Sulfate Reduction in Peat from a New Jersey Pinelands Cedar Swamp

Microbial sulfate reduction rates in acidic peat from a New Jersey Pine Barrens cedar swamp in 1986 were similar to sulfate reduction rates in freshwater lake sediments. The rates ranged from a low of 1.0 nmol cm⁻³ day⁻¹ in February at 7.5- to 10.0-cm depth to 173.4 nmol cm⁻³ day⁻¹ in July at 5.0- to 7.5-cm depth. The presence of living Sphagnum moss at the surface generally resulted in reduced rates of sulfate reduction. Pore water sulfate concentrations and water table height also apparently affected the sulfate reduction rate. Concentrations of sulfate in pore water were nearly always higher than those in surface water and groundwater, ranging from 26 to 522 μM. The elevated pore water sulfate levels did not result from the evapotranspiratory concentration of infiltrating stream water or groundwater, but probably resulted from oxidation of reduced sulfur compounds, hydrolysis of ester sulfates present in the peat, or both. The total sulfur content of peat that had no living moss at the surface was 164.64 ± 1.5 and 195.8 ± 21.7 μmol g (dry weight)⁻¹ for peat collected from 2.5 to 5.0 and 7.5 to 10.0 cm, respectively. Organosulfur compounds accounted for 84 to 88% of the total sulfur that was present in the peat. C-bonded sulfur accounted for 91 to 94% of the organic sulfur, with ester sulfate being only a minor constituent. Reduced inorganic sulfur species in peat from 2.5 to 7.5 cm were dominated by H₂S-FeS (68%), while pyritic sulfide was the predominant inorganic sulfur species in the peat from depths of 7.5 to 10.0 cm (75%).     

Effects of repeated (NH4)2SO4 application on sulfur pools in soil,soil microbial biomass,and ground vegetation of two watersheds in the Black Forest/Germany

The effect of repeated (NH₄)₂SO₄ applications (3 × 700 kg ha^–1 in 1988, 1991, and 1994, respectively) on S pools in soil, soil microbial biomass, and ground vegetation was studied at two Norway spruce (Picea abies L. [Karst.]) sites in the Black Forest/Germany. In both eco-systems, most of the total S pool was located in the soil. The soil also was the predominant compartment for retention of applied SO₄ ^2--S. The fractions of organic and inorganic S forms in the initial soil S content, and the retention of experimentally applied S was different for both sites. In the podzol Schluchsee, organic S accounted for 92% of total S. In the cambisol Villingen, the S pool consisted of 33% organic S and 67% inorganic S. The retention of applied S in various compartments of both ecosystems reflected these proportions. Only minor amounts of fertilized S (<1%) was retained in the spruce trees, ground vegetation, and soil microbial biomass. However, between 51% (Villingen) and 72% (Schluchsee) of the applied S was retained in the soil. In the Schluchsee podzol, 75% of retained fertilizer S was accumulated as ester sulfate, whereas SO₄ ^2-adsorption and precipitation of Al hydroxy sulfates were restricted by dissolved organic matter in the soil solution. In the Villingen cambisol, SO₄ ^2- adsorption was the dominant process of S retention, although 20% of the fertilized S again was retained as ester sulfate. The significant relevance of organic S forms in the retention of fertilizer S in both soils emphasizes the need for models which include the formation and re-mineralization of organic S compounds, especially of ester sulfates, for correctly simulating and predicting the retention and remobilization of S in acid forest soils subject to changing atmospheric N and S deposition.     

