Sizeable net export of base cations from a Carpathian flysch catchment indicates their geogenic origin while the 26Mg/24Mg, 44Ca/40Ca and 87Sr/86Sr isotope ratios in runoff are indistinguishable from atmospheric input.

Nutrient imbalances may negatively affect the health status of forests exposed to multiple stress factors, including drought and bark beetle calamities. We studied the origin of base cations in runoff from a small Carpathian catchment underlain by base-poor flysch turbidites using magnesium (Mg), calcium (Ca) and strontium (Sr) isotope composition of 10 ecosystem compartments. Our objective was to constrain conclusions drawn from long-term hydrochemical monitoring of inputs and outputs. Annual export of Mg, Ca and Sr exceeds 5-to-15 times their atmospheric input. Mass budgets per se thus indicate sizeable net leaching of Mg, Ca and Sr from bedrock sandstones and claystones. Surprisingly, δ26Mg, δ44Ca and 87Sr/86Sr isotope ratios of runoff were practically identical to those of atmospheric deposition and soil water but significantly different from bedrock isotope ratios. We did not find any carbonates in the studied area as a hypothetical, easily dissolvable source of base cations whose isotope composition might corroborate the predominance of geogenic base cations in the runoff. Marine carbonates typically have lower δ26 Mg and 87Sr/86Sr ratios, and silicate sediments often have higher δ26Mg and 87Sr/86Sr ratios than runoff at the study site. Mixing of these two sources, if confirmed, could reconcile the flux and isotope data.

Forest growth responds more to air pollution than soil acidification.

The forests of central Europe have undergone remarkable transitions in the past 40 years as air quality has improved dramatically. Retrospective analysis of Norway spruce (Picea abies) tree rings in the Czech Republic shows that air pollution (e.g. SO2 concentrations, high acidic deposition to the forest canopy) plays a dominant role in driving forest health. Extensive soil acidification occurred in the highly polluted "Black Triangle" in Central Europe, and upper mineral soils are still acidified. In contrast, acidic atmospheric deposition declined by 80% and atmospheric SO2 concentration by 90% between the late 1980s and 2010s. In this study we oserved that annual tree ring width (TRW) declined in the 1970s and subsequently recovered in the 1990s, tracking SO2 concentrations closely. Furthermore, recovery of TRW was similar in unlimed and limed stands. Despite large increases in soil base saturation, as well as soil pH, as a result of repeated liming starting in 1981, TRW growth was similar in limed and unlimed plots. TRW recovery was interrupted in 1996 when highly acidic rime (originating from more pronounced decline of alkaline dust than SO2 from local power plants) injured the spruce canopy, but recovered soon to the pre-episode growth. Across the long-term site history, changes in soil chemistry (pH, base saturation, Bc/Al soil solution ratio) cannot explain observed changes in TRW at the two study sites where we tracked soil chemistry. Instead, statistically significant recovery in TRW is linked to the trajectory of annual SO2 concentrations or sulfur deposition at all three stands.

Long-term rise in riverine dissolved organic carbon concentration is predicted by electrolyte solubility theory.

The riverine dissolved organic carbon (DOC) flux is of similar magnitude to the terrestrial sink for atmospheric CO2, but the factors controlling it remain poorly determined and are largely absent from Earth system models (ESMs). Here, we show, for a range of European headwater catchments, that electrolyte solubility theory explains how declining precipitation ionic strength (IS) has increased the dissolution of thermally moderated pools of soluble soil organic matter (OM), while hydrological conditions govern the proportion of this OM entering the aquatic system. Solubility will continue to rise exponentially with declining IS until pollutant ion deposition fully flattens out under clean air policies. Future DOC export will increasingly depend on rates of warming and any directional changes to the intensity and seasonality of precipitation and marine ion deposition. Our findings provide a firm foundation for incorporating the processes dominating change in this component of the global carbon cycle in ESMs.

Changes in forest nitrogen cycling across deposition gradient revealed by δ15N in tree rings.

