Priming effects in different soil types induced by fructose, alanine, oxalic acid and catechol additions

It is well established that certain substrate additions to soils may accelerate or retard the mineralisation of soil organic matter. But up to now, research on these so called ‘priming effects’ was almost exclusively conducted with arable soils and with plant residues or glucose as additives. In this study, the effects of the uniformly ¹⁴C-labelled substrates fructose, alanine, oxalic acid and catechol on the mineralisation of soil organic carbon (SOC) from different horizons of two forest soils (Haplic Podzol and Dystric Cambisol) and one arable soil (Haplic Phaeozem) under maize and rye cultivation were investigated in incubation experiments for 26 days. Apart from the controls, all samples received substrate additions of 13.3 μg substrate-C mg⁻¹ C_org. During the incubation, CO₂-evolution was measured hourly and the amount of ¹⁴CO₂ was determined at various time intervals. In almost all soils, priming effects were induced by one or several of the added substrates. The strongest positive priming effects were induced by fructose and alanine and occurred in the Bs horizon of the Haplic Podzol, where SOC mineralisation was nearly doubled. In the other soil samples, these substrates enhanced SOC mineralisation by +10 to +63%. Catechol additions generally reduced SOC mineralisation by −12 to −43% except in the EA horizon of the Haplic Podzol where SOC-borne CO₂-evolution increased by +46%. Oxalic acid also induced negative as well as positive priming effects ranging from −24 to +82%. The data indicate that priming effects are ubiquitously occurring in surface and subsoil horizons of forest soils as well as in arable soils. Although a broad variety of soils was used within this study, relationships between soil properties and priming effects could not be ascertained. Therefore, a prediction on occurrence and magnitude of priming effects based on relatively easily measurable chemical and physical soil properties was not possible. Nevertheless, the data suggest that positive priming effects are most pronounced in forest soils that contain SOC of low biodegradability, where the added substrates may act as an important energy source for microbial metabolism.     

Sulfur speciation in well‐aerated and wetland soils in a forested catchment assessed by sulfur K‐edge X‐ray absorption near‐edge spectroscopy (XANES)

In forested catchments, retention and remobilization of S in soils and wetlands regulate soil and water acidification. The prediction of long‐term S budgets of forest ecosystems under changing environmental conditions requires a precise quantification of all relevant soil S pools, comprising S species with different remobilization potential. In this study, the S speciation in topsoil horizons of a soil toposequence with different groundwater influence and oxygen availability was assessed by synchrotron‐based X‐ray absorption near‐edge spectroscopy (XANES). Our investigation was conducted on organic (O, H) and mineral topsoil (A, AE) horizons of a Cambisol–Stagnosol–Histosol catena. We studied the influence of topography (i.e., degree of groundwater influence) and oxygen availability on the S speciation. Soil sampling and pretreatment were conducted under anoxic conditions. With increasing groundwater influence and decreasing oxygen availability in the sequence Cambisol–Stagnosol–Histosol, the C : S ratio in the humic topsoil decreased, indicating an enrichment of soil organic matter in S. Moreover, the contribution of reduced S species (inorganic and organic sulfides, thiols) increased systematically at the expense of intermediate S species (sulfoxide, sulfite, sulfone, sulfonate) and oxidized S species (ester sulfate, SO ). These results support the concept of different S‐retention processes for soils with different oxygen availability. Sulfur contents and speciation in two water‐logged Histosols subject to permanently anoxic and temporarily oxic conditions, respectively, were very different. In the anoxic Histosol, reduced S accounted for 57% to 67% of total S; in the temporarily oxic Histosol, reduced S was only 43% to 54% of total S. Again, the extent of S accumulation and the contribution of reduced S forms to total S closely reflected the degree of O₂ availability. Our study shows that XANES is a powerful tool to elucidate key patterns of the biogeochemical S cycling in oxic and anoxic soil environments. In contrast to traditional wet‐chemical methods, it particularly allows to distinguish organic S compounds in much more detail. It can be used to elucidate microbial S‐metabolism pathways in soils with different oxygen availability by combining soil inventories and repeated analyses of a sample in different stages of field or laboratory incubation experiments under controlled boundary conditions and also to study (sub)microspatial patterns of S speciation in aggregated soils.     

