The seasonal variation in soil water acid neutralizing capacity in peaty podzols in Mid-Wales

Between 1985 and 1990, bulk precipitation and soil solution from the organic (Oh) and mineral (Bs) horizons of a well developed podzol were regularly sampled at a moorland catchment in Mid-Wales. Samples were analysed for pH, major cations, major anions, and dissolved organic carbon (DOC). Acid neutralizing capacity (ANC) was estimated by the charge balance method. Average monthly ANC of soil solutions from the Oh horizon varied seasonally, with a maximum in July and a minimum in February. In contrast, H⁺ concentrations varied little. Solute deposition, dominated by sodium and chloride, also varied seasonally with a winter maximum, which is reflected in the soil solution chemical composition. In the Oh horizon during winter, the increase in base cation (Na) concentrations led to release of H⁺ through ion exchange. ANC declined in the absence of any buffering mechanism. In summer, the depletion of exchangeable acidity that occurred in winter, was replenished by H⁺ produced by the dissociation of organic acids. During this period, organic anions contribute to an increase in ANC, while H⁺ concentrations remained similar to those in winter. These processes probably influenced the acidity and ANC of Bs horizon soil solutions but to a lesser extent than in the Oh horizon. Other mechanisms such as weathering and ion exchange involving H⁺ and Al may buffer solution acidity in the mineral soil.     

Characterizing Episodic Stream Acidity During Stormflows in the Great Smoky Mountains National Park

Episodic acidification of surface waters has been observed in the Great Smoky Mountains National Park, similar to other forested watersheds with base-poor bedrock in the eastern US receiving acids from atmospheric deposition. Three remote, forested, high-elevation streams were selected in the Little Pigeon River watershed for study; two of which brook trout have extirpated, and believed to have resulted from severe acidity during stormflows. This research characterized stream chemistry during episodes in order to better understand potential factors that contribute to rapid drops in pH and acid neutralizing capacity (ANC) during stormflows. Autosamplers initialized by sondes, collected samples during storm events for analysis of pH, ANC, cations, and anions over a 15-month period. ANC and pH depressions, and increased concentrations in sulfate, nitrate, and organic acids were observed for all storms at each study site. ANC contribution analysis indicated sulfate was the strongest contributor to ANC depressions, but nitrate, cation dilution, and organic acids were also significant in some cases. Acidic deposition appears to be the primary source of episodic acidification, supported also by the finding that larger stormflows preceded by long, dry periods resulted in significantly larger pH depressions. It appears stream acidification episodes may be driven by acid deposition. However, this study documents the variability of several ion contributors to observed stormflow ANC depressions illustrating the spatial and temporal complexity of watershed processes that influence this phenomenon.     

Regional monitoring of lake acidification in Finland

The primary objective of this monitoring is to detect long-term Long-Range Transboundary Air Pollution (LRTAP) induced changes in the water quality of small lakes, throughout Finland, with low conductivity. The monitored lakes (n=171, sampled every autumn since 1990 and in 1987) have a smaller watershed (usually headwater or seepage lakes), a larger lake/catchment ratio, and lower base cation concentrations, alkalinity and pH than Finnish lakes on average. The monitoring network provides background data for air pollution dose/response studies, critical load calculations and for the modelling of acidification scenarios. The declining sulphate deposition seems to be reflected in small headwater lakes all over southern and central Finland as a lowering of the sulphate concentration in the waters. Nitrate concentrations in these lakes have been typically low in the autumn. The base cation concentration is not generally declining, as it is in deposition in many areas. The sulphate concentration in lakes has declined more than base cations. Hydrologically, the recent years have been quite variable because of varying annual precipitation. The variation in alkalinity and pH in typical Finnish lakes is dependent on the content of humic material derived from catchments. The monitoring period is too short to reveal consistent trends in major ion chemistry. However, signs of improvement in recent years can be seen; in comparing 1993 to 1987, years with similar organic acidity and base cations, it seems that the sulphate decline in lakes monitored is compensated by a significant rise in both alkalinity and pH.     