Tree rings provide valuable insight into past environmental changes. This study aimed to evaluate perturbations in tree ring width (TRW) and δ15N alongside soil acidity and nutrient availability gradients caused by the contrasting legacy of air pollution (nitrogen [N] and sulphur [S] deposition) and tree species (European beech, Silver fir and Norway spruce). We found consistent declines of tree ring δ15N, which were temporarily unrelated to the changes in the TRW. The rate of δ15N change in tree rings was related to the contemporary foliar carbon (C) to phosphorus (P) ratio. This observation suggested that the long-term accumulation of 15N depleted N in tree rings, likely mediated by retained N from deposition, was restricted primarily to stands with currently higher P availability. The shifts observed in tree-ring δ15N and TRW suggest that acidic air pollution rather than changes in stand productivity determined alteration of N and C cycles. Stable N isotopes in tree rings provided helpful information on the trajectory of the N cycle over the last century with direct consequences for a better understanding of future interactions among N, P and C cycles in terrestrial ecosystems.

Catchment Runoff in Industrial Areas Exports Legacy Pollutant Zinc from the Topsoil Rather than Geogenic Zn.

In highly industrialized, densely populated parts of Central Europe, mobilization of legacy Zn pollution from forest ecosystems may negatively affect the quality of water resources. To test this hypothesis, we determined the 66Zn/64Zn isotope ratios of 15 Zn reservoirs and fluxes in an acidified, spruce die-back affected mountain-slope catchment in northern Czech Republic. The δ66Zn values of precipitation, organic horizon, and runoff were statistically indistinguishable. In contrast, δ66Zn values of bedrock orthogneiss and mineral soil were significantly different from δ66Zn values of runoff. The magnitude of within-site Zn isotope fractionations appeared to be relatively small. Despite the large potential source of Zn in bedrock, runoff exported mostly young pollutant Zn that had been temporarily stored in the organic horizon. This conclusion was corroborated by comparing Zn input-output mass balances in the polluted northern catchment and in a relatively unpolluted catchment situated 250 km to the south. Seven-times higher Zn export via runoff at the northern site was controlled by a combination of 10-times higher atmospheric Zn input and five-times higher DOC leaching, compared to the southern site. In industrial areas, atmospherically deposited Zn is leached from headwater catchments in a direct analogy to leaching of highly toxic pollutant Pb.

Cleaner air reveals growing influence of climate on dissolved organic carbon trends in northern headwaters.

Surface water browning, the result of increasing concentrations of dissolved organic matter (DOM), has been widespread in northern ecosystems in recent decades. Here, we assess a database of 426 undisturbed headwater lakes and streams in Europe and North America for evidence of trends in DOM between 1990 and 2016. We describe contrasting changes in DOM trends in Europe (decelerating) and North America (accelerating), which are consistent with organic matter solubility responses to declines in sulfate deposition. While earlier trends (1990-2004) were almost entirely related to changes in atmospheric chemistry, climatic and chemical drivers were equally important in explaining recent DOM trends (2002-2016). We estimate that riverine DOM export from northern ecosystems increased by 27% during the study period. Increased summer precipitation strengthened upward dissolved organic carbon trends while warming apparently damped browning. Our results suggest strong but changing influences of air quality and climate on the terrestrial carbon cycle, and on the magnitude of carbon export from land to water.

Controls on δ26Mg variability in three Central European headwater catchments characterized by contrasting bedrock chemistry and contrasting inputs of atmospheric pollutants.

Magnesium isotope ratios (26Mg/24Mg) can provide insights into the origin of Mg pools and fluxes in catchments where Mg sources have distinct isotope compositions, and the direction and magnitude of Mg isotope fractionations are known. Variability in Mg isotope compositions was investigated in three small, spruce-forested catchments in the Czech Republic (Central Europe) situated along an industrial pollution gradient. The following combinations of catchment characteristics were selected for the study: low-Mg bedrock + low Mg deposition (site LYS, underlain by leucogranite); high-Mg bedrock + low Mg deposition (site PLB, underlain by serpentinite), and low-Mg bedrock + high Mg deposition (site UDL, underlain by orthogneiss). UDL, affected by spruce die-back due to acid rain, was the only investigated site where dolomite was applied to mitigate forest decline. The δ26Mg values of 10 catchment compartments were determined on pooled subsamples. At LYS, a wide range of δ26Mg values was observed across the compartments, from -3.38 ‰ (bedrock) to -2.88 ‰ (soil), -1.48% (open-area precipitation), -1.34 ‰ (throughfall), -1.19 ‰ (soil water), -0.99 ‰ (xylem), -0.95 ‰ (needles), -0.82 ‰ (bark), -0.76 ‰ (fine roots), and -0.76 ‰ (runoff). The δ26Mg values at UDL spanned 1.32 ‰ and were thus less variable, compared to LYS. Magnesium at PLB was isotopically relatively homogeneous. The δ26Mg systematics was consistent with geogenic control of runoff Mg at PLB. Mainly atmospheric/biological control of runoff Mg was indicated at UDL, and possibly also at LYS. Our sites did not exhibit the combination of low-δ26Mg runoff and high-δ26Mg weathering products (secondary clay minerals) reported from several previously studied sites. Six years after the end of liming at UDL, Mg derived from dolomite was isotopically undetectable in runoff.