Bodenentwicklung am Rande oligotropher Moore im Raum Berlin

Soil development in the surrounding of oligotrophic mires in the Berlin region Polygenetic soils, surrounding oligotrophic kettle hole mires in the valley and aeolian sand areas of the Berlin region, were investigated. The typical soil catena is formed by the sequence of Ombric Histosol (Niedermoor), Ombric Histosol/Albi‐gleyic Podzol (Moor‐Podsol‐Gley), Albi‐gleyic Podzol (Nasspodsol‐Gley), Gleyic Podzol (Podsol‐Gley), and Dystri‐gleyic Arenosol (Gley‐Podsol‐Braunerde) (German soil classifications in parenthesis). Field and laboratory work showed, that the investigated soils were strongly related to each other and that their development depends on the trophy of the mire and groundwater fluctuations during the Holocene. Compared with the Bh‐horizon of terrestrial soils the Gh‐horizon is nearly free of Fe and Mn, but very rich in pedogenic Al‐oxides and rich in organic matter. The genesis of the soils is explained as follows: 1. The development of different Gleyic Podzols was due to rise of groundwater. Consequently the Bh and Bs horizons of Podzols surrounding the mire were converted to Gh and Gr horizons. 2. Humic substances and Al in the Gh and Gr horizons were not re‐mobilized due to the rise of groundwater, whereas Fe and Mn were reduced and removed by groundwater. 3. At the periphery of the mire Fe was enriched in the Go horizon of the Gley‐Podzols but not Mn. 4. The fact that the mire is completely surrounded by Podzol‐Gleys, indicates, that movement of the groundwater from the central parts of mires towards the periphery is an essential pedogenetic factor.     

Influence of Sulfur Fertility on Wheat Yield Performance on Alluvial and Upland Soils

Abstract: In recent years, sulfur (S) deficiencies in winter wheat (Triticum aestivum L.) have become more common, particularly on coarse‐textured soils. In Study I, field experiments were conducted in 2001/2002 through 2003/2004 on Mississippi River alluvial soils (Experiment I) and an upland, loessial silt loam (Experiment II) to evaluate the influence of spring S rates of 0, 5.6, 11.2, and 22.4 kg ha^?1 and a fall rate of 22.4 kg sulfate (SO₄)‐S ha^?1 on grain yield of three varieties. In Study II, field experiments were conducted in 2001/2002 and 2004/2005 on alluvial soils to evaluate the influence of spring S rates of 0, 5.6, 11.2, and 22.4 kg SO₄‐S ha^?1 in fields where S‐deficiency symptoms were present. Grain yield response to applied S occurred only on alluvial, coarse‐textured, very fine sandy loam soils (Study II) that had soil SO₄‐S levels less than the critical level of 8 mg kg^?1 and organic‐matter contents less than 1 g kg^?1 in the 0‐ to 15‐, 15‐ to 30‐, and 30‐ to 45‐cm depths. Soil pH increased with soil depth. Optimum S rate was 11.2 kg SO₄‐S ha^?1 in 2001/2002 and 5.6 kg SO₄‐S ha^?1 in 2004/2005. On the upland, loessial silt loam soil, soil SO₄‐S levels accumulated with depth, whereas organic‐matter content and pH decreased. In the loessial soils, average soil SO₄‐S levels in the 15‐ to 30‐ and 30‐ to 45‐cm soil depths were 370% greater than SO₄‐S in the surface horizon (0 to 15 cm).     