华南红壤的交换性碱和交换性酸

本文提出了一个同时测定土壤的交换性酸和交换性碱的简易方法。将土壤的交换性酸和交换性碱区分为:Na-交换性酸、Ba-交换性酸和SO₄-交换性碱、F-交换性碱。用推荐的方法,在野外对华南地区由不同母质发育的砖红壤、赤红壤、红壤等10个剖面进行了测定。结果表明,红壤类土壤含有相当量的交换性碱,但其数量比交换性酸少。酸性母质发育的土壤的交换性酸和交换性碱量大于由基性岩发育的土壤者。红壤的交换性酸和碱的量随电性盐浓度的增高而增大,浓度大于0.1N后,数量基本不变。     

The role of weathering and forestry in determining the acidity of Lakes in Sweden

The long term acidity level of a lake is determined by the balance between acidity input to the catchment and the generation of alkalinity in the catchment. If the input of acidity through biomass net production and the production of alkalinity through weathering of minerals can be estimated, then the steady-state acidity level can be calculated for the lake under a certain acid deposition rate. Such a calculation has been carried out for 8 lakes ranging from acid to neutral. For lakes with the most sensitive soils in the catchment, the critical acid deposition load that will permit the lake to stay neutral, may be less than zero acidity, indicating that the forest growth is contributing to the acidification of very sensitive system under the present forest managements methods.     

Acid neutralizing capacity of solutions containing organic acids isolated from Finnish lakes

Organic vs. bicarbonate contribution to Gran alkalinity was studied using empirical measurements. Distilled water with various amounts of bicarbonate and organic acids was equilibrated with synthetic air during Gran titrations. Natural organic acids isolated from Finnish lakes were used as a carbon source for these solutions. The experimental design corresponded to computer simulations made by Cantrell et al. (1990). The results indicate that the discrepancy between the Gran ANC and the ANC calculated from anion deficit can be explained partly by the organic acids, which remain unprotonated in the titration. The unprotonated fraction of organic acids was on average 5.5 and 6.2 eq per mg of dissolved organic carbon (DOC), when pH ranges of 3.0–4.0 and 3.5–4.5 for Gran plot regression were used, respectively. The acid neutralizing capacity provided by organic acids varied from 18 to 75 eq/L, depending on the initial pH and DOC concentration and the pH range of the Gran plot regression. The results of empirical Gran titrations agree with the theoretical calculations made by Cantrell et al. (1990).     

impact of high aluminium loading on a small catchment area (thuringia slate mining area) – geochemical transformations and hydrological transport

A field study was performed on the effects of acid mine leachate from slate mine tailings seeping into a small river passing through the tailings. Before entering the tailings the river water has high alkalinity which neutralizes acidity upon mixing with leachate within the tailings. Donwstreams of the tailings the pH of the river water ranges about pH = 8, the water contains high concentrations of sulfate (≈1500 μmol/1 and particulate bound aluminium (≈80 μmol/I), but low concentrations of dissolved aluminium (≈3 μmol/1). It is therefore assumed that AI(OH)₃ colloids are precipitated during the neutralisation process and transported out of the tailings. The concentration of particulate bound aluminium along the river shows a strong correlation with the concentration of sulfate, which indicates that particulate bound aluminium is conservative. It therefore seems that under dry weather conditions (under most of the sampling was performed) no chemical retention mechanism exists which confines the distribution of aluminium to a restricted part of the catchment area. In contrast, the white river sediment is rich in both aluminium and sulfate, which suggests the temporary formation of aluminium hydroxosulfate minerals. Favorable (i.e. acidic) conditions may prevail at high discharges where the acidity accumulated in the tailings is flushed into the river with its subsequent acidification.     