Experimental addition of nitrogen to a whole forest ecosystem at Gårdsjön, Sweden (NITREX): Nitrate leaching during 26 years of treatment.

Chronic high deposition of nitrogen (N) to forest ecosystems can lead to increased leaching of inorganic N to surface waters, enhancing acidification and eutrophication. For 26 years nitrogen has been added as ammonium nitrate (NH4NO3) at 40 kg N ha-1 yr-1 to a whole forested catchment ecosystem at Gårdsjön, Sweden, to experimentally simulate the transition from a N-limited to N-rich state. Over the first 10 years of treatment there was an increasing amount of nitrate (NO3-) and to a lesser extent ammonium (NH4+) lost in runoff, but then N leaching stabilised, and for the subsequent 16 years the fraction of N added lost in runoff remained at 9%. NO3- concentrations in runoff were low in the summer during the first years of treatment, but now are high throughout the year. High frequency sampling showed that peaks in NO3- concentrations generally occurred with high discharge, and were enhanced if high discharge coincided with occasions of N addition. Approximately 50% of the added N has gone to the soil. The added N is equivalent to 140 years of ambient N deposition. At current ambient levels of N deposition there thus appears to be no immediate risk of N saturation at this coniferous forest ecosystem, and by inference to other such N-limited forests in Scandinavia.

Comparison of the impacts of acid and nitrogen additions on carbon fluxes in European conifer and broadleaf forests.

Increased reactive nitrogen (N) loadings to terrestrial ecosystems are believed to have positive effects on ecosystem carbon (C) sequestration. Global "hot spots" of N deposition are often associated with currently or formerly high deposition of sulphur (S); C fluxes in these regions might therefore not be responding solely to N loading, and could be undergoing transient change as S inputs change. In a four-year, two-forest stand (mature Norway spruce and European beech) replicated field experiment involving acidity manipulation (sulphuric acid addition), N addition (NH4NO3) and combined treatments, we tested the extent to which altered soil solution acidity or/and soil N availability affected the concentration of soil dissolved organic carbon (DOC), soil respiration (Rs), microbial community characteristics (respiration, biomass, fungi and bacteria abundances) and enzyme activity. We demonstrated a large and consistent suppression of soil water DOC concentration driven by chemical changes associated with increased hydrogen ion concentrations under acid treatments, independent of forest type. Soil respiration was suppressed by sulphuric acid addition in the spruce forest, accompanied by reduced microbial biomass, increased fungal:bacterial ratios and increased C to N enzyme ratios. We did not observe equivalent effects of sulphuric acid treatments on Rs in the beech forest, where microbial activity appeared to be more tightly linked to N acquisition. The only changes in C cycling following N addition were increased C to N enzyme ratios, with no impact on C fluxes (either Rs or DOC). We conclude that C accumulation previously attributed solely to N deposition could be partly attributable to their simultaneous acidification.

Pollution control enhanced spruce growth in the "Black Triangle" near the Czech-Polish border.

Norway spruce (Picea abies (L.) Karst.) stands in certain areas of Central Europe have experienced substantial dieback since the 1970s. Understanding the reasons for this decline and reexamining the response of forests to acid deposition reduction remains challenging because of a lack of long and well-replicated tree-ring width chronologies. Here, spruce from a subalpine area heavily affected by acid deposition (from both sulfur and nitrogen compounds) is evaluated. Tree-ring width measurements from 98 trees between 1000 and 1350m above sea level (a.s.l.) reflected significant May-July temperature signals. Since the 1970s, acid deposition has reduced the growth-climate relationship. Efficient pollution control together with a warmer but not drier climate most likely caused the increased growth of spruce stands in this region, the so-called "Black Triangle," in the 1990s.

Assessing recovery from acidification of European surface waters in the year 2010: evaluation of projections made with the MAGIC model in 1995.

