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.     

Seasonal variations in the chemical composition of dissolved organic matter in organic forest floor layer leachates of old-growth Scots pine (Pinus sylvestris L.) and European beech (Fagus sylvatica L.) stands in northeastern Bavaria, Germany

Organic matter dissolved in thepercolation water of forest soils contributeslargely to element cycling and transport ofnatural and anthropogenic compounds. The wayand extent to which these processes areaffected depends on the amount and the chemicalcomposition of soluble organic matter. Becausethe amount of soluble organic matter variesseasonally with changes in the microbialactivity in soil, it seems reasonable to assumethat there may be also seasonal changes in thechemical composition of dissolved organicmatter. We examined dissolved organic matter inthe seepage waters of organic forest floorlayers over a 27-month period (1997–1999) intwo forest ecosystems, a 160-year-old Scotspine (Pinus sylvestris L.) stand and a90-year-old European beech (Fagussylvatica L.) forest. The forest floorleachates were analysed for bulk dissolvedorganic C, C in hydrophilic and hydrophobicdissolved organic matter fractions,lignin-derived phenols (CuO oxidation),hydrolysable neutral carbohydrates and uronicacids, hydrolysable amino sugars, and stablecarbon isotope composition. In addition, westudied the samples by use of liquid-state¹³C-nuclear magnetic resonance (NMR)spectroscopy.For both investigated forest sites we foundthat the dissolved organic carbonconcentrations in forest floor leachates werelargest during summer. They peaked after rainstorms following short dry periods (106–145 mgdissolved organic C l^–1). The proportionsof C in the hydrophilic fractions were largestin winter and spring whereas in summer andautumn more C was found in the hydrophobicfraction. According to liquid-state ¹³C-NMR spectroscopy, summer and autumn samples hadlarger abundances of aromatic and aliphaticstructures as well as larger proportions ofcarboxyl groups whereas the winter and springsamples were dominated by resonances indicatingcarbohydrates. Wet-chemical analyses confirmedthese results. Winter and spring samples wererich in neutral carbohydrates and amino sugars.The summer and autumn samples contained morelignin-derived phenols which were also strongeroxidised than those in the winter and springsamples. Seasonal changes of ¹³C valueswere found to reflect the changes in thechemical composition of dissolved organicmatter. Most negative values occurred whenisotopically light lignin-derived compoundswere abundant and less negative values whencarbohydrates predominated.The different vegetation, age of thestands, and underlying mineral soils resultedin different concentrations of dissolvedorganic carbon and in differences in thedistribution between hydrophobic andhydrophilic organic carbon. Despite of this,the results suggest that the trends in temporalvariations in the composition of dissolvedorganic matter in forest floor seepage waterwere remarkably similar for both sites.Dissolved organic matter in winter and springseems to be mainly controlled by leaching offresh disrupted biomass debris with a largecontribution of bacterial and fungal-derivedcarbohydrates and amino sugars. Dissolvedorganic matter leached from the forest floor insummer and autumn is controlled by thedecomposition processes in the forest floorresulting in the production of stronglyoxidised, water-soluble aromatic and aliphaticcompounds. The chemical composition ofdissolved organic matter in forest floorseepage water in winter and spring indicateslarger mobility, larger biodegradability, andless interaction with metals and organicpollutants than that released during summer andautumn. Thus, the impact of dissolved organicmatter on transport processes may varythroughout the year due to changes in itscomposition.     

Controls on the dynamics of dissolved organic carbon and nitrogen in a Central European deciduous forest

Despite growing attention concerning therole of dissolved organic matter (DOM) inelement cycling of forest ecosystems, thecontrols of concentrations and fluxes of bothdissolved organic carbon (DOC) and nitrogen(DON) under field conditions in forest soilsremain only poorly understood. The goal ofthis project is to measure the concentrations and fluxes of DON, NH₄ ⁺, NO₃ ^–and DOC in bulkprecipitation, throughfall, forest floorleachates and soil solutions of a deciduousstand in the Steigerwald region (northernBavaria, Germany). The DOC and DONconcentrations and fluxes were highest inleachates originating from the Oa layer of theforest floor (73 mg C L^–1, 2.3 mg NL^–1 and about 200–350 kg C, 8–10 kg Nha^–1 yr^–1). They were observed to behighly variable over time and decreased in themineral topsoil (17 mg C L^–1, 0.6 mg NL^–1 and about 50–90 kg C, 2.0 to 2.4 kg Nha^–1 yr^–1). The annual variability ofDOC and DON concentrations and subsequentialDOC/DON ratios was substantial in allsolutions. The DOC and DON concentrations inthroughfall were positively correlated withtemperature. The DOC and DON concentrationsdid not show seasonality in the forest floorand mineral soil. Concentrations were notrelated to litterfall dynamics but didcorrespond in part to the input of DOC and DONfrom throughfall. The throughfall contributionto the overall element fluxes was higher forDON than for DOC. Concentrations and fluxes ofDON were significantly correlated to DOC inthroughfall and the Oi layer. However, thecorrelation was weak in Oa leachates. Inaddition, seasonal and annual variation ofDOC/DON ratios indicated different mechanismsand release rates from the forest floor forboth components. The concentrations of DOC andDON in forest floor leachates were in mostcases dependent neither on the pH value orionic strength of the solution, nor on thewater flux or temperature changes. As aconsequence, the DOC and DON fluxes from theforest floor into the mineral soil werelargely dependent on the water flux if annualand biweekly time scales are considered.     