复配改良剂表施对高降雨量地区茶园底层强酸性土壤酸度的调控

Strongly acidic soils (pH < 5.0) are detrimental to tea (Camellia sinensis) production and quality. Little information exists on the ability of surface amendments to ameliorate subsoil acidity in the tea garden soils. A 120-d glasshouse column leaching experiment was conducted using commonly available soil ameliorants. Alkaline slag (AS) and organic residues, pig manure (PM) and rapeseed cake (RC) differing in ash alkalinity and C/N ratio were incorporated alone and in combination into the surface (0--15 cm) of soil columns (10 cm internal diameter × 50 cm long) packed with soil from the acidic soil layer (15--30 cm) of an Ultisol (initial pH = 4.4). During the 120-d experiment, the soil columns were watered (about 127 mm over 9 applications) according to the long-term mean annual rainfall (1 143 mm) and the leachates were collected and analyzed. At the end of the experiment, soil columns were partitioned into various depths and the chemical properties of soil were measured. The PM with a higher C/N ratio increased subsoil pH, whereas the RC with a lower C/N ratio decreased subsoil pH. However, combined amendments had a greater ability to reduce subsoil acidity than either of the amendments alone. The increases in pH of the subsoil were mainly ascribed to decreased base cation concentrations and the decomposition of organic anions present in dissolved organic carbon (DOC) and immobilization of nitrate that had been leached down from the amended layer. A significant (P < 0.05) correlation between alkalinity production (reduced exchangeable acidity -- N-cycle alkalinity) and alkalinity balance (net alkalinity production -- N-cycle alkalinity) was observed at the end of the experiment. Additionally, combined amendments significantly increased (P < 0.05) subsoil cation concentrations and decreased subsoil Al saturation (P < 0.05). Combined applications of AS with organic amendments to surface soils are effective in reducing subsoil acidity in high-rainfall areas. Further investigations under field conditions and over longer timeframes are needed to fully understand their practical effectiveness in ameliorating acidity of deeper soil layers under naturally occurring leaching regimes.     

Validating a Simple Equation to Predict and Analyze Organic Anion Charge in Swedish Low Ionic Strength Surface Waters

Acid neutralising capacity (ANC) is substituted by CBALK, a term that has been theoretically introduced in the early 1990s, to evaluate a simple pH equilibrium model used for Swedish surface waters. The CBALK approach with its simple three pK_a organic acid analogue is re-evaluated with a new data set of 900 stream water samples. End-point alkalinity and TOC suffice to predict air equilibrated pH in the range 4.5 to 7.5 within 0.08 pH units. This is equivalent to an error in the charge balance of about 5 ueq L^?1. In the studied pH range it renders more precise predictions than when using ANC. The model equations can be used to estimate the effect of organic carbon or carbon dioxide on ambient pH during episodes as well as for sample quality control.     

Does Acidification Policy Follow Research in Northern Sweden? The Case of Natural Acidity During the 1990's

The situation in northern Sweden did not figure prominently in the intense period of research during the 1980's that laid the basis for many acidification-related policies now in effect in Europe and Sweden. Northern Sweden has not only relatively low acid deposition levels and significant sources of natural acidity, but also intense episodes of pH decline during spring flood that are a major focus of liming activity. Controversy over that liming and natural acidity has led to scientific advances. These include discovery of a correlation between sulfur in snow and the anthropogenic contribution to the subsequent spring flood ANC decline, but also that natural organic acidity is responsible for most of the spring pH decline in the region. This paper compares the developments in liming policy with the scientific developments of relevance to the region during the last decade. Considerable discrepancies are noted which create opportunities for revising remediation policies to better reflect the state of knowledge in 2000.     