Non-cellulosic neutral sugar contribution to mineral associated organic matter in top- and subsoil horizons of two acid forest soils

We investigated the polysaccharide composition of bulk and mineral-bound (density fractions >2 g cm⁻³) organic matter in topsoil and subsoil horizons of a Podzol and a Cambisol. Total sugar contents were generally higher in the Cambisol than in the Podzol. For most horizons of both soils, the sugars were enriched in the mineral-bound organic matter fraction. This fraction showed a monosaccharide distribution typical for microbial sugars, whereas in bulk soil horizons higher contributions of plant-derived sugars were observed. A strong relationship with the ¹⁴C activity of the dense fraction suggests that microbial-derived polysaccharides are most likely stabilised preferentially by mineral interactions compared to plant-derived polysaccharides.     

Examination of ester sulfates in Podzolic and Regosolic soils using an immobilized arylsulfatase reactor

The enzyme kinetics of an immobilized arylsulfatase reactor were examined. We found that the optimum operating conditions for the reactor were pH 7.0 and 25°C, using p-nitrophenyl sulfate in acetate buffer. The Michaelis constant (K _m) of immobilized arylsulfatase was 5.29 mM, compared with a K _m of 2.18 mM for soluble arylsulfatase from the same source (Helix pomatia). Since arylsulfatase hydrolyzes organic ester sulfate linkages, the immobilized arylsulfatase reactor was used to examine ester sulfate compounds in two soils subjected to different fertility management schemes. Soil samples were obtained from the Ap horizons of a Podzol from S-amended wheat plots and a Regosol from dykeland hayfield plots which had received additions of NH₄NO₃ and compost. The distribution of S in these soils was examined in the fall of 1993 and the spring of 1994. Soil organic matter was extracted and separated into three molecular weight fractions (<500, 500–10 000, >10 000). There was no difference in the ester sulfate content for the >10 000 fraction of control and S-amended Podzol soils; however, the S-amended samples had significantly higher quantities of hydrolysable ester sulfates than controls for the 500–10 000 range, indicating that S amendments resulted in the incorporation of ester sulfate into this lower molecular weight fraction. Both control and NH₄NO₃ treatments to the Regosol showed significantly higher quantities of hydrolysable ester sulfates in the >10 000 fraction, while compostamended plots showed no difference between the >10 000 and 500–10 000 fractions due to suspected microbial degradation of high molecular weight organic S compounds in the compost. Since there was no significant effect of sampling time, this study indicated that naturally occurring low molecular weight ester sulfate compounds accumulate in soil and persist during storage. Hydrolysable ester sulfates constituted 35–55% of the hydriodic acid-reducible S in these different soils and probably represent an important and easily mineralizable portion of total ester sulfates.     

Soil-solution chemistry in a low-elevation spruce-fir ecosystem,Howland, Maine

Soil solutions were collected monthly by tension and zero-tension lysimeters in a low-elevation red spruce stand in east-central Maine from May 1987 through December 1992. Soil solutions collected by Oa tension lysimeters had higher concentrations of most constituents than the Oa zero-tension lysimeters. In Oa horizon soil solutions growing season concentrations for SO₄, Ca, and Mg averaged 57, 43, and 30 μmol L^?1 in tension lysimeters, and 43, 28, and 19 μmol L^?1 in zero-tension lysimeters, respectively. Because tension lysimeters remove water held by the soil at tensions up to 10 kPa, solutions are assumed to have more time to react with the soil compared to freely draining solutions collected by zero-tension lysimeters. Solutions collected in the Bs horizon by both types of collectors were similar which was attributed to the frequency of time periods when the water table was above the Bs lysimeters. Concentrations of SO₄ and NO₃ at this site were lower than concentrations reported for most other eastern U.S. spruce-fir sites, but base cation concentrations fell in the same range. Aluminum concentrations in this study were also lower than reported for other sites in the eastern U.S. and Ca/Al ratios did not suggest inhibition of Ca uptake by roots. Concentrations of SO₄, Ca, K, and Cl decreased significantly in both the Oa and Bs horizons over the 56-month sampling period, which could reflect decreasing deposition rates for sulfur and base cations, climatic influences, or natural variation. A longer record of measured fluxes will be needed to adequately define temporal trends in solution chemistry and their causes.     