Characterization of solid and dissolved carbon in a spruce-fir Spodosol

Organic substances are an integral part of the biogeochemistry of many elements in forest ecosystems. However, our understanding of the composition, chemistry, and reactions of these materials are incomplete and sometimes inconsistent. Therefore, we examined in detail dissolved organic carbon (DOC) in forest floor leachates over a two-year period (1992–1993), soil C, and DOC adsorption by a mineral soil to determine the relationship between soil solid and solution C characteristics in a spruce-fir ecosystem. The structural composition of DOC, DOC fractions (hydrophobic and hydrophilic acids, hydrophilic neutrals), and soil samples from the organic and mineral horizons were also analyzed using¹³C nuclear magnetic resonance (NMR) spectroscopy.Total DOC in forest floor leachates ranged from 7.8 to 13.8 mmol L^–1 with an average of 8.6 mmol L^–1. Concentrations were highest in September of both 1992 and 1993. Fractionation of the forest floor DOC indicated these solutions contained high organic acid contents that averaged 92% of the total DOC. Hydrophobic acids were also preferentially adsorbed by the B horizon. The¹³C NMR data suggested alkyl, carbohydrate, aromatic, and carboxylic C were the primary constituents for organic and mineral soils, DOC, and DOC fractions. Compositional changes of C were observed as aromatic and carbohydrate decreased, whereas alkyl, methoxy, and carbonyl moieties increased with depth. However, C composition changed little among the three organic layers based on the similarity of alkyl/carbohydrates ratios as determined from NMR area integration, suggesting that in this acid soil, decomposition proceeds rather slowly. Hydrophobic acids contained high contents of aromatic C, whereas hydrophilic acids were comprised primarily of carboxylic C. Hydrophilic neutrals were rich in carbohydrate C. Results indicated that these DOC fractions were unaltered during the isolation process. Carboxylic C groups appeared to dissolve easily and were probably the primary contributor to organic acidity in our organic dominate leachates. Results also suggested that DOC materials adsorbed on the B horizon underwent further biodegradation. Several seasonal patterns of C composition were observed in the forest floor leachates and DOC fractions collected between 1992 and 1993.Overall, the evidence from this study suggested that (i) DOC levels were mainly controlled by biological activity, (ii) forest floor DOC was comprised primarily of organic acids, (iii) contact of soil leachates with B horizon material affected DOC quantitatively and qualitatively, (iv) phenolic, carboxylic, and carbonyl C appeared to dissolve readily in the forest Oa horizon, (v) DOC materials adsorbed on the B horizon selectively underwent further decomposition, and (vi) C composition is a function of the extent of decomposition and DOC fractions.     

Concentrations and fluxes of dissolved organic carbon in an age-sequence of white pine forests in Southern Ontario,Canada

We determined concentrations and fluxes of dissolved organic carbon (DOC) in precipitation, throughfall, forest floor and mineral soil leachates from June 2004 to May 2006 across an age-sequence (2-, 15-, 30-, and 65-year-old) of white pine (Pinus strobus L.) forests in southern Ontario, Canada. Mean DOC concentration in precipitation, throughfall, leachates of forest floor, Ah-horizon, and of mineral soil at 1 m depth ranged from ∼2 to 7, 9 to 18, 32 to 88, 20 to 66, and 2 to 3 mg DOC L⁻¹, respectively, for all four stands from April (after snowmelt) through December. DOC concentration in forest floor leachates was highest in early summer and positively correlated to stand age, aboveground biomass and forest floor carbon pools. DOC fluxes via precipitation, throughfall, and leaching through forest floor and Ah-horizon between were in the range of ∼1 to 2, 2 to 4, 0.5 to 3.5, and 0.1 to 2 g DOC m⁻², respectively. DOC export from the forest ecosystem during that period through infiltration and groundwater discharge was estimated as ∼7, 4, 3, and 2 g DOC m⁻² for the 2-, 15-, 30-, and 65-year-old sites, respectively, indicating a decrease with increasing stand age. Laboratory DOC sorption studies showed that the null-point DOC concentration fell from values of 15 to 60 mg DOC L⁻¹ at 0 to 5 cm to <15 mg DOC L⁻¹ at 50 cm. Specific ultraviolet light absorption at 254 nm (SUVA₂₅₄) increased from precipitation and throughfall to a maximum in forest floor and decreased with mineral soil depth. No age-related pattern was observed for SUVA₂₅₄ values. DOC concentration in forest floor soil solutions showed a positive exponential relationship with soil temperature, and a negative exponential relationship with soil moisture at all four sites. Understanding the changes and controls of DOC concentrations, chemistry, and fluxes at various stages of forest stand development is necessary to estimate and predict DOC dynamics on a regional landscape level and to evaluate the effect of land-use change.     