Ion input/output budgets for five wetlands constructed for acid coal mine drainage treatment

Five wetlands, each 6 m wide and 30 m long and containing 30 cm of an organic substrate (Sphagnum peat to which limestone and fertilizer were surface-applied on a quarterly basis, Sphagnum peat, sawdust, straw/manure, spent mushroom compost), were exposed to controlled inputs of acid coal mine drainage (AMD; pH 2.89, soluble Fe, Mn, and SO₄ ^2? concentrations of 119, 19, and 3132 mg L^?1, respectively) at a mean flow rate of 8513 L da^?1 for 111 weeks, beginning in July of 1989. All wetlands were net sources, rather than sinks, for base cations (Ca²⁺, Mg²⁺, Na⁺, K⁺). The Sphagnum peat wetland was the least effective in treating the AMD, retaining 35% of the soluble Fe influx, but not retaining substantial H⁺, soluble Mn, soluble Al, SO₄ ^2?, or acidity. The straw/manure and mushroom compost wetlands were the most effective in treating the AMD, retaining 53 and 67% of the H⁺ influx, 80 and 78% of the soluble Fe influx, 7 and 20% of the soluble Mn influx, 54 and 53% of the soluble Al influx, 15 and 11% of the SO₄ ^2? influx, and 57 and 63% of the acidity influx. For these two wetlands especially, treatment effectiveness was substantially diminished during the cold winter months of January through March. Moreover, from March through July of the final year of the study, treatment effectiveness was minimal with outflow pH and concentrations of soluble Fe, Mn, Al, SO₄ ^2? and acidity that were similar to inflow values. Decreases in treatment effectiveness over time appeared to be related to a decrease in the ability to counter the substantial acid load entering the wetlands in the AMD. Lime or limestone dissolution and bacterial dissimilatory sulfate reduction may have contributed substantially to pH improvement and acidity consumption in the straw/manure and mushroom compost wetlands, but after 2 years the cumulative input of acidity apparently had overwhelmed biotic and abiotic alkalinity generating mechanisms, as reflected in a progressive decrease in both substrate pH and abiotic acid neutralization capacity (ANC) over time, especially in the surface substrates. Also over time, effluent H⁺ and acidity concentrations became more like influent and H⁺ and acidity concentrations. Although samples of wetland interstitial water were not collected for chemical analysis, as substrate pH and ANC decreased and as influent and effluent water chemistry became more similar, it is likely that wetland interstitial water became progressively more acidic, potentially inhibiting bacterial processes that could contribute to effective treatment, favoring dissolution rather than formation of insoluble metal precipitates, and thereby contributing to the eventual failure of the wetlands to effectively treat the AMD. In general, when constructed wetlands are used to treat particularly acidic (pH<4) AMD, if abiotic and biotic alkalinity generation cannot balance the influent acid load, long-term effective treatment will not be achieved.     

Seasonal variations of water chemistry in oligotrophic streams and rivers in Kejimkujik National Park,Nova Scotia

The seasonal patterns of flow and the concentrations of color, Mg, Ca, H⁺, Na, Cl, organic anions, SO₄, and Gran alkalinity are examined for five streams or rivers in Kejimkujik National Park (Lower Mersey River, Atkins Brook, Grafton Brook, Pebbleloggitch Brook, and Beaverskin Brook). These range in organic color and acidity from very darkwater Atkins Brook (average 191 Hazen units, pH 4.2) to clearwater Beaverskin Brook (5 Hazen units, pH 5.5). In general, most dissolved substances are present in a relatively large concentration during the high-flow period of winter-spring (most notably color, Mg, H⁺, Ca, Na, organic anions, and SO₄). In contrast, Gran alkalinity generally occurs in its highest concentration during the lowflow period. These observations suggest that during the high-flow period, substances are “flushed” from the terrestrial watersheds of these rivers and streams.     

Estimating organic acid contributions to surface water acidity in Quebec (Canada)

Inorganic ion balances for lake waters lying on the Canadian Shield in the province of Quebec, Canada, consistently show significant anion deficits (mean deficit 70 to 90 μeq L^?1). Models taking into account organic anions have been tested for their ability to eliminate this anion deficit. The data set consisted of the chemical composition (pH, all major ions, major trace metals, dissolved organic and inorganic C, total alkalinity) of ≈1200 lakes from four hydrographic regions. The relative performances of three models (the 1983 Oliver et al. model and two derived models) were evaluated by comparing the capacity of each model to compensate fully for the anionic deficit of the waters. The study showed that without calibration all models systematically underestimated the anionic deficit. The two derived models were recalibrated and validated by regional discrimination of the data; charge balances calculated with the recalibrated models were markedly improved. Based on calculated anion deficits, the contribution of natural organic acids to Quebec surface water acidity increases from southwest to northeast and greatly exceeds that previously reported.     

