Contribution of canopy leaching to sulphate deposition in a Scots pine forest

Radioactive sulphate (35SO4) was applied to the soil below a Scots pine forest on 23 June 1989, and its movement into the canopy and into throughfall and stemflow was measured over 4 months. The specific activity, Bq (mg S)(-1), of the canopy increased monotonically; uptake by current-year (1989) expanding needles was initially twice as fast as by older needles or live twigs. By 10 October the canopy average specific activity was 62 Bq (mg S)(-1). The specific activity of net throughfall (throughfall + stemflow - rain), deduced from measurements from six throughfall collectors, six stemflow collectors and two rain collectors, fell rapidly from 12.6 Bq (mg S)(-1) in late July to <1 Bq (mg S)(-1) in mid-August. The results suggest (assuming rapid equilibration of 35S with sulphate in soil) that root-derived sulphate contributed c. 3% of sulphate in net throughfall and that dry deposition of SO2 and sulphate particles contributed c. 97% of the 0.56 g S m(-2) measured in net throughfall over the period. Simultaneous measurements of SO2 at canopy height and of NH3 above and within the canopy gave mean concentrations of 5.9 and 0.86 microg m(-3), respectively, sufficient to account for the sulphate measured in net throughfall only if codeposition of NH3 and SO2 occurred to canopy surfaces. The large values of specific activity observed in July, however, indicate that throughfall composition may be closely related to recent soil input of sulphate, and that equilibrium cannot be safely assumed. The possibility of a significant contribution of soil-derived sulphate to sulphate deposition in net throughfall cannot be ruled out on the basis of this experiment.     

Mercury in contaminated sediments and pore waters enriched in sulphate (Tagus Estuary,Portugal)

Three sediment cores, collected nearby the effluent of a chlor-alkali industry, were sliced in 0.5-cm layers and centrifuged for pore water extraction. Mercury, Fe and Mn were determined in the solids as total concentration, hydroxylamine extractable fraction and HCl extractable fraction. Sulphur was determined in the HCl extraction. Total and reactive mercury, chlorinity, S(2-), SO(4)(2-), total Fe, and total Mn were measured in pore waters. The solids contained 3.0-60 nmol g(-1) of total Hg and pore waters 70-5800 pM of total Hg and 1.8-76 pM of reactive mercury. Pore waters presented 2.3-94 times more sulphate than the overlying estuarine waters due to the input from the industry. In layers where hydroxylamine extractable Fe exhibited a broad maximum (precipitation of Fe-oxides) sulphate was reduced to S(2-). The competition between the high content of SO(4)(2-) and Fe(III) as electron acceptors, in chemical reactions occurring in the upper sediments, may explain the co-existence of S(2-) and Fe-oxides in the same layers. Mercury was detected in the hydroxylamine extracts (20-29 nmolg(-1)) in the layers where Fe-oxides were formed, and reactive dissolved Hg showed minimum concentrations. The excess of sulphate in pore waters favoured the abundant Fe-oxides in the upper solid sediments, which appear to work as a barrier limiting the escape of mercury to the water column.     

Sulphur isotopic investigation of a polluted raised bog and the uptake of pollutant sulphur by Sphagnum

The sulphur content and sulphur isotopic composition of Sphagnum as well as anionic compositions and sulphur isotope ratios of rainwater inputs and bog waters have been measured at Thorne Moors, a raised bog in eastern England. Rainwater sulphate isotopic composition shows the sulphur input at this site to be dominated by anthropogenic pollution from fossil fuel burning. Strong depletion of sulphate (low SO4(2-)/Cl-) and enrichment in 34S in sulphate occurs at depth in the bog porewaters due to bacterial sulphate reduction. Some surface waters have low SO4(2-)/Cl-) and are 34S enriched due to removal of sulphate by downward diffusion into a sulphate-reducing zone. Other sites have high SO4(2-)/Cl-) which appears to result from oxidation of organically bound sulphur in the peat. Sulphur is present in Sphagnum at around 0.2% by weight and is depleted by 0 to -9 per thousand in the heavier 34S isotope compared to sulphate. Comparison with similar data from pristine coastal sites shows that sulphur incorporation into Sphagnum is enhanced in the polluted site (as Sphagnum sulphur concentrations are higher at lower total sulphur inputs) and that sulphur incorporation is accompanied by a smaller isotopic shift than in the pristine sites. The data support a model of preferential incorporation of partially reduced sulphur species (probably HSO3-) into Sphagnum. In pristine sites these are only available as oxidation products of sulphide formed by sulphate reduction and are 32S depleted. In polluted sites this source is augmented by sulphur(IV) species in atmospheric inputs and the resultant mixture is less depleted in 32S. Thus, in the polluted sites more HSO3- is available for uptake and the isotopic shift between Sphagnum and aqueous sulphur species is smaller.     