Incorporation of 35SO 4 2− into sediments of three New York lakes

Intact sediment cores were obtained from three New York lakes in May, July, and October 1981. Radioactive S (as ³⁵SO ₄ ²⁻ ) was added to the overlying water and cores were incubated without atmospheric exchange for one week near lake bottom temperatures. Headspace flux of 0₂ as an index of sediment respiration rates varied among lakes and seasonally within lakes. Acidic South Lake had the lowest respiration rate at all seasons and also the smallest net incorporation of the ³⁵SO ₄ ²⁻ . Summer net isotope transformation into ester sulfate and non-HI reducible S (pyrite and C-bonded S) constituents was 88.6%, 89.4%, and 59.7% of total sediment isotope for Oneida, Deer, and South, respectively. Seasonal variation of net isotope incorporation was observed in each lake as were differences in ³⁵SO ₄ ²⁻ partitioning into major S pools. Of the S constituents analyzed, HCl digestible S (volatile sulfides) was the smallest pool, while ester sulfate and non-HI reducible S together accounted for greater than 50% of S isotope transformation in all lakes. In addition, ester sulfate is the major product of dissolved SO ₄ ²⁻ transformation and its formation results in less alkalinity generation than the formation of non-HI reducible S constituents. Thus ester sulfate transformation processes must be considered in calculating alkalinity generation by lake sediments. Financial support provided by Office of Water Research Technology (Project No. 13-096-NY). Financial support provided by Office of Water Research Technology (Project No. 13-096-NY).     

Sulfur dynamics in mineral horizons of two northern hardwood soils. A column study with 35S

Sulfur dynamics of two Spodosols were ascertained using soil columns constructed from homogenized mineral soil from nothern hardwood ecosystems at the Huntington Forest (HF) in the Adirondack Mountains of New York and Bear Brook Watershed in Maine (BBWM). Columns were leached for 20 weeks with a simulated throughfall solution with³⁵SO₄ ^2-. Sulfur constituents were similar to those of other Spodosols, with the organic S fractions (C-bonded S and ester sulfate) constituting over 90% of total S. HF soil columns had higher total S (14.9 mol S g^-1) than that for the BBWM soil columns (7.4 mol g^-1) primarily due to higher C-bonded S in the former.Initially, adsorbed SO₄ ^- accounted for 5 and 4% of total S for the BBWM and HF soil columns, respectively. After 20 weeks, adsorbed SO₄ ^2- decreased (81%) in BBWM and increased (33%) in HF soil columns. For both HF and BBWM soil columns, C-bonded S increased and ester sulfate decreased, but only for HF columns was there a net mineralization of organic S (5.6% of total S). The greatest decrease in ester sulfate occurred at the top of the columns.Leaching of³⁵S was less than 0.5% of the³⁵S added due to its retention in various S constituents. There was an exponential decrease in³⁵S with column depth and most of the radioisotope was found in C-bonded S (70–88 and 70–91% for BBWM and HF, respectively). The rapid turnover of adsorbed SO^2- ₄ was reflected in its high specific activity (834 and 26 kBq mol^-1 S for BBWM and HF, respectively). The lower specific activity of adsorbed SO₄ ^2- in HF was attributable to greater isotopic dilution by non-radioactive SO^2- ₄ derived from greater organic S mineralization in the HF versus the BBWM columns.Both soil columns initially had high levels of NO^- ₃ which resulted in the generation of H⁺ and net retention of SO₄ ^2- in the early phase of the experiment due to pH dependent sulfate adsorption; later NO₃ ^- decreased and SO₄ ^2- was desorbed. Leaching of NIO₃ ^- and SO₄ ^2- was correlated with losses of Mg²⁺ and Ca²⁺ of which the latter was the dominant cation.Analyses using both S mass balances and radioisotopes corroborate that for BBWM soil columns, SO^2- ₄ adsorption-desorption dominated the S biogeochemistry while in HF soil columns, organic S mineralization-immobilization processes were more important. It is suggested that similar techniques can be applied to soils in the field to ascertain the relative importances of SO₄ ^2- adsorption processes and organic S dynamics.     

Models of sulfur dynamics in forest and grassland ecosystems with emphasis on soil processes

The major S constituents in terrestrial ecosystems include inorganic SO ₄ ^2– , C-bonded S and ester sulfate with the organic fractions constituting the major soil S pools. Conceptual models of S dynamics link inorganic SO ₄ ^2– flux to organic sulfur transformations and other elements such as N and C. Mass balance models have been useful in ascertaining whether a system is at steady-state with respect to adsorption processes and/or nutritional demands of vegetation for S. Chemical equilibrium/surface complexation models have been used to evaluate the effects of a complex of factors, including effects of pH on SO₄ ^– adsorption and precipitation; these models have not generally been integrated into ecosystem models of S dynamics. Models such as ILWAS, Birkenes, Storgama, Trickle-Down and MAGIC were developed to ascertain surface water acidification processes within watersheds; these models incorporated SO₄ ^2– adsorption in some formulation combined with hydrological considerations. None of these models explicitly treat organic S transformations and fluxes. In contrast, grassland ecosystem models detail organic S transformations, but give little attention to adsorption and hydrologic factors. More detailed simulation models of S transformations in forest and grassland soils have recently been developed, but these results have yet to be incorporated into ecosystem and watershed models.     