Copper mobility and toxicity of soil percolation water to bacteria in a metal polluted forest soil

In order to assess the success of in situ remediation of coniferous forest soil polluted by a Cu–Ni smelter, the total Cu concentration in soil percolation water, the fluxes of Cu down through the soil profile, and the toxicity of soil percolation water to soil bacteria were studied. Total Cu in percolation water was also fractionated into free ionic and complexed forms. The toxicity of the percolation water was measured by the [³H]-thymidine incorporation method, which measures bacterial growth rates. Soil percolation water was collected during one growing season by zero tension lysimeters inserted at depths of 0.2 and 0.4 m in the soil. The treatments consisted of a control, mulch application to the forest floor (M) and mulch application after removing the polluted organic soil layer (MR). The mulch consisted of a mixture of compost and woodchips (1/1; vol/vol). Analysis of Cu species and dissolved organic carbon (DOC) indicated that DOC leached from the mulch and complexed Cu into forms that were less toxic to soil bacteria. At 0.2 m depth percolation water toxicity was 19% lower in the M and 42% lower in the MR treatment than in the control. Toxicity correlated with the Cu²⁺ concentration, which was 61 and 84% lower in the M and MR treatments, respectively, compared to the control. However, there were signs that total Cu had leached down through the soil profile, the leaching being more pronounced in the MR treatment.     

Effects of forest clear-cutting on the carbon and nitrogen fluxes through podzolic soil horizons

Effects of clear-cutting on the dissolved fluxes of organic C (DOC), organic N (DON), NO₃ ^– and NH₄ ⁺ through surface soil horizons were studied in a Norway spruce dominated mixed boreal forest in eastern Finland. Bulk deposition, total throughfall and soil water from below the organic (including understorey vegetation and, after clear-cutting, also logging residues), eluvial and illuvial horizons were sampled weekly from 1993 to 1999. Clear-cutting was carried out in September 1996. The removal of the tree canopy decreased the deposition of DOC and DON to the forest floor and increased that of NH₄ ⁺ and NO₃ ^– but did not affect the deposition of total N (DTN, <3 kg ha^–1 a^–1). The leaching of DOC and DON from the organic horizon increased over twofold after clear-cutting (fluxes were on an average 168 kg C and 3.3 kg N ha^–1 a^–1), but the increased outputs were effectively retained in the surface mineral soil horizons. Inorganic N deposition was mainly retained by the logging residues and organic horizon indicating microbial immobilization. Increased NO₃ ^– formation reflected as elevated concentrations in the percolate from below the mineral soil horizons were observed especially in the third year after clear-cutting. However, the changes were small and the increased leaching of DTN from below the illuvial horizon remained small (<0.4 kg ha^–1 a^–1) and mainly DON. Effects of clear-cutting on the transport of C and N to surface waters will probably be negligible.     

Vertical transport of dissolved organic C and N under long-term N amendments in pine and hardwood forests

At the Harvard Forest, Massachusetts, a long-term effort is under way to study responses in ecosystem biogeochemistry to chronic inputs of N in atmospheric deposition in the region. Since 1988, experimental additions of NH₄NO₃ (0, 5 and 15 g N m^–2 yr^–1) have been made in two forest stands:Pinus resinosa (red pine) and mixed hardwood. In the seventh year of the study, we measured solute concentrations and estimated solute fluxes in throughfall and at two soil depths, beneath the forest floors (Oa) and beneath the B horizons.Beneath the Oa, concentrations and fluxes of dissolved organic C and N (DOC and DON) were higher in the coniferous stand than in the hardwood stand. The mineral soil exerted a strong homogenizing effect on concentrations beneath the B horizons. In reference plots (no N additions), DON composed 56% (pine) and 67% (hardwood) of the total dissolved nitrogen (TDN) transported downward from the forest floor to the mineral soil, and 98% of the TDN exported from the solums. Under N amendments, fluxes of DON from the forest floor correlated positively with rates of N addition, but fluxes of inorganic N from the Oa exceeded those of DON. Export of DON from the solums appeared unaffected by 7 years of N amendments, but as in the Oa, DON composed smaller fractions of TDN exports under N amendments. DOC fluxes were not strongly related to N amendment rates, but ratios of DOC:DON often decreased.The hardwood forest floor exhibited a much stronger sink for inorganic N than did the pine forest floor, making the inputs of dissolved N to mineral soil much greater in the pine stand. Under the high-N treatment, exports of inorganic N from the solum of the pine stand were increased >500-fold over reference (5.2 vs. 0.01 g N m^–2 yr^–1), consistent with other manifestations of nitrogen saturation. Exports of N from the solum in the pine forest decreased in the order NO₃-N> NH₄-N> DON, with exports of inorganic N 14-fold higher than exports of DON. In the hardwood forest, in contrast, increased sinks for inorganic N under N amendments resulted in exports of inorganic N that remained lower than DON exports in N-amended plots as well as the reference plot.     