Organic sulfur forms in mineral top soils of the Marsh in Schleswig‐Holstein,Northern Germany

Little is known about the nature of organic sulfur (S) in soils of the Marsh in Schleswig‐Holstein, Northern Germany. In addition to total and inorganic S, we determined two organic S fractions (ester sulfate‐sulfur and carbon‐bonded sulfur) in 14 aerated mineral top horizons of two salt marshes and ten dyked polder soils of different age. All soils developed from marine sediments. Total S concen‐trations ranged from 153 to 950 mg kg^—1. Organic S was the main S constituent (range from 53 to 99% with a median of 97%). Higher inorganic S levels were found only in the salt marshes due to soluble sulfate (15 to 47%). The younger marsh soils (salt marshes and soils of a polder dyked in 1978) had unique high S contents of 0.9 to 2.4% in their organic matter, whereas the S contents of the organic matter in older marsh soils were at only 0.6%. This S‐rich organic matter is a heritage of a former anoxic marine environment. In most horizons the carbon‐bonded S was the dominant sulfur form. However, both carbon‐bonded S and ester sulfate‐S did not relate to soil age. This limits the benefit of the wet chemical fractionation procedure used for studying the fate of organic S in marsh soils.     

Analysis of sulfur compounds in acid sulfate soils and other recent marine soils

Abstract

A refined scheme for the semi micro chemical analysis of sulfur fractions in soils is presented. Pyrite is analyzed, as iron, after extraction in HNO₃. Non‐pyrite iron is excluded by a pretreatment with HF/H₂SO₄. Water‐soluble sulfate and jarosite [KFe₃(SO₄)₂(OH)₆], the other dominant sulfur fractions in acid sulfate soils, are analyzed turbidimetrically, as sulfate, after successive extractions by EDTA.3Na (water soluble plus exchangeable SO₄) and by hot 4 M HCl (jarosite). These methods are simpler, less bulky and more specific than most existing procedures.

Introduction of elemental sulfur analysis permits estimation of organic sulfur fraction as well. Sums of individual sulfur fractions agree well with separate total sulfur determinations.

The proposed analysis of pyrite permits also distinction of the components Fe₂O₃, FeO and FeS₂ in soils and rocks².     

Use of a coupled equilibrium model to describe the buffering of protons and hydroxyl ions in some acid soils

The buffering of protons and hydroxyl ions in acid soils was studied by the addition of small amounts of HCl, H₂SO₄, and NaOH in consecutive batch experiments using surface soils and subsoils from two Cambisols and one Podzol. A chemical equilibrium model was used to study the main buffer processes. The model included inorganic complexation and multiple cation exchange, and also the solubility of jurbanite and Al(OH)₃ for the subsoils. Buffering of protons was predicted quite well by the model for the surface soil of the Spodi-Dystric and Spodic Cambisols, suggesting that multiple cation exchange was the main buffer process. For the Podzol surface soil, however, the model overestimated proton buffering by cation exchange considerably. Hydroxyl buffering in acid surface soils could be described well by the model for the Podzol soil only. For the Cambisols, hydroxyl buffer reactions included not only cation exchange, but also solubilization of large amounts of organic matter and presumably deprotonation of dissolved organic carbon (DOC). Modelling proton and hydroxyl buffering in subsoils suggested that equilibrium with AJ(OH)₃ was not maintained for the Podzol and spodic Cambisol. Sulphate sorption had to be considered to describe titration experiments in all three soils. The assumption of jurbanite being in equilibrium with soil extracts was useful only for the Spodi-Dystric Cambisol.     