Trends in atmospheric ammonium concentrations in relation to atmospheric sulfate and local agriculture

Ammonium (NH(4)(+)) concentrations in air and precipitation at the Institute of Ecosystem Studies (IES) in southeastern New York, USA declined over an 11-year period from 1988 to 1999, but increased from 1999 to 2001. These trends in particulate NH(4)(+) correlated well with trends in particulate SO(4)(2-) over the 1988-2001 period. The NH(4)(+) trends were not as well correlated with local cattle and milk production, which declined continuously throughout the period. This suggests that regional transport of SO(4)(2-) may have a greater impact on concentrations of NH(4)(+) and subsequent deposition than local agricultural emissions of NH(3). Ammonium concentrations in precipitation correlated significantly with precipitation SO(4)(2-) concentrations for the 1984-2001 period although NH(4)(+) in precipitation increased after 1999 and SO(4)(2-) in precipitation continued to decline after 1999. The correlation between NH(4)(+) and SO(4)(2-) was stronger for particulates than for precipitation. Particulate NH(4)(+) concentrations were also correlated with particulate SO(4)(2-) concentrations at 31 of 35 eastern U.S. CASTNet sites that had at least 10 years of data. Air concentrations of NH(4)(+) and SO(4)(2-) were more strongly correlated at the sites that were located within an agricultural landscape than in forested sites. At most of the sites there was either no trend or a decrease in NH(4)(+) dry deposition during the 1988-2001 period. The sites that showed an increasing trend in NH(4)(+) dry deposition were generally located in the southeastern U.S. The results of this study suggest that, in the northeastern U.S., air concentrations of NH(4)(+) and subsequent deposition may be more closely linked to SO(4)(2-) and thus SO(2) emissions than with NH(3) emissions. These results also suggest that reductions in S emissions have reduced NH(4)(+) transport to and NH(4)(+)-N deposition in the Northeast.     

Response of needle sulphur and nitrogen concentrations of Scots pine versus Norway spruce to SO2 and NO2

The results of two field studies and an open-top chamber fumigation experiment showed that the response of mature Scots pine to SO(2) and NO(2) differed from that of mature Norway spruce. Moreover, the response of pine seedlings to SO(2) and NO(2) differed from that of mature trees. The greater increase in the needle total S concentrations of pine suggested more abundant stomatal uptake of SO(2) compared to spruce. Both pine seedlings and mature trees also seemed to absorb more N from atmospheric deposition. Mature pine was able to assimilate SO(4)(2-) derived from SO(2) into organic S more effectively than mature spruce at the high S and N deposition sites, whereas both pine and spruce seedlings accumulated SO(4)-S under NO(2)+SO(2) exposure. Spruce, in turn, accumulated SO(4)-S even when well supplied with N. Net assimilation of SO(4)(2-) in conifer seedlings was enhanced markedly by elevated temperature. To protect the northern coniferous forests against the harmful effects of S and N deposition, it is recommended that the critical level for SO(2) as a growing season mean be set at 5-10 microg m(-3) and NO(2) at 10-15 microg m(-3), depending on the 'effective temperature sum' and/or whether SO(2) and NO(2) occur alone or in combination.     

Temporal evolution of redox processes and free Cd dynamics in a metal-contaminated soil after rewetting

Soil testing procedures to address metals bioavailability currently use air-dried soil rewetted almost until saturation. Such practices may influence the redox state of soil and the related dynamics of metals. To assess this potential impact, a metal-contaminated soil was air-dried and rewetted to 90% water holding capacity. We monitored over a 21-day incubation period the temporal changes of soil redox potential and solution Cd concentration (either total or free). Other physico-chemical parameters were followed notably pH, ionic strength (I) and the concentrations of NO(3)(-), Mn, Fe and SO(4)(2-) in solution. Soil redox potential showed the progressive establishment of strong reducing conditions in soil, in agreement with the temporal changes of NO(3)(-), Mn, Fe and SO(4)(2-) concentrations. It decreased by 13 pe units over the culture period leading to sulphate-reducing conditions (pe<-3) within only 21days. Solution Cd concentration increased transitorily over the first 100-150h of incubation (2-fold increase) in relation with the parallel increase in the concentration of competing cations for adsorption (Ca, Mg). It steeply decreased over the last 300h of incubation (30-fold decrease) as a result of Cd precipitation as Cd sulphides. This biphasic evolution of Cd dynamics was related to the temporal changes of Cd resupply from the solid phase. Using the technique of DGT we described the kinetics of Cd resupply over time and needed to invoke the existence of two pools of Cd.     