Dissolved organic sulphur in soil water under <Emphasis Type="Italic">Pinus sylvestris</Emphasis> L. and <Emphasis Type="Italic">Fagus sylvatica</Emphasis> L. stands in northeastern Bavaria,Germany variations with seasons and soil depth

Organically bound species have been identified as prominent and mobile forms of nitrogen and phosphorus in soils. Since a large portion of sulphur (S) in soil is bonded to carbon (C) also dissolved organic S likely is a significant constituent in soil water. To investigate the role of dissolved organic forms in leaching and cycling of S in forest soils, we examined concentrations, fluxes, and chemical composition of organic S in forest floor leachates and in soil solutions of Rendzic Leptosols under 90-year-old European beech (Fagus sylvatica L.) and Haplic Arenosols under 160-year-old Scots pine (Pinus sylvestris L.) for 27 months. These soils are low in adsorbed SO₄^2- and receive little atmospheric S depositions at present. The chemical composition of organic S was estimated by fractionation with XAD-8 and wet-chemical characterisation (HI reduction) of binding forms. Although not as prominent as the organic forms of other nutrient elements, organic S proved to be an important contributor to S dissolved in forest floor leachates and in mineral soil solutions. Dissolved organic matter contained on average 29% of total S in forest floor leachates at the pine site and 34% at the beech site. The largest portion of organic S occurred in the subsoil solutions under beech in summer and autumn (up to 53%). Mean concentrations of organic S peaked (up to 1.1 mg l^-1) in summer after rainstorms that followed dry periods. Fluxes with forest floor leachates and at 90 cm soil depth were largest in autumn because of huge amounts of rainfall. Organic S contributed significantly to the fluxes of S in the subsoils under beech comprising on average 39% of total dissolved S at 90 cm depth. Organic S produced in the forest floor layers was mainly in the hydrophilic fraction of dissolved organic matter (62 ± 6% at the pine site, 85 ± 4% at the beech site). The major binding form of organic S in the hydrophobic fraction was C-bonded S while in the hydrophilic fraction ester sulphate S, possibly associated with carbohydrates, was more prominent. Since the hydrophobic fraction increased in summer and autumn, C-bonded S was of greater importance during that time of the year than in winter and spring. With depth, concentrations and composition of organic S (and also of C) hardly changed at the pine site because of little retention of dissolved organic matter, presumably because of the small sorption capability of that soil. At the beech where organic C showed a marked decrease with depth, only a slight decrease in organic S, exclusively from the hydrophobic fraction, was found indicating that organic S was mobile compared with organic C. This was probably due to the concentration of S in the hydrophilic fraction of dissolved organic matter. Because of being concentrated in the mobile hydrophilic fraction, ester sulphate S was more mobile in the soil under beech than C-bonded S.     

Structural and Mechanistic Analysis of the Choline Sulfatase from Sinorhizobium melliloti: A Class I Sulfatase Specific for an Alkyl Sulfate Ester