Adsorption and translocation of sulfur in some tropical acid soils

In view of growing concern about sulfur (S) deficiency, we attempted to study the effect of soil characteristics on the adsorption and translocation of S in soils. Laboratory experiments were conducted with five surface soils collected from three regions in the state of Orissa (Eastern India). In an adsorption study, all the soils were equilibrated with graded doses of potassium sulfate (K₂SO₄). Freundlich adsorption isotherms provided good fit to S adsorption data. Free Fe₂O₃ and Al₂O₃ in the soils were primarily responsible for retaining added S in soils. Further, studies on the movement of sulfate‐S in 30‐cm plexiglass columns, where radio‐labeled S along with water (5 cm) was applied as gypsum and K₂SO₄, showed that K₂SO₄‐S migrated deeper than gypsum‐S. Sulfur moved deeper in case of initially water‐saturated soils than in initially air‐dry soils.     

Soil sulphur speciation in two glacier forefield soil chronosequences assessed by S K‐edge XANES spectroscopy

In regions with little atmospheric input of sulphur (S) and S‐poor parent material, the bio‐availability of S, which is dependent on its speciation, may limit ecosystem production and succession. In our study, soil S speciation in two glacier forefield soil chronosequences (Hailuogou Glacier, Gongga Shan, China; Damma Glacier, Swiss Alps) was investigated for the first time. Different S species were quantified by synchrotron‐based X‐ray absorption near‐edge structure (XANES) spectroscopy at the S K‐edge. Both chronosequences show similar patterns and pedogenetic trends of their topsoil S status. Topsoil concentrations of total S were correlated with the concentrations of organic carbon and pedogenic Fe/Al oxyhydroxides. Both moraine materials contained inorganic sulphides, which in the topsoil were oxidized within 30 (Hailuogou) or 75 years (Damma) of soil development after deglaciation. About 50% of total S in the fresh moraine material at Hailuogou and 75% of that in the 15 year‐old soil at Damma was organically‐bound. During initial soil development, the contribution of organic S to total S increased at the expense of inorganic sulphide and sulphate, resulting in organic S percentages > 90% of total topsoil S after 30 (Hailuogou) and 75 (Damma) years of pedogenesis. Organic S compounds with electronic oxidation states of the S atom > + 1.5 (sulphoxides, sulphones, sulphonates and ester sulphates) dominated the organic S pool in all soils. Hence, microbial degradation of non‐sulphide organic S (sulphonates and ester sulphates) is probably important to mitigate S scarcity caused by limited availability of SO₄^2?‐S in these soils. Changes in topsoil S speciation during initial stages of pedogenesis and ecosystem succession in glacier forefields under a cool, humid climate appear to be governed by combined effects of mineral weathering (oxidation of inorganic sulphides and formation of S‐adsorbing sesquioxides), accumulation and microbial turnover of soil organic matter and the type of vegetation succession.     

Sequential transformation rates of soil organic sulfur fractions in two-step mineralization process

To understand the organic sulfur (S) stabilization in volcanic soils, we investigated organic S transformation rates and their relationships to soil properties in incubation experiments using forest soils from the Nikko volcanic region, central Japan. We hypothesized that carbon (C)-bonded S would first be transformed into ester sulfate-S and then into inorganic sulfate-S. We separately calculated the rates of decrease of C-bonded S (velocity 1, v ₁) and ester sulfate-S (velocity 2, v ₂) concentrations. During incubation, the ester sulfate-S concentration increased in two soils characterized by a high concentration of both ammonium oxalate-extractable aluminum (Al_o) and pyrophosphate-extractable Al (Al_p), whereas the C-bonded S concentration decreased in all soils. A large proportion of the S that was lost in the incubation experiments consisted of C-bonded S rather than ester sulfate-S. Velocity 2 was negatively correlated with both of Al_o and Al_p contents when soils were incubated at 20 °C. These results suggest that when C-bonded S is transformed into ester sulfate-S, complete mineralization to inorganic sulfate is inhibited, because ester sulfate-S is stabilized due to organo–mineral association. Incubation temperatures significantly affected v ₂. Thus, production of inorganic sulfate by mineralization of ester sulfate-S appeared to be regulated by soil Al contents and temperatures. Velocity 1 was proportional to soil pH ranging from 4.5 to 5.5, indicating that the degradation of C-bonded S is pH dependent.     

