptake rate and capacity remained unaffected. Molybdate concentrations ≥100 μm altered the mineral nutrient composition of plant tissues, although the levels of sulphur metabolites (sulphate, water‐soluble non‐protein thiols and total sulphur) were not altered. Moreover, the levels of nitrogen metabolites (nitrate, amino acids, proteins and total nitrogen), which are generally strongly affected by sulphate deprivation, were not affected. The root water‐soluble non‐protein thiol content was increased, and the tissue nitrate levels decreased, only at 200 μm Na₂MoO₄.
• Evidently, molybdenum toxicity in Chinese cabbage was not due to the direct interference of molybdate with the uptake and subsequent metabolism of sulphate.