Hydrolysis of organic sulfate esters proceeds by two distinct mechanisms, water attacking at either sulfur (S–O bond cleavage) or carbon (C–O bond cleavage). In primary and secondary alkyl sulfates, attack at carbon is favored, whereas in aromatic sulfates and sulfated sugars, attack at sulfur is preferred. This mechanistic distinction is mirrored in the classification of enzymes that catalyze sulfate ester hydrolysis: arylsulfatases (ASs) catalyze S–O cleavage in sulfate sugars and arylsulfates, and alkyl sulfatases break the C–O bond of alkyl sulfates. Sinorhizobium meliloti choline sulfatase (SmCS) efficiently catalyzes the hydrolysis of alkyl sulfate choline-O-sulfate (k_cat/K_M = 4.8 × 10³ s^? 1 M^? 1) as well as arylsulfate 4-nitrophenyl sulfate (k_cat/K_M = 12 s^? 1 M^? 1). Its 2.8-Å resolution X-ray structure shows a buried, largely hydrophobic active site in which a conserved glutamate (Glu386) plays a role in recognition of the quaternary ammonium group of the choline substrate. SmCS structurally resembles members of the alkaline phosphatase superfamily, being most closely related to dimeric ASs and tetrameric phosphonate monoester hydrolases. Although > 70% of the amino acids between protomers align structurally (RMSDs 1.79–1.99 Å), the oligomeric structures show distinctly different packing and protomer–protomer interfaces. The latter also play an important role in active site formation. Mutagenesis of the conserved active site residues typical for ASs, H₂¹⁸O-labeling studies and the observation of catalytically promiscuous behavior toward phosphoesters confirm the close relation to alkaline phosphatase superfamily members and suggest that SmCS is an AS that catalyzes S–O cleavage in alkyl sulfate esters with extreme catalytic proficiency.     

In situ S‐isotope compositions of sulfate and sulfide from the 3.2 Ga Moodies Group,South Africa: A record of oxidative sulfur cycling

Sulfate minerals are rare in the Archean rock record and largely restricted to the occurrence of barite (BaSO₄). The origin of this barite remains controversially debated. The mass‐independent fractionation of sulfur isotopes in these and other Archean sedimentary rocks suggests that photolysis of volcanic aerosols in an oxygen‐poor atmosphere played an important role in their formation. Here, we report on the multiple sulfur isotopic composition of sedimentary anhydrite in the ca. 3.22 Ga Moodies Group of the Barberton Greenstone Belt, southern Africa. Anhydrite occurs, together with barite and pyrite, in regionally traceable beds that formed in fluvial settings. Variable abundances of barite versus anhydrite reflect changes in sulfate enrichment by evaporitic concentration across orders of magnitude in an arid, nearshore terrestrial environment, periodically replenished by influxes of seawater. The multiple S‐isotope compositions of anhydrite and pyrite are consistent with microbial sulfate reduction. S‐isotope signatures in barite suggest an additional oxidative sulfate source probably derived from continental weathering of sulfide possibly enhanced by microbial sulfur oxidation. Although depositional environments of Moodies sulfate minerals differ strongly from marine barite deposits, their sulfur isotopic composition is similar and most likely reflects a primary isotopic signature. The data indicate that a constant input of small portions of oxidized sulfur from the continents into the ocean may have contributed to the observed long‐term increase in Δ³³S_sulfate values through the Paleoarchean.     

Phloem transport of sulfur in Ricinus

Mature leaves of Ricinus communis fed with ³⁵SO ₄ ^2- in the light export labeled sulfate and reduced sulfur compounds by phloem transport. Only 1–2% of the absorbed radiosulfur is exported to the stem within 2–3 h, roughly 12% of ³⁵S recovered was in reduced form. The composition of phloem translocate moving down the stem toward the root was determined from phloem exudate: 20–40% of the ³⁵S moved in the form of organic sulfur compounds, however, the bulk of sulfur was transported as inorganic sulfate. The most important organic sulfur compound translocated was glutathione, carrying about 70% of the label present in the organic fraction. In addition, methionine and cysteine were involved in phloem sulfur transport and accounted for roughly 10%. Primarily, the reduced forms of both, glutathione and cysteine are prsent in the siever tubes.Abbreviations CySH cysteine - GSH glutathione - GSSG glutathione disulfide - NEM N-ethylmaleimide - CyS-SCy cystine     

The influence of organic soil amendments on sulfate adsorption and sulfur availability in a Brazilian Oxisol