Sulphur speciation and biogeochemical cycling in long-term arable cropping of subtropical soils: evidence from wet-chemical reduction and S K-edge XANES spectroscopy

Agriculture has claimed a large share of terrestrial environments in the tropics and subtropics through cultivation of native grasslands or forests. The impact of this anthropogenic change on speciation, dynamics, and ecological significance of sulphur (S) compounds is still poorly understood. We combined degradative wet-chemical reduction and S K-edge X-ray absorption near edge structure (XANES) spectroscopy techniques to evaluate the impact of long-term agricultural management of native grassland soils in South African Highveld on the amount, form and dynamics of S species. Sulphur XANES in the humic substances extracted by 0.1 m NaOH/0.4 m NaF solution showed the presence of strongly reduced (polysulphides, disulphides, thiols, monosulphides and thiophenes), intermediate (sulphoxides and sulphonates) and strongly oxidized (ester sulphates) organic-S. It showed that strongly oxidized-S is the predominant form (39–54%) of the total organic-S in the humic substances, and organic-S in the intermediate oxidation state represented 30–37% (78–93% of which was attributed to sulphonates). The strongly reduced organic-S comprised only 17–24% of the total organic-S. We did not find a close correlation between the results of a degradative wet-chemical procedure and XANES spectroscopy conducted in both the bulk soils (ester SO₄-S from XANES versus HI-fractionation, r = 0.27; P < 0.05) and the humic substance extracts (ester SO₄-S from XANES versus HI-fractionation, r= 0.39; P < 0.05). The ratio of reduced-S to strongly oxidized-S (R-S/O-S) in the humic substances decreased from 0.61 to 0.21, while the ratio of intermediate-S to strongly oxidized-S (I-S/O-S) declined from 0.93 to 0.61 after 90 years of arable cropping of the native grassland soils. Hence, there was a shift in oxidation state towards strongly oxidized-S (+6) and, thereby, a change in the relative proportion of the organic-S moieties associated with each oxidation state following cultivation of the native grassland soils. Therefore, we conclude that changes in land-use practice brought about not only quantitative change but also altered the composition of organic-S functional groups in these native subtropical grassland soils.     

Differentiation between adsorbed and precipitated sulphate in soils and at micro-sites of soil aggregates by sulphur K-edge XANES

To investigate the potential of synchrotron‐based X‐ray Absorption Near‐Edge Structure spectroscopy (XANES) at the sulphur (S) K‐edge for a discrimination of adsorbed and precipitated sulphate in soils and soil particles, XANES spectra of ionic sulphate compounds and Al/Fe hydroxy sulphate minerals were compared with spectra of SO₄^2? adsorbed to ferrihydrite, goethite, haematite, gibbsite or allophane. Ionic sulphate and hydroxy sulphate precipitates had broader white‐lines (WL) at 2482.5 eV (full width at half maximum (FWHM) of edge‐normalized spectra, 2.4–4.2 eV; Al hydroxy sulphates, 3.0 eV) than SO₄^2? adsorbed to Al/Fe oxyhydroxides or allophane (FWHM, 1.8–2.4 eV). The ratio of the white‐line (WL) height to the height of the post‐edge feature at 2499 eV (WL/PEF) was larger for SO₄^2? adsorbed to Al/Fe oxyhydroxides or allophane (8.1–11.9) than for Al/Fe hydroxy sulphates and ionic sulphates (3.9–5.7). The WL/PEF ratio of edge‐normalized S K‐edge XANES spectra can be used to distinguish adsorbed from precipitated SO₄^2? in soils and also at microsites of soil particles. The contribution of adsorbed and precipitated SO₄^2? to the total SO₄^2? pool can be roughly quantified. Adsorbed ester sulphate may result in overestimation of precipitated SO₄^2?. The spectra of most soils could be fitted by linear combination fitting (LCF), yielding a similar partitioning between adsorbed and precipitated SO₄^2? as an evaluation of the WL/PEF ratio. The SO₄^2? pool of German forest soils on silicate parent material in most cases was strongly dominated by adsorbed SO₄^2?; however, in three German forest soils subject to elevated atmospheric S deposition, a considerable portion of the SO₄^2? pool was precipitated SO₄^2?, most likely Al hydroxy sulphate. The same is true for Nicaraguan Eutric and Vitric Andosols subject to high volcanogenic S input. In the subsoil of the Vitric Andosol, adsorbed SO₄^2? and Al hydroxy sulphate coexist on a micron scale.     