In 1999 we used the MAGIC (Model of Acidification of Groundwater In Catchments) model to project acidification of acid-sensitive European surface waters in the year 2010, given implementation of the Gothenburg Protocol to the Convention on Long-Range Transboundary Air Pollution (LRTAP). A total of 202 sites in 10 regions in Europe were studied. These forecasts can now be compared with measurements for the year 2010, to give a "ground truth" evaluation of the model. The prerequisite for this test is that the actual sulfur and nitrogen deposition decreased from 1995 to 2010 by the same amount as that used to drive the model forecasts; this was largely the case for sulfur, but less so for nitrogen, and the simulated surface water [NO3(-)] reflected this difference. For most of the sites, predicted surface water recovery from acidification for the year 2010 is very close to the actual recovery observed from measured data, as recovery is predominantly driven by reductions in sulfur deposition. Overall these results show that MAGIC successfully predicts future water chemistry given known changes in acid deposition.

Metal and proton toxicity to lake zooplankton: a chemical speciation based modelling approach.

The WHAM-FTOX model quantifies the combined toxic effects of protons and metal cations towards aquatic organisms through the toxicity function (FTOX), a linear combination of the products of organism-bound cation and a toxic potency coefficient for each cation. We describe the application of the model to predict an observable ecological field variable, species richness of pelagic lake crustacean zooplankton, studied with respect to either acidification or the impacts of metals from smelters. The fitted results give toxic potencies increasing in the order H(+) < Al < Cu < Zn < Ni. In general, observed species richness is lower than predicted, but in some instances agreement is close, and is rarely higher than predictions. The model predicts recovery in agreement with observations for three regions, namely Sudbury (Canada), Bohemian Forest (Czech Republic) and a subset of lakes across Norway, but fails to predict observed recovery from acidification in Adirondack lakes (USA).

Does stream water chemistry reflect watershed characteristics?

In this study, we investigated the relationships between stream water chemistry and watershed characteristics (topography--mean altitude and slope; climate--mean annual temperature and precipitation; geology--geochemical reactivity; land cover; inhabitation--population density, road density and number of municipalities). We analyzed the concentrations of the major anions (Cl, F, NO3, SO4, SiO2), cations (Ca, Mg, Na, K, Mn, Fe, Al), trace elements (Li, Sr, Cu), ABS245, TDP (total dissolved phosphorus), pH, and conductivity at 3,220 diverse watersheds covering a wide variety of watershed characteristics in the Czech Republic. We used marginal and partial multivariate analyses to reveal the most important variables. The partial analysis showed that only 14% of the variance could be assigned to a specific factor and that 41% of the variance is shared among the factors, which indicated complex interactions between the watershed characteristics.

Long-term changes in aluminum fractions of drainage waters in two forest catchments with contrasting lithology.

Aluminum (Al) chemistry was studied in soils and waters of two catchments covered by spruce (Picea abies) monocultures in the Czech Republic that represent geochemical end-members of terrestrial and aquatic sensitivity to acidic deposition. The acid-sensitive Lysina catchment, underlain by granite, was compared to the acid-resistant Pluhuv Bor catchment on serpentine. Organically-bound Al was the largest pool of reactive soil Al at both sites. Very high median total Al (Alt) concentrations (40 micromol L(-1)) and inorganic monomeric Al (Ali) concentrations (27 micromol L(-1)) were observed in acidic (pH 4.0) stream water at Lysina in the 1990s and these concentrations decreased to 32 micromol L(-1) (Alt) and 13 micromol L(-1) (Ali) in the 2000s. The potentially toxic Ali fraction decreased in response to long-term decreases in acidic deposition, but Ali remained the largest fraction. However, the organic monomeric (Alo) and particulate (Alp) fractions increased in the 2000s at Lysina. In contrast to Lysina, marked increases of Alt concentrations in circum-neutral waters at Pluhuv Bor were observed in the 2000s in comparison with the 1990s. These increases were entirely due to the Alp fraction, which increased more than 3-fold in stream water and up to 8-fold in soil water in the A horizon. Increase of Alp coincided with dissolved organic carbon (DOC) increases. Acidification recovery may have increased the content of colloidal Al though the coagulation of monomeric Al.

Increased dissolved organic carbon (DOC) in Central European streams is driven by reductions in ionic strength rather than climate change or decreasing acidity.