Changes in dissolved lignin-derived phenols, neutral sugars, uronic acids, and amino sugars with depth in forested Haplic Arenosols and Rendzic Leptosols

A major part of the dissolved organic matter produced in the organic layers of forest ecosystems and leached into the mineral soil is retained by the upper subsoil horizons. The retention is selective and thus dissolved organic matter in the subsoils has different composition than dissolved organic matter leached from the forest floor. Here we report on changes in the composition of dissolved organic matter with soil depth based on C-to-N ratios, XAD-8 fractionation, wet-chemical analyses (lignin-derived CuO oxidation products, hydrolysable sugars and amino sugars) and liquid-state ¹³C nuclear magnetic resonance (NMR) spectroscopy. Dissolved organic matter was sampled directly beneath the forest floor using tension-free lysimeters and at 90cm depth by suction cups in Haplic Arenosols under Scots pine (Pinus sylvestris L.) and Rendzic Leptosols under European beech (Fagus sylvatica L.) forest. At both sites, the concentrations of dissolved organic carbon (DOC) decreased but not as strongly as reported for deeply weathered soils. The decrease in DOC was accompanied by strong changes in the composition of dissolved organic matter. The proportion of the XAD-8-adsorbable (hydrophobic) fraction, carboxyl and aromatic C, and the concentrations of lignin-derived phenols decreased whereas the concentrations of sugars, amino sugars, and nitrogen remained either constant or increased. A general feature of the compositional changes within the tested compound classes was that the ratios of neutral to acidic compounds increased with depth. These results indicate that during the transport of dissolved organic matter through the soils, oxidatively degraded lignin-derived compounds were preferentially retained while potentially labile material high in nitrogen and carbohydrates tended to remain dissolved. Despite the studied soils' small capacity to sorb organic matter, the preferential retention of potentially refractory and acidic compounds suggests sorption by the mineral soil matrix rather than biodegradation to govern the retention of dissolved organic matter even in soils with a low sorption capacity.     

Leaching of dissolved organic carbon,dissolved organic nitrogen,and other solutes from coarse woody debris and litter in a mixed forest in New York State

Coarse woody debris (CWD) may play a role in nutrient cycling in temperate forests through the leaching of solutes, including dissolved organic carbon (DOC) and dissolved organic nitrogen (DON), to the underlying soil. These fluxes need to be considered in element budget calculations, and have the potential to influence microbial activity, soil development, and other processes in the underlying soil, but studies on leaching from CWD are rare. In this study, we collected throughfall, litter leachate, and CWD leachate in situ at a young mixed lowland forest in NY State, USA over one year. We measured the concentrations of DOC, DON, NH₄⁺, NO₃⁻, dissolved organic sulfur, SO₄²⁻, Cl⁻, Al, Ca, K, Mg, Na, and P, estimated the flux of these solutes in throughfall, and measured the cover of CWD to gain some insight into possible fluxes from CWD. Concentrations of DOC were much higher in CWD leachate than in throughfall or litter leachate (15 vs. 0.7 and 1.6 mM, respectively), and greater than reported values for other leachates from within forested ecosystems. Other solutes showed a similar pattern, with inorganic N being an exception. Our results suggest that microsite scale fluxes of DOC from CWD may be An high relative to throughfall and litter leaching fluxes, but since CWD covered a relatively small fraction (2%) of the forest floor in our study, ecosystem scale fluxes from CWD may be negligible for this site. Soil directly beneath CWD may be influenced by CWD leaching, in terms of soil organic matter, microbial activity, and N availability. Concentrations of some metals showed correlations to DOC concentrations, highlighting the possibility of complexation by DOM. Several solute concentrations in throughfall, including DOC, showed positive correlations to mean air temperature, and fewer showed positive correlations in litter leachate, while negative correlations were observed to precipitation, suggesting both biological and hydrologic control of solute concentrations.