Soil management practices that involve additions of organic materials may influence plant sulfur availability in highly-weathered, acid soils. This study evaluated the effects of organic additions on sulfate adsorption and sulfur availability in a limed (3,4 t ha^-1) and unlimed Typic Haplustox soil of the Cerrado Region of Brazil. In unlimed soil, the proportion of applied sulfate (600 kg S ha^-1 as gypsum) that was adsorbed temporarily decreased over two cropping seasons by incorporation of 10 t dry matter ha^-1 crop^-1 of guinea grass (Panicum maximum Jacq.) but not when a similar quantity of a tropical legume, feijâo de porco (Canavalia ensiformis L.), was added. Liming reduced sulfate adsorption and resulted in sulfate leaching to a depth of 30 to 45 cm. Both plant materials temporarily reduced sulfate adsorption in laboratory studies when added to an unlimed soil at a rate equivalent to 40 t ha^-1. Analysis of soil properties affected by organic additions and liming showed significant correlations between sulfate adsorption and soil pH, extractable aluminum, calcium and magnesium, and surface charge. Maize dry matter yields increased by 1.3 to 3.5 t ha^-1 with addition of both organic materials. However, only the feijâo de porco treatment resulted in increases in sulfur uptake for the years in which organic materials were applied. Determining the effects of organic material additions on plant sulfur availability is complicated by the combined effects of sulfur mineralization, sulfate adsorption, and the plant's ability to utilize adsorbed subsoil sulfate.Joint contribution of Cornell University and CPAC-EM- BRAPA. This research was supported by USAID through the Title XII CRSP subgrant SM-CRSP-10 from North Carolina State University     

Cycling of inorganic and organic sulfur in peat from Big Run Bog,West Virginia

Total S concentration in the top 35 cm of Big Run Bog peat averaged 9.7 mol·g — wet mass^–1 (123 mol·g dry mass^–1). Of that total, an average of 80.8% was carbon bonded S, 10.4% was ester sulfate S, 4.5% was FeS₂­S, 2.7% was FeS­S, 1.2% was elemental S, and 0.4% was SO₄ ^2–­S. In peat collected in March 1986, injected with³⁵S­SO₄ ^2– and incubated at 4 °C, mean rates of dissimilatory sulfate reduction (formation of H₂S + S⁰ + FeS + FeS₂), carbon bonded S formation, and ester sulfate S formation averaged 3.22, 0.53, and 0.36 nmol·g wet mass^–1·h^–1, respectively. Measured rates of sulfide oxidation were comparable to rates of sulfate reduction. Although dissolved SO₄ ^2– concentrations in Big Run Bog interstitial water (< 200 µM) are low enough to theoretically limit sulfate reducing bacteria, rates of sulfate reduction integrated throughout the top 30–35 cm of peat of 9 and 34 mmol·m^–2·d^–1 (at 4 °C are greater than or comparable to rates in coastal marine sediments. We suggest that sulfate reduction was supported by a rapid turnover of the dissolved SO₄ ^2– pool (average turnover time of 1.1 days). Although over 90% of the total S in Big Run Bog peat was organic S, cycling of S was dominated by fluxes through the inorganic S pools.     

Biogeochemical cycling of sulfur and iron in sediments of a south-east Asian mangrove,Phuket Island,Thailand

Benthic sulfate reduction and sediment pools of sulfur and iron were examined during January 1992 at 3 stations in the Ao Nam Bor mangrove, Phuket, Thailand. Patterns of sulfate reduction rates (0–53 cm) reflected differences in physical and biological conditions at the 3 stations, and highest rates were found at the vegetated site within the mangrove (Rhizophora apiculata) forest. Due to extended oxidation of mangrove sediments, a large portion of the added³⁵S-label was recovered in the chromium reducible pools (FeS₂ and S⁰) (41–91% of the reduced sulfur). Pyrite was the most important inorganic sulfur component, attaining pool sizes 50–100 times higher than acid volatile pools (FeS). HCl-extractable (0.5 M HCl) iron pools, including Fe(II)_HCl and Fe(III)_HCl, were generally low and Fe(III)_HCl was only present in the upper surface layers (0–5 cm). Maximum concentrations of dissolved Fe²⁺ (35–285 M) occurred just about the depth where dissolved H₂S accumulated. Furthermore Fe²⁺ and H₂S coexisted only where concentrations of both were low. There was an accumulation of organic sulfur in the deep sediment at 2 stations in the inner part of the mangrove. The reoxidation of reduced sulfides was rapid, and storage of sulfur was minor in the upper sediment layers, where factors like bioturbation, the presence of roots, or tidal mixing enhance oxidation processes.Author of correspondence.     