Sulphur dioxide adsorption in Scots pine canopies exposed to high ammonia emissions near a Cu-Ni smelter in SW Finland

Since 1994 the nickel-processing plant at the Cu-Ni smelter at Harjavalta, south-west Finland, has emitted considerable amounts of NH(3) into the atmosphere. The effects of NH(3) emissions on nitrogen and sulphur deposition in throughfall and the foliar nutrient status were investigated in a Scots pine stand at 0.5 km distance. Bulk deposition, stand throughfall and percolation water (20 cm depth) samples were collected at 4-week intervals during 1992-1998. pH and the Ca, Mg, K, NH(4) and SO(4) concentrations were determined on the samples. NH(3) emissions have strongly increased the scavenging of SO(2) from the air in the pine stand, and the increased levels of N and S deposition were clearly evident as increased foliar N and S concentrations and larger needle size. The increased input of SO(4) into the forest floor was not associated with an increase in the leaching of Ca and Mg from the surface soil layers.     

A remediation strategy based on active phytoremediation followed by natural attenuation in a soil contaminated by pyrite waste

Phytoremediation of metal-polluted soils can be promoted by the proper use of soil amendments and agricultural practices. A 4-year phytoremediation programme was applied to a site affected by the toxic spill of pyrite residue at Aznalcóllar (Spain) in 1998, contaminated with heavy metals (Zn, Cu, Pb, Cd) and arsenic. This consisted of active phytoremediation, using organic amendments (cow manure and compost) and lime and growing two successive crops of Brassica juncea (L.) Czern., followed by natural attenuation without further intervention. Changes in soil pH, extractable metal and As concentrations, organic carbon content and microbial biomass was evaluated. The initial oxidation of metal sulphides from pyrite residues released soluble metals and reduced soil pH to extremely acidic values (mean 4.1, range 2.0-7.0). The addition of lime (up to 64 t ha(-1)) increased soil pH to adequate values for plant growth, resulting in a significant decrease in DTPA-extractable metal concentrations in all plots. The natural attenuation phase showed also a decrease in extractable metals. Organic treatments increased the soil total organic carbon, which led to higher values of microbial biomass (11.6, 15.2 and 14.9 g kg(-1) TOC and 123, 170 and 275 microg g(-1) biomass-C in control, compost and manure plots, respectively). Active phytoremediation followed by natural attenuation, was effective for remediation of this pyrite-polluted soil.     

Soil solution nitrogen and cations influenced by (NH4)2SO4 deposition in a coniferous forest

The effects of chronically enhanced (NH(4))(2)SO(4) deposition on ion concentrations in soil solution and ionic fluxes were investigated in a Picea abies plot at Grizedale forest, NW England. Soil cores closed at the base and containing a ceramic suction cup sampler were 'roofed' and watered every 2 weeks with bulk throughfall collected in the field. Treatments consisted of the inclusion of living roots from mature trees in the lysimeters and increasing (NH(4))(2)SO(4) deposition (NS treatment) to ambient + 75 kg N ha(-1) a(-1). Rainfall, throughfall and soil solutions were collected every 2 weeks during 18 months, and analysed for major cations and anions. NO(3)(-) fluxes significantly increased following NS treatment, and were balanced by increased Al(3+) losses. Increased SO(4)(2-) concentrations played a minor role in controlling soil solution cation concentrations. The soil exchange complex was dominated by Al and, during the experimental period, cores of all treatments 'switched' from Ca(2+) to Al(3+) leaching, leading to mean [Formula: see text] molar ratios in soil solution of NS treated cores of 0.24. The experiment confirmed that the most sensitive soils to acidification (through deposition or changing environmental conditions) are those with low base saturation, and with a pH in the lower Ca, or Al buffer ranges.     

