Natural and anthropogenic acidity sources for Finnish Lakes

The headwater lakes in peat-rich areas in Finland commonly have high organic matter concentrations and are surrounded by soils and bedrock poor in bases. As a result the organic acid load on the watercourses is generally high. The significance of the organic vs anthropogenic acidity in 78 moderately acid lakes (pH range 4.3 to 7.1, TOC range 0.6 to 33.9 mg L^?1) was evaluated in areas receiving different levels of acid deposition. The lakes were sampled during autumn overturn, and their water quality (mean TOC = 10.9 mg L^?1, mean pH = 5.9) represents rather well the average water quality in small lakes in Finland. According to the correlation and regression analyses, TOC is a better predictor of pH than non-marine sulfate. Base cation concentrations are important in determining the sensitivity of the lakes to organic and anthropogenic acidity. The highest minerogenic acid contribution is found in high-deposition areas, while the percent organic acid contribution is greater in low deposition areas although TOC levels are comparable in both areas. It would appear that the pH of humic lakes is determined to a greater extent by individual watershed characteristics than by their geographical location at the present atmospheric loadings received in Finland.     

Organic versus anthropogenic acidity in tributaries of the kejimkujik watersheds in Western Nova Scotia

Dilute waters (Ca = 0.3 to 0.8 mg L^?1) respond by depressed pH levels throughout the year to existing atmospheric wet deposition of sulphate (20 kg ha^?1yr^?1).This occurs in southwest Nova Scotia particularly during the cold, wet season when runoff is high. Colored waters of similar Ca levels receiving runoff from peaty catchments exhibit pH values one unit lower (4.7 to 4.1) than those of catchments of similar Ca levels but free from peat deposits (pH > 5.3). In colored streams sulphate and organic anions show opposing cyclic patterns while the negative gran alkalinity is the near mirror image of sulphate. Sulphate anion peaks during the high spring discharge when the organic anion concentration is lowest. Sulphate suddenly drops during the summer months during periods of high evapotranspiration, low water table and runoff, when the concentration of organic anions is highest. Both Al and Fe follow cyclic patterns similar to that of the organic anions while H⁺ reflects that of the sulphate anion. Hydrogen ion concentration is always higher than that of sulphate in very colored waters, particularly during the summer months when organic anion concentrations are very high. Analysis of data in the tributaries in the Kejimkujik watersheds indicates that while considerable organic acidity is present in colored waters, anthropogenic sulphate further increases the free acidity of these waters, particularly at times of high discharge.     

Factors controlling the removal of sulfate and acidity from the waters of an acidified lake

Although Lake Anna, an impoundment in Central Virginia, receives acid mine drainage (AMD) from Contrary Creek, the effects of the AMD pollution on the lake are less severe than expected. Previous work at Lake Anna has shown that bacterial sulfate reduction in the lake sediments plays an important role in the recovery of the lake from the AMD inputs. Sulfate removal rates were measured in sediment microcosms under a variety of experimental conditions to determine the factors controlling the rate of sulfate and acidity removal from the lake water. Sulfate removal rates were not significantly different over the short term (3 weeks) in summer sediment microcosms incubated at 6 vs 26 °C. Winter sediment microcosms showed no significant sulfate removal during the 18 day experiment when incubated at either 6 or 28 °C. Thus there is a strong seasonal temperature effect in Lake Anna sediments but no significant short term effect. Simulated AMD, with and without Fe, was added to sediment microcosms collected from an unpolluted part of the lake. The microcosms with Fe had significantly higher rates of sulfate removal indicating that Fe plays an important role in transporting sulfate to the sediment and/or in preventing oxidation of the reduced sulfide. After 27 days, from 54 to 96% of the added sulfate in the simulated AMD was recovered as FeS or S⁰ in the top 4 cm of sediment. In a separate experiment, ³⁵S-SO _inf4 ^sup2? was found to attach to precipitating Fe oxyhydroxides