Comparative Aspects of Sulfur Mineralization in Sediments of a Eutrophic Lake Basin

The net mineralization of organic sulfur compounds in surface sediments of Wintergreen Lake was estimated from a mass-balance budget of sulfur inputs and sediment sulfur concentrations. The net mineralization of organic sulfur inputs is <50% complete, which is consistent with the dominance of organic sulfur (>80% of total sulfur) in sediment. Although sediment sulfur is predominantly organic, sulfate reduction is the most significant process in terms of the quantities of sulfur transformed in surface sediments. Rates of sulfate reduction in these sediments average 7 mmol/m² per day. On an annual basis, this rate is 19-fold greater than net rates of organic sulfur mineralization and 65-fold greater than sulfate ester hydrolysis.     

Organic Carbon Degradation in Arctic Marine Sediments,Svalbard: A Comparison of Initial and Terminal Steps

Degradation of marine organic matter under anoxic conditions involves microbial communities working in concert to remineralize complex substrates to CO ₂ . In order to investigate the coupling between the initial and terminal steps of this sequence in permanently cold sediments, rates of extracellular enzymatic hydrolysis and sulfate reduction were measured in parallel cores collected from 5 fjords on the west and northwest coast of Svalbard, in the high Arctic. Inventories of total dissolved carbohydrates were also measured in order to evaluate their potential role in carbon turnover. Polysaccharide hydrolysis rates exhibited substrate-related and, to a lesser extent, depth-related differences (p < 0.0001); laminarin hydrolysis was consistently most rapid at nearly all depths and sites, and fucoidan hydrolysis was least rapid. Although there was a high degree of variability in parallel cores, sulfate reduction rates also exhibited statistically significant depth-and station-related differences. A comparison with data from previous investigations in Svalbard sediments suggests that this variability is linked to substrate availability rather than to organism distribution. Total dissolved carbohydrate concentrations were comparable to those measured in more temperate sediments, and likely comprise a considerable fraction of porewater dissolved organic carbon. A comparison of dissolved carbohydrate inventories with hydrolysis and sulfate reduction rates suggests that the turnover of carbon through the dissolved pool occurs quite rapidly, on the order of a few days to weeks. The transformation of particulate to dissolved organic matter must also be sufficiently rapid to maintain the measured rates of terminal remineralization.     

Selectivity in biomineralization of barium and strontium

The desmid green alga Closterium moniliferum belongs to a small number of organisms that form barite (BaSO₄) or celestite (SrSO₄) biominerals. The ability to sequester Sr in the presence of an excess of Ca is of considerable interest for the remediation of ⁹⁰Sr from the environment and nuclear waste. While most cells dynamically regulate the concentration of the second messenger Ca²⁺ in the cytosol and various organelles, transport proteins rarely discriminate strongly between Ca, Sr, and Ba. Herein, we investigate how these ions are trafficked in C. moniliferum and how precipitation of (Ba,Sr)SO₄ crystals occurs in the terminal vacuoles. Towards this goal, we simultaneously visualize intracellular dynamics of multiple elements using X-ray fluorescence microscopy (XFM) of cryo-fixed/freeze-dried samples. We correlate the resulting elemental maps with ultrastructural information gleaned from freeze-fracture cryo-SEM of frozen-hydrated cells and use micro X-ray absorption near edge structure (micro-XANES) to determine sulfur speciation. We find that the kinetics of Sr uptake and efflux depend on external Ca concentrations, and Sr, Ba, and Ca show similar intracellular localization. A highly ion-selective cross-membrane transport step is not evident. Based on elevated levels of sulfate detected in the terminal vacuoles, we propose a “sulfate trap” model, where the presence of dissolved barium leads to preferential precipitation of (Ba,Sr)SO₄ due to its low solubility relative to SrSO₄ and CaSO₄. Engineering the sulfate concentration in the vacuole may thus be the most direct way to increase the Sr sequestered per cell, an important consideration in using desmids for phytoremediation of ⁹⁰Sr.     