Buffering processes in a boreal dissolved organic carbon-rich stream during experimental acidification

The role of organic acids on surface water acidity as well as their buffering during anthropogenic acidification and subsequent recovery was studied in a field experiment on a total organic carbon (TOC)-rich stream draining the Svartberget catchment in northern Sweden. H(2)SO(4) was added to the stream to increase SO(4)(2-) concentration by 90 microeq l(-1) for 30 h. About 60% of the added H(+) was buffered by protonation of organic acids, another 20% was buffered by base cations released from the surface of the stream channel and only ca. 20% of the added acid remained unbuffered. TOC concentrations (27 mg l(-1)), and site density of carboxylic groups--8.6 microeq (mg TOC)(-1)--remained stable during the experiment. Two models of organic acid dissociation (a triprotic model and a monoprotic pH-dependent pKa model) were fitted to the experimental results. These models explained the observed variations in organic anions, but the model parameters were quite different from those reported by studies in Northern America and Central Europe. This experiment had substantially more buffering effect of TOC between pH 4.4 and 5.3, which is an environmentally important pH range.     

Foliar sulphur species in pine: a new indicator of a forest ecosystem under air pollution stress

An eleven-year foliar sulphur (S) monitoring program was carried out from 1976 to 1986 near a sulphur recovery-gas plant in west-central Alberta, Canada, as part of a case study designed to determine the effects of chronic, low concentration sulphur gas emissions on the forest ecosystem surrounding the gas plant. Measurements of both foliar total sulphur (ST) and foliar inorganic sulphur (SO4-S) concentration in lodgepole x jack pine trees at the end of each of the 11 growing seasons were taken to provide an indication of S loading of the forest from industrial sulphur emissions. To measure the state of the forest ecosystem, foliar ST was separated into foliar accumulated sulphur (inorganic sulphur or SO4-S) and foliar assimilated sulphur (organic sulphur or S0) and the ratio of SO4-S/S0 taken. Foliar S0 was calculated as the difference between foliar ST and foliar SO4-S. The median SO4-S/S0 ratio, with all three years of needles considered, varied from 0.29 at a reference location (AV) to 0.88 at the location with the highest stress (AI). The corresponding mean values ranged from 0.3 at the reference location to 2.2 at the location of highest stress. The mean seasonal photosynthetic rate of current year's foliage of the pine trees and soil pH were reduced at a stressed location (AI) compared to the reference location (AV), between 1976 and 1981. Over this same time period the mean foliar SO4-S/S0 ratio increased from 0.4 +/- 0.1 to 1.0 +/- 0.3 at the stressed location (AI) and remained nearly the same at the reference location (AV) at 0.3 +/- 0.1. This research suggests that the foliar SO4-S/S0 ratio is a useful indicator of the state of forest ecosystems under S air pollution stress. It is concluded that foliar S separated into various fractions has potential as an early warning environmental management tool.     

Acid-sensitive waters of the English Lake District: a steady-state model of streamwater chemistry in the upper Duddon catchment

Data on deposition and streamwater chemistry, obtained for the upper catchment of the River Duddon in the 1970s and 1980s, are reviewed. These data, together with soil chemical data, are used to deduce key processes in the deposition-catchment interaction, the analysis being based on current concepts of acidification. The processes are incorporated into a steady-state model that allows streamwater compositions to be calculated. The large baseflow pH range (5-7) of Duddon streams is accounted for in the model by a range of base cation weathering rates. Other processes invoked are evapotranspiration, the uptake of nitrogen by plants, dissolution of Al(OH)(3) in the mineral soil, precipitation of Al(OH)(3) in the baserock zone and in streamwater, Al(3+) hydrolysis, and reactions of the carbonate system. Both cation exchange and sulphate adsorption are ignored, because they are assumed to influence rates-of-change between steady states, but not steady-state water compositions per se. The model can be used to estimate variations in streamwater composition with flow. Model calculations suggest that a 50% decrease in depositional acidifying components (sulphur oxides and NH(4)(+)) would result in increases of up to 1 pH unit in streamwaters with present-day baseflow pH values of 5 or less. It appears that water quality in the upper Duddon is currently more sensitive to inputs of NH(4)(+) than of H(2)SO(4). To improve the reliability of model predictions, more information is required on (a) the pH dependence of base cation weathering, (b) transformations involving nitrogen, (c) aluminium chemistry and (d) partial pressures of CO(2) in soil and baserock.     