Adsorption of dissolved organic carbon and sulfate by acid forest soils in the Fichtelgebirge,FRG

The adsorption of dissolved organic carbon (DOC) and sulfate was examined in mineral horizons of acid soils from damaged (Oberwarmensteinach) and healthy (Wülfersreuth) Norway spruce forested sites in the Fichtelgebirge (NE-Bavaria). The A horizons of both sites desorbed DOC at all levels added, whereas the B horizons (Bs and Bv) retained added DOC at levels > 5 mmol C kg^?1. An initial mass isotherm used on the B horizon data indicated that these soils have a greater affinity for DOC than B horizons from Spodosols in the northeastern U.S. Sulfate was only retained at high solution levels, and retention was pH dependent. Nitrate and sulfate additions (1000 μeq L^?1 anion) had minor effects on DOC adsorption. Overall, there was little difference in DOC or sulfate retention at the two sites, indicating atmospheric deposition inputs have not affected these processes.     

Sulfur mineralization in two soils amended with organic manures,crop residues,and green manures

The mineralization of sulfur (S) was investigated in a Vertisol and an Inceptisol amended with organic manures, green manures, and crop residues. Field‐moist soils amended with 10 g kg^—1 of organic materials were mixed with glass beads, placed in pyrex leaching tubes, leached with 0.01 M CaCl₂ to remove the mineral S and incubated at 30 °C. The leachates were collected every fortnight for 16 weeks and analyzed for SO₄‐S. The amount of S mineralized in control and in manure‐amended soils was highest in the first week and decreased steadily thereafter. The total S mineralized in amended soils varied considerably depending on the type of organic materials incorporated and soil used. The cumulative amounts of S mineralized in amended soils ranged from 6.98 mg S (kg soil)^—1 in Inceptisol amended with wheat straw to 34.38 mg S (kg soil)^—1 in Vertisol amended with farmyard manure (FYM). Expressed as a percentage of the S added to soils, the S mineralized was higher in FYM treated soils (63.5 to 67.3 %) as compared to poultry manure amended soils (60.5 to 62.3 %). Similarly the percentage of S mineralization from subabul (Leucaena leucocephala) loppings was higher (53.6 to 55.5 %) than that from gliricidia (Gliricidia sepium) loppings (50.3 to 51.1 %). Regression analysis clearly indicated the dependence of S mineralization on the C : S ratio of the organic materials added to soil. The addition of organic amendments resulted in net immobilization of S when the C : S ratio was above 290:1 in Vertisol and 349:1 in Inceptisol. The mineralizable S pool (S_o) and first‐order rate constant (k) varied considerably among the different types of organic materials added and soil. The S_o values of FYM treated soils were higher than in subabul, gliricidia, and poultry manure treated soils.     