Sulfur cycling in a forested Sphagnum bog in northern Minnesota

The mass balance and internal cycle of sulfur within a small forested,Sphagnum bog in northern Minnesota are presented here based on a 4-year record of hydrologic inputs and outputs (precipitation, throughfall, streamflow, upland runoff) and a 3-year measurement of plant growth and sulfur uptake. Concentrations and accumulation rates of inorganic and organic sulfur species were measured in porewater. The bog is a large sink for sulfur, retaining 37% of the total sulfur input. Because of the relatively large export of organic S (21% of inputs), retention efficiency for total-S (organic S + SO ₄ ⁼ ; 37%) is less than that for SO ₄ ⁼ (58%). There is a dynamic cycle of oxidation and reduction within the bog. Annual oxidation and recycling of S is equal to total inputs in the center of the bog. Plants receive 47% of their uptake requirement from atmospheric deposition, 5% from retranslocation from foliage, and the remainder from sulfur remineralized from peat. Mineralization is most intense in the aerobic zone above the water table. Inorganic sulfur species comprise <5% of the total sulfur burden within the peat.     

Factors affecting production of COS and CS2 in Leucaena and Mimosa species

Carbon disulfide (CS₂) and carbonyl sulfide (COS) are colorless, foul-smelling, volatile sulfur compounds with biocidal properties. Some plants produce CS₂ or COS or both. When used as an intercrop or forecrop, these plants may have agronomic potential in protecting other plants. Most of the factors which affect production of these plant-generated organic sulfides are unknown. We determined the effects of sulfate concentration, plant age, nitrogen fixation, drought stress, root injury (through cutting), and undisturbed growth on COS production in Leucaena retusa or Leucaena leucocephala and the effect of some of these factors on CS₂ production in Mimosa pudica. In addition, we determined if organic sulfides were produced in all Leucaena species. When L. retusa and M. pudica seedlings were grown in a plant nutrient medium with different sulfate concentrations (50 to 450 mg SL^-1), COS or CS₂ from crushed roots generally increased with increasing sulfate concentration. COS production was highest (74 ng mg^-1 dry root) for young L. retusa seedlings and declined to low amounts (<5 ng mg^-1 dry root) for older seedlings. Nitrogen fixation reduced the amounts of COS or CS₂ produced in L. leucocephala and M. pudica. Under conditions of undisturbed growth, root cutting, or drought stress, no COS production was detected in 4-to 8-weeks-old L. retusa plants. COS or CS₂ or both was obtained from crushed roots or shoots of all 13 known Leucaena species.     

Seasonality of sulfate reduction and pore water solutes in a marine fish farm sediment: the importance of temperature and sedimentary organic matter

Sulfate reduction and pore water solutes related to sulfur cycling and anaerobic processes (short chain fatty acids (SCFA), SO₄ ^2–, TCO₂, NH₄ ⁺, dissolved sulfides (H₂S) and CH₄) were examined during one year at a marine fish farm. Mineralization of fish farm waste products was rapid in this non-bioturbated, organic rich sediment. Stimulation of sulfate reduction rates (SRR) occurred primarily in the surface layers where the organic matter was deposited. Acetate was the most important (<99%) of the measured SCFA attaining high concentrations during summer months (up to 4.7 mM). The acetate profiles exhibited distinct seasonal cycles, where periods with high concentrations in the pore waters were found coincident with a high pool of particulate organic matter in the surface sediments and a low activity of the sulfate reducing bacteria (early spring and late summer). Periods with low acetate pools occurred when sulfate reduction rates were high in early summer and in winter were pools of particulate organic matter were decreasing. Methane production was observed concurrent with sulfate reduction in the microbial active surface layers in late summer. Subsurface peaks of SO₄ ^2–, TCO₂, NH₄ ⁺ and H₂S were evident in July and August due to rapid mineralization in these surface layers. With decreasing autumn water temperatures mineralization rates declined and subsurface peaks of these solutes disappeared. A strong relationship was found between pore water TCO₂, and NH₄ ⁺. Ratios between TCO₂, and NH₄ ⁺ were low compared to a control site, attaining minimum values in mid-summer. This indicated rapid nitrogen mineralization of nitrogen rich labile substrates in the fish farm sediment during the entire season.     