Temporal trends in DOC concentration and flux were investigated at two geochemically distinct forested catchments in western Czech Republic. Mean discharge-weighted DOC concentrations averaged 18.8 mg L(-1) at the acidic Lysina catchment, and 20.2 mg L(-1) at base-rich and well-buffered Pluhuv Bor. Between 1993 and 2007 DOC in streamwater increased significantly in both catchments: the mean annual increase was 0.42 mg L(-1) yr(-1) (p < 0.001) at Lysina and 0.43 mg L(-1) yr(-1) (p < 0.001) at Pluhuv Bor, resulting in cumulative increases of 64 and 65%, respectively. These long-term increases in streamwater DOC were correlated with only modest increases in stream pH in both catchments, but large declines in ionic strength (IS), that resulted from declining atmospheric deposition. Neither catchment has undergone changes in soil-water pH, yet DOC concentrations tripled in the soil-water of both catchments. We conclude that changes in ionic strength of soil-water and streamwater, rather than acidity, are the primary drivers of changes in streamwater DOC in this region. Temperature, precipitation and discharge show no statistically significant trends during the study period, suggesting that climate change has played no role in the changes in DOC that we have observed.

Rising trends of dissolved organic matter in drinking-water reservoirs as a result of recovery from acidification in the Ore Mts., Czech Republic.

The concentration of chemical oxygen demand (COD), a common proxy for dissolved organic matter (DOM), was measured at seven drinking-water reservoirs and four streams between 1969 and 2006. Nine of them showed significant DOM increases (median COD change +0.08 mg L(-1) yr(-1)). Several potential drivers of these trends were considered, including air temperature, rainfall, land-use and water sulfate concentration. Temperature and precipitation influenced inter-annual variations, but not long-term trends. The long-term DOM increase was significantly associated with declines of acidic deposition, especially sulfur deposition. Surface water sulfate concentrations decreased from a median of 62 mg L(-1)-27 mg L(-1) since 1980. The magnitude of DOM increase was positively correlated with average DOM concentration (R(2) = 0.79, p < 0.001). Simultaneously, DOM concentration was positively correlated with the proportion of Histosols within the catchments (R(2) = 0.79, p < 0.001). A focus on the direct removal of DOM by water treatment procedures rather than catchment remediation is needed.

The effect of reduced atmospheric deposition on soil and soil solution chemistry at a site subjected to long-term acidification, Nacetín, Czech Republic.

During the 1990s the emissions of SO(2) fell dramatically by about 90% in the Czech Republic; the measured throughfall deposition of sulphur to a spruce forest at Nacetín in the Ore Mts. decreased from almost 50 kg ha(-1) in 1994 to 15 kg ha(-1) in 2005. The throughfall flux of Ca decreased from 17 kg ha(-1) in 1994 to 9 kg ha(-1) in 2005; no change was observed for Mg. The deposition of nitrogen ranged between 15 and 30 kg ha(-1) with no statistically significant trend in the period 1994-2005. The desorption of previously stored sulphur and the decrease of Ca deposition are the main factors controlling the recovery of soil solution. The pH of the soil solution at a depth of 30 cm remains unchanged, and the Al concentration decreased from 320 micromol l(-1) in 1997 to 140 micromol l(-1) in 2005. The enhanced leaching of base cations relative to no acidified conditions has continued, although the Ca concentration decreased from 110 microeq l(-1) in 1997 to 25 microeq l(-1) in 2005 in the mineral soil solution at 30 cm depth. This dramatic change was not observed for Mg concentration in soil solution, because its deposition remained stable during the observed period. Similar patterns were observed in the deeper soil solution at 90 cm. The reduction in Ca availability resulted in lower uptake by tree assimilatory tissues, measured as concentration in needles. Since 2005, the leaching of nitrate observed in soil solution at 30 cm depth has disappeared. By 2003 a similar situation occurred at 90 cm. Higher incorporation into the trees after 1997 could be an important factor. With respect to the formerly high sulphur deposition and consequently released aluminium, which could have negatively influenced the biotic immobilization driven by microbes and fungi, the recovery may have positively impacted and therefore improved retention in the ecosystem during recent years. The delay in the successful retention of nitrogen in the ecosystem was probably caused by the high mineralization of organic matter after improvement of chemical parameters in the organic horizon (increase in pH and decrease in Al concentration). It seems that high mineralization of stored organic matter after decades of high acidic deposition could be an important factor affecting the high losses of nitrogen in spruce forest ecosystems.

Tree species (Picea abies and Fagus sylvatica) effects on soil water acidification and aluminium chemistry at sites subjected to long-term acidification in the Ore Mts., Czech Republic.