Titratable Acidity and Alkalinity of Red Soil Surfaces

The surfaces of red soils have an apparent amphotenc character, carrying titratable acidity and titratable alkalinity simultaneously. The titratable acidity arises from deprotonation of hydroxyl groups of hydrous oxide-type surfaces and dissociation of weak-acid functional groups of soil organic matter, while the titratable alkalinity is derived from release of hydroxyl groups of hydrous oxide-type surfaces. The titratable acidity and titratable alkalinity mainly depended on the composition and content of iron and aluminum oxides in the soils. The results showed that the titratable acidity and titratable alkalinity were in significantly positive correlation not only with the content of amorphous aluminum oxide(Alo) and iron oxide(Feo) extracted with acid ammonium oxalate solution, free iron ox-ide(Fed) extracted with sodium dithionite-citrate-bicarbonate (DCB) and clays, but also with the zero point of charge (ZPC) of the samples. Organic matter made an important contribution to the titratable acidity.     

Relationships between afforestation,water chemistry and fish stocks in an upland catchment in south west Scotland

The soils and waters in the Galloway hills of south-west Scotland have undergone considerable acidification during the present century. The aims of this study were to examine the extent to which afforestation can influence water chemistry, and the occurrence of fish stocks within an individual catchment in this area. Studies were carried out at 45 sites in the Bladnoch catchment during 1994. River water samples were collected at all sites and determinations made of pH, total organic carbon, calcium and monomeric aluminium concentrations. In order to quantify the size and abundance of fish populations, electrofishing was carried out at 21 of the sites. Estimates of afforestation were made by a combination of field surveys and the use of 1∶:10 000 scale ordnance survey maps. The presence of coniferous trees had a substantial affect on water chemistry. In areas where the whole catchment was afforested, the water pH was 0.7 units lower than in unafforested areas (p<0.001). Afforestation was also correlated with low concentrations of calcium, and increases in the concentrations of monomeric aluminium and total organic carbon. There was a clear relationship between fish populations and water chemistry. Numbers of trout were positively correlated with pH (r ²=0.69; p<0.001), and with concentrations of calcium (r ²=0.55; p<0.001). The study has shown that salmonid fish populations are sensitive to acidity and the associated changes in river water chemistry; these problems were exacerbated by afforestation.     

Chemical and microbial diagenesis of humic matter in freshwaters

The importance of microbial activity in changing the chemical properties of humic material in brown waters was measured as a function of pH, acid neutralization capacity (ANC), and pK_a affinity spectrum from brownwater samples kept in aquaria and sterile flasks. Changes to the humic matter in non-sterile microcosms caused increases in pH and ANC and loss of strong organic acid pK_a sites. Microbial activity was shown to be the main contributor to a decrease in acidity of humic material as samples kept under sterile conditions showed less change than non-sterile ones. Microbial processes were shown to be mostly due to sessile organisms on the walls of the aquaria and in sediments. Our data suggest that acid-base properties of brownwaters can be modified based on residence times, as well as by temperature in their basins. Assuming similar starting humic materials, microbial degradation may account for the lower acidity measured in lakes and large rivers, compared to headwaters.     

Calculating critical loads for acidity with the simple mass balance method

The critical load for acid deposition to forest soils, groundwater and surface water can be calculated using a simple mass balance model, taking into account all sources of acidity and alkalinity in the system. The model is very simple to apply, and the major difficulty lies primarily in the estimation of reasonable values for the required input data such as the weathering rate. Methods for its estimation are indicated here. Examples are given for the application of the simple mass balance method (SMB) to Dutch and Swedish forest soils, lakes and shallow groundwater. This work outlines and explains the actual application of the consept as it is being carried out regionally for all European nations.     