Ammonium fluoride extraction for determining inorganic sulphur in acid forest soils

Current methods for determining inorganic sulphur (S) in aerated mineral soil horizons often result in underestimates. To overcome this defect we developed a new method combining a batch extraction with 0.5 m NH₄F solution at a soil:solution ratio of 1:5 with a subsequent analysis of the mobilized SO₄^2– by ion chromatography. The ammonium fluoride extraction enables us to characterize inorganic sulphate in non‐calcareous forest soils. It is more efficient than conventional procedures in which inorganic S is extracted with phosphate or bicarbonate solution. In contrast to the extraction with strongly alkaline reagents (NaOH, KOH, LiOH), the NH₄⁺–NH₃ buffer system in NH₄F prevents the pH of the suspension from exceeding 9.0 and thus the undesired conversion of organic S into SO₄^2– by auto‐oxidation and hydrolysis of ester sulphate. In a comparison we demonstrated that the inorganic S in six German forest soils is underestimated by up to 50% or 200 kg S ha^?1 in the uppermost 60 cm, if it is assessed by extraction with 0.016 m KH₂PO₄ or 0.5 m NaHCO₃ instead of 0.5 m NH₄F. Conversely, the pool of ester sulphate is overestimated almost threefold.     

Effects of acid sulphate on DOC release in mineral soils: the influence of SO42− retention and Al release

Dissolved organic carbon (DOC) in acid‐sensitive upland waters is dominated by allochthonous inputs from organic‐rich soils, yet inter‐site variability in soil DOC release to changes in acidity has received scant attention in spite of the reported differences between locations in surface water DOC trends over the last few decades. In a previous paper, we demonstrated that pH‐related retention of DOC in O horizon soils was influenced by acid‐base status, particularly the exchangeable Al content. In the present paper, we investigate the effect of sulphate additions (0–437 µeq l^?1) on DOC release in the mineral B horizon soils from the same locations. Dissolved organic carbon release decreased with declining pH in all soils, although the shape of the pH‐DOC relationships differed between locations, reflecting the multiple factors controlling DOC mobility. The release of DOC decreased by 32–91% in the treatment with the largest acid input (437 µeq l^?1), with the greatest decreases occurring in soils with very small % base saturation (BS, < 3%) and/or large capacity for sulphate (SO₄^2?) retention (up to 35% of added SO₄^2?). The greatest DOC release occurred in the soil with the largest initial base status (12% BS). These results support our earlier conclusions that differences in acid‐base status between soils alter the sensitivity of DOC release to similar sulphur deposition declines. However, superimposed on this is the capacity of mineral soils to sorb DOC and SO₄^2?, and more work is needed to determine the fate of sorbed DOC under conditions of increasing pH and decreasing SO₄^2?.     

Changes in the concentrations and speciation of aluminum in response to an experimental addition of ammonium sulfate to the bear Brook Watershed,Maine, USA

An understanding of the biogeochemistry of aluminum (Al) in acid-sensitive terrestrial and aquatic ecosystems is critical to assessments of the effects of acidic deposition. Bear Brook Watershed, Maine, USA includes paired watersheds, East Bear and West Bear. Starting in November 1989, experimental additions of ammonium sulfate ((NH₄)₂SO₄; 900 mol/ha-yr) have been made to West Bear Brook Watershed. Chemical analysis of soil and stream waters were conducted to evaluate the speciation of Al prior to (1987–89) and following (1989–92) the experimental treatments. Before the treatments, soilwater Al occurred largely as inorganic monomeric Al (Ali). Concentrations of organic monomeric Al (Alo), Ali and dissolved organic C (DOC) were high in soil solutions draining the E horizon, and decreased in the lower mineral soilwater (Bs horizon) and streamwater. Streamwater concentrations of monomeric Al (Alm) were largely in the form of Alo. After the (NH₄)₂SO₄ treatments were initiated in the West Bear Brook Watershed, concentrations of Alm increased in soilwater and streamwater, largely as Ali. These increases in Al accompanied decreases in pH and increases in concentrations of SO₄ ^2? and NO₃ ^? in drainage waters. Increases in stream concentrations of Al were particularly evident during high flow events. This pattern, coupled with the increases in concentrations of Ali in upper soilwaters in response to the (NH₄)₂SO₄ addition, suggests that episodic increases in Ali were due to inputs of water entering the stream from shallow hydrologic flowpaths.