Effects of nitrogen with and without acidified sulphur on an ectomycorrhizal community in a Sitka spruce (Picea sitchensis Bong. Carr) forest

This preliminary study investigated the effects of enhanced nitrogen (NH4NO3 at 48 kg ha(-1) y(-1)), sulphur (Na2SO4 at 50 kg ha(-1) y(-1)), acidified nitrogen and sulphur (H2SO4 + NH4NO3) at pre-stated doses (pH 2.5), and acidified nitrogen and sulphur deposition at double these doses on the ectomycorrhizal community associated with a 13-year-old Sitka spruce (Picea sitchensis) forest. Sulphur deposition had little impact on below ground ectomycorrhizal diversity, but stimulated sporocarp production. Nitrogen inputs increased below ground colonisation compared to acidified nitrogen and sulphur, largely due to an increase in Tylospora fibrillosa colonisation. Sporocarp production and ectomycorrhizal root colonisation by Lactarius rufus were reduced in the nitrogen treated plots. These observations suggest that nitrogen deposition to a young plantation may suppress ectomycorrhizal fungi producing large sporocarps. It is proposed that enhanced nitrogen deposition increases ectomycorrhizal nitrogen assimilation, consuming more carbon and leaving less for extrametrical mycelium and sporocarp development.     

Response of the Plastic Lake catchment, Ontario, to reduced sulphur deposition

As a consequence of decreases in the emission rate of sulphur in eastern North America in the late 1970s and early 1980s, sulphate deposition in central Ontario declined by about 40%, but has remained constant for about six years. Plastic Lake, a small, dilute lake on the Precambrian shield that the authors have studied since 1979, acidified between the start of the study and about 1986, but since then has not changed. The authors also monitored the chemistry of streamwater draining the Plastic Lake catchment. Water quality of runoff from an upland site improved rapidly (pH and alkalinity increased, SO4(2-) and Al decreased), but two factors offset these improvements. A small wetland area downstream reversed most of these changes, resulting in a constant output of strong acid from the catchment. In addition, in extremely dry years (1983, 1987, 1989) there were very high concentrations of SO4(2-) in the streamwater, suggesting substantial re-oxidation of reduced S in the catchment.     

Bulk deposition in a rural area located around a large coal-fired power station, northeast Spain

This work focuses on bulk deposition in a rural area located around a large coal-fired power station in northeast Spain. Deposition chemistry was characterised by high concentrations of SO(4)(2-), Ca(2+) and NH(4)(+), which were relatively high when compared with other rural areas. Monthly bulk deposition evolution of major ions was the result of two superimposed patterns: one pattern related to the volume of precipitation and the other showed the seasonal influence of the major ionic sources. A major local origin was attributed to bulk deposition of SO(4)(2-), NH(4)(+), and Ca(2+), whereas a relatively higher contribution of an external source was deduced for NO(3)(-), Na(+) and Cl(-). The SO(4)(2-) concentrations showed a significant correlation with the local SO(2) emissions. High levels of Ca(2+) were due to the high alkalinity of soils in the study area, although an external origin was attributed to the frequent air mass intrusions from the Sahara. Sources of NH(4)(+) were related to intensive livestock farming in the area. Total suspended particles exert a marked influence over bulk deposition and neutralisation. Thus, despite the high emissions of SO(2) in the area, neutral pH values have always been attained given that the concentrations of Ca(2+) and NH(4)(+) account for the total neutralisation of NO(3)(-) and SO(4)(2-).     

Simulating the long-term chemistry of an upland UK catchment: major solutes and acidification

CHUM-AM was used to investigate changes in soil and water chemical variables in four moorland sub-catchments in Cumbria UK, to which non-marine S deposition has declined by 65% since the 1970s. The principal processes represented in the model comprise N and S uptake and release, water movements, the binding of cations by soil organic matter, chemical interactions in solution, and chemical weathering. CHUM-AM reproduced reasonably well the current soil pH and pools of N and S, and changes in streamwater chemistry over the period 1970-2000, notably decreases in the concentrations of alkaline earth cations and sulphate, and increases in pH. The model also predicts streamwater pH-Al relationships in agreement with observations. Predictive calculations suggest that constant atmospheric deposition of N at present rates will lead to N saturation and re-acidification, whereas a 50% reduction in N would stabilise soil and streamwater pH at about the present levels.     