Detoxification of SO2 in conifers differing in SO2-tolerance

Contents of organic sulfur, sulfate and the inorganic cations K⁺, Ca²⁺, Mg²⁺, Mn²⁺ and Na⁺ were compared in needles of three conifer species differing in tolerance to chronic SO₂ immissions. Sulfate and organic sulfur compounds were also measured in bark and wood. Field material was collected from Norway Spruce (Picea abies (L.) Karst.), Colorado Spruce (Picea pungens Engelm.) and Scots Pine (Pinus sylvestris L.) at sites where the SO₂ concentration in air was high, and at another site where it was low. In general, sulfate contents were higher but cation contents lower at the sites where SO₂ concentrations were high than where they were low. Up to 114mmol · (kg DW)^–1 sulfate was measured in fouryear-old needles of Norway Spruce from the Erzgebirge (annual mean of SO₂ in air 32 nl · 1^–1). Sulfate accumulation in this SO₂-sensitive conifer increased with SO₂ concentration in ambient air and with needle age, indicating that the main part of the sulfate resulted from the oxidative detoxification of SO₂. Loss of inorganic cations from ageing needles was reduced, or cation levels even increased, with increasing needle age, while sulfate accumulated. Apparently, cations served as counter-ions for sulfate, which is sequestered in the vacuoles. Individual trees differed in regard to the nature of cations which accumulated with sulfate. Calcium, potassium and magnesium were the dominating cations. Sodium levels were very low. Needles of the SO₂-tolerant conifers Colorado Spruce and Scots Pine growing next to Norway Spruce in the Erzgebirge did not accumulate, or accumulated less, sulfate with increasing needle age as compared to needles of Norway Spruce. However, somewhat more sulfate was found in the bark of the SO₂-tolerant species than in the bark of Norway Spruce. Scots Pine contained distinctly more sulfate in the wood than the other conifers. Since accumulation of organic sulfur compounds could not be observed with increasing needle age, or in bark and wood, reduction does not appear to play a major role in the detoxification of SO₂ by the investigated species. Physiological mechanisms permitting Colorado Spruce and Scots Pine to avoid the sulfate accumulation in the needles and the accompanying sequestration of cations that are observed in neighbouring Norway Spruce are discussed on the basis of the obtained data.Abbreviations S_org organic sulfur compounds Died June 10, 1991, aged 29, in a traffic accident. He initiated this work.This work was supported by the Sonderforschungsbereich 251 of the University of Würzburg and by the Projektgruppe Bayern zur Erforschung der Wirkung von Umweltschadstoffen (PBWU). The authors with to thank Prof. Dr. W Kaiser and Prof. Dr. W. Urbach (both Julius-von-Sachs-Institut, University of Würzburg, Germany) for HPLC-analysis and ICP-analysis.     

Reduction of Sulfur Compounds in the Sediments of a Eutrophic Lake Basin

Concentrations of various sulfur compounds (SO₄²⁻, H₂S, S⁰, acid-volatile sulfide, and total sulfur) were determined in the profundal sediments and overlying water column of a shallow eutrophic lake. Low concentrations of sulfate relative to those of acid-volatile sulfide and total sulfur and a decrease in total sulfur with sediment depth implied that the contribution of dissimilatory sulfur reduction to H₂S production was relatively minor. Addition of 1.0 mM Na₂³⁵SO₄ to upper sediments in laboratory experiments resulted in the production of H₂³⁵S with no apparent lag. Kinetic experiments with ³⁵S demonstrated an apparent K_m of 0.068 mmol of SO₄²⁻ reduced per liter of sediment per day, whereas tracer experiments with ³⁵S indicated an average turnover time of the sediment sulfate pool of 1.5 h. Total sulfate reduction in a sediment depth profile to 15 cm was 15.3 mmol of sulfate reduced per m² per day, which corresponds to a mineralization of 30% of the particulate organic matter entering the sediment. Reduction of ³⁵S⁰ occurred at a slower rate. These results demonstrated that high rates of sulfate reduction occur in these sediments despite low concentrations of oxidized inorganic compounds and that this reduction can be important in the anaerobic mineralization of organic carbon.