Alkalinity regulation in maine headwater lakes: Terrestrial vs. lacustrine contributions in summer

Twenty-seven Maine lakes in felsic terrane were sampled in May and October 1986, bracketing the summer interval of minimum flushing, in order to statistically test a hydrogeochemical process model that separates Gran alkalinity (ANC) production into terrestrial vs lacustrine components. Significant ANC increases over the 5 mo were restricted to relatively shallow lakes with large contiguous watersheds, and/or lakes where contact zones in the local bedrock offered increased potential for summer groundwater inflow. Summer ANC increases depended mainly on terrestrial contributions; in-lake alkalinity generation was 16±5 meq m^?2 over 5 mo, of which ca. 11 meq m^?2 resulted from biological assimilation of directly-deposited nitrate-N. The remaining 5±5 meq m^?2 cannot be assigned with confidence, but is thought to reflect lacustrine sulfate reduction. The over-summer changes in ANC and conductance of Maine headwater lakes in upland granitic terrane approached statistical detection limits resulting from pure analytical and sampling error. This convergence highlights the importance of even small analytical biases when analyzing limnological time series, and confirms the utility (statistical efficiency) of the one-time, comparative sampling design adopted during the U.S. EPA's Eastern Lake Survey (ELS).     

recent lake acidification and recovery trends in southern quebec,canada

A total of 51 lakes in southern Quebec, Canada, were sampled between 1985 and 1993 to study changes in water chemistry following reductions in SO₂ emissions (main precursor of acid precipitation). Time series analysis of precipitation chemistry revealed significant reductions in concentrations and deposition of SO₄ ^2- from 1981 to 1992 in southern Quebec as well as reductions in concentrations and deposition of base cations (Ca²⁺, Mg²⁺), NO₃ ^- and H⁺ in the western section of the study area. Reductions in atmospheric inputs of SO₄ ^2- have resulted in decreased lakewater SO₄ ^2- concentrations in the majority of the lakes in our study, although only a small fraction (9 of 37 lakes used in the temporal analysis) have improved significantly in terms of acidity status (pH, acid neutralizing capacity – ANC). The main response of the lakes to decreased SO₄ ^2- is a decrease in base cations (Ca²⁺+Mg²⁺), which was observed in 17 of 37 lakes. Seventeen lakes also showed significant increases in dissolved organic carbon (DOC) over the period of study. The resulting increases in organic acidity as well as the decrease in base cations could both play a role in delaying the recovery of our lakes.     

Assessing the contribution of individual dissolved ions to depressions in acid neutralising capacity of streams in the adirondack and Catskill Mountains,New York

Methods for quantifying the influence of different ions on depressions in ANC, based on those used by Molot et al. (1989), have been employed on streams in the Adirondack and Catskill Mountains of New York. Streams were intensively monitored during the Episodic Response Project of the US EPA Baseflow values were determined for each variable, and for each low-ANC sample the proportion of ANC depression (relative to baseflow) contributed by each ion was calculated, In the Catskill streams Ca²⁺ dilution and NO₃ ^– increases were major causes of ANC depression; SO₄ ^2– dilution and Al mobilisation increased ANC. In the Adirondack streams Ca²⁺ and Na⁺ dilution, and NO₃ ^– and SO₄ ^2– increases, all contributed to ANC depressions. Inter-stream differences in results were linked to differences in stream acidity; in both regions Ca²⁺ dilution dominated ANC depressions in circumneutral streams, whereas NO₃ ^– increases were dominant in acidic streams. Organic anions contributed more to ANC depressions in acidic streams. Al buffering, was negligible in circumneutral streams, but more than halved ANC depressions in the most acidic stream. Individual base cation behaviour differed widely, suggesting that caution should be used when treating them as a uniform group.