Contribution of heavy metals and As-loaded lupin root mineralization to the availability of the pollutants in multi-contaminated soils

White lupin (Lupinus albus L.) is an annual crop that has been used for phytostabilization of acidified multi-contaminated soils. Once the culture cycle is over, after shoot harvesting, a progressive transference of contaminants from roots to soil may take place as decomposition of roots occurs. An incubation experiment with Cu, Zn, Cd, and As-loaded roots of white lupin and soils with different pH values and concentrations of these contaminants from the area affected by a mine spill at Aznalcóllar (near Seville, Spain) was performed in order to assess the effect of the decomposition of the roots to the pH and (NH4)2SO4-extractable levels of these pollutants in the soils. Pollutants loaded-roots were mineralized (56 d) at a ratio similar to animal manures (15.8-19.4% of total organic carbon) in soil. The estimated root inputs of contaminants in comparison to their extractable concentrations in soil were high, especially in the control, non-contaminated and neutral contaminated soils. However, the extractable concentrations of the toxic elements in the soil were mainly governed by soil pH. Hence, the correction and maintenance of the soil pH within the range 5-6 after lupin culture is essential for long-time phytostabilization of acidified multi-contaminated soils.     

Recharge processes drive sulfate reduction in an alluvial aquifer contaminated with landfill leachate

Natural attenuation of contaminants in groundwater depends on an adequate supply of electron acceptors to stimulate biodegradation. In an alluvial aquifer contaminated with leachate from an unlined municipal landfill, the mechanism of recharge infiltration was investigated as a source of electron acceptors. Water samples were collected monthly at closely spaced intervals in the top 2 m of the saturated zone from a leachate-contaminated well and an uncontaminated well, and analyzed for delta(18)O, delta(2)H, non-volatile dissolved organic carbon (NVDOC), SO(4)(2-), NO(3)(-) and Cl(-). Monthly recharge amounts were quantified using the offset of the delta(18)O or delta(2)H from the local meteoric water line as a parameter to distinguish water types, as evaporation and methanogenesis caused isotopic enrichment in waters from different sources. Presence of dissolved SO(4)(2-) in the top 1 to 2 m of the saturated zone was associated with recharge; SO(4)(2-) averaged 2.2 mM, with maximum concentrations of 15 mM. Nitrate was observed near the water table at the contaminated site at concentrations up to 4.6 mM. Temporal monitoring of delta(2)H and SO(4)(2-) showed that vertical transport of recharge carried SO(4)(2-) to depths up to 1.75 m below the water table, supplying an additional electron acceptor to the predominantly methanogenic leachate plume. Measurements of delta(34)S in SO(4)(2-) indicated both SO(4)(2-) reduction and sulfide oxidation were occurring in the aquifer. Depth-integrated net SO(4)(2-) reduction rates, calculated using the natural Cl(-) gradient as a conservative tracer, ranged from 7.5x10(-3) to 0.61 mM.d(-1) (over various depth intervals from 0.45 to 1.75 m). Sulfate reduction occurred at both the contaminated and uncontaminated sites; however, median SO(4)(2-) reduction rates were higher at the contaminated site. Although estimated SO(4)(2-) reduction rates are relatively high, significant decreases in NVDOC were not observed at the contaminated site. Organic compounds more labile than the leachate NVDOC may be present in the root zone, and SO(4)(2-) reduction may be coupled to methane oxidation. The results show that sulfur (and possibly nitrogen) redox processes within the top 2 m of the aquifer are directly related to recharge timing and seasonal water level changes in the aquifer. The results suggest that SO(4)(2-) reduction associated with the infiltration of recharge may be a significant factor affecting natural attenuation of contaminants in alluvial aquifers.     

Changes in soil organic carbon storage under grassland as evidenced by changes in sulphur input-output budgets

Information about temporal changes in soil organic carbon (C) pools may be obtained indirectly from changes in input-output budgets of organically combined nutrients such as sulphur (S). Sulphur budgets were therefore evaluated for Northern Ireland (NI) for the period 1940-1990, inclusive. These budgets indicated that the land or soil had acted first as a sink but then as a source for S, and that reserves of soil S built up between 1940 and 1965 were totally depleted by the mid-1980s. Pooled data from six long-term soil-monitoring sites on undisturbed grassland suggested that negative S budgets from the late-1970s onwards had been due to the net mineralization of soil organic matter and thus were indicative of net losses of organic C from surface soil horizons. There was some evidence that the decline in rainfall and fertiliser S inputs from the mid-1960s may have precipitated the breakdown of soil organic matter.