The effect of European beech (Fagus sylvatica) and Norway spruce (Picea abies) on acid deposition and soil water chemistry was studied at a site in the Ore Mts., Czech Republic, that has been subjected to decades of elevated acidic deposition. Dry deposition onto the spruce canopy significantly increased acid input to the soil in comparison to the beech canopy. As a result soil waters were more acidic; Al, SO4(2-), and NO3- concentrations were significantly higher; and Ca and K concentrations were lower in the spruce stand than in the beech stand. The concentrations of potentially toxic inorganic aluminium (Al(in)) were, on average, three times higher in the spruce stand than in the beech stand. Thus, Al played a major role in neutralizing acid inputs to mineral soils in the spruce stand. Despite the higher dissolved organic carbon (DOC) concentrations in spruce organic soil solutions, organic Al (Al(org)) accounted for only 30% of total Al (Al(tot)), whereas in beech organic soil solutions Al(org) was 60% of Al(tot). Soil waters in the beech stand exhibited Al(in) concentrations close to solubility with jurbanite (Al(SO4)OH.5H2O). The more acidic soil waters in the spruce stand were oversaturated with respect to jurbanite. The Bc/Al(in) ratio (Bc = Ca + Mg + K) in O horizon leachate was 4.6 and 70 in spruce and beech stands, respectively. In beech mineral soil solutions, the Bc/Al(in) ratio declined significantly to about 2. In the spruce stand, mineral soil solutions had Bc/Al(in) values below the critical value of 1. The observed Bc/Al(in) value of 0.4 at 30 cm depth in the spruce stand suggests significant stress for spruce rooting systems. A more favourable value of 31 was observed for the same depth in the beech stand. The efficiency of the spruce canopy in capturing acidic aerosols, particulates, and cloud water has resulted in the long-term degradation of underlying soils as a medium for sustainable forest growth.

Is a universal model of organic acidity possible: comparison of the acid/base properties of dissolved organic carbon in the boreal and temperate zones.

The acid/base properties of dissolved organic carbon (DOC) are an important feature of soil and surface waters. Large differences in the acid/base properties of DOC found by different studies might be interpreted as spatial and temporal differences in these properties. Different analytical techniques, however, may explain some of the differences. We used a combination of ion-exchange techniques, titration, and surface water chemistry data to evaluate DOC character from two substantially different areas--the relatively pristine boreal zone of Sweden and the heavily acidified temperate zone of the Czech Republic. We found a significantly higher site density (amount of carboxylic groups per milligram of DOC) for the Swedish sites (10.2 microequiv/mg of DOC +/- 0.6) as compared to the Czech sites (8.8 microequiv/mg of DOC +/- 0.5). This suggests a slightly higher buffering capacity for Swedish DOC. A triprotic model of a type commonly incorporated in biogeochemical models was used for estimating the DOC dissociation properties. For Swedish sites, the following constants were calibrated: pKa1 = 3.04, pKa2 = 4.51, and pKa3 = 6.46, while the constants for Czech sites were pKa1 = 2.5, pKa2 = 4.42, and pKa3 = 6.7. Despite differences in site density values, both models predict very similar dissociation and thus pH buffering by DOC in the environmentally important pH range of 3.5-5.0. This can be incorporated into models to make reliable estimates of the effect of organic acids on pH and buffering in different regions.

Evaluation of different approaches to quantify strong organic acidity and acid-base buffering of organic-rich surface waters in Sweden.

The role of organic acids in buffering pH in surface waters has been studied using a small brownwater stream (26mg L(-1) TOC) draining a forested catchment in Northern Sweden. Under the conditions of elevated pressure of CO2 stream field pH was changed between 3.5 and 6.1 during the acidification and alkalinization experiment. Acid-base characteristics of the natural organic matter were also determined using a high precision potentiometric method for a concentrated sample from the same stream. We compared the predictions from the Windermere Humic Aqueous Model (WHAM Model V), a model derived from the potentiometric titration (diprotic/monoprotic acid model) and a previously derived triprotic acid model which only uses alkalinity and TOC as input variables. The predicted buffering characteristics of all three models are very similar in the pH range 4.5-7 which suggests that during routine analysis alkalinity and TOC are sufficient to give a good estimate of organic acid anion charge contribution in a large range of surface waters. A slightly adjusted version of WHAM V successfully describes the organic charge contribution in a large number of sampled surface water lakes, which were previously used to calibrate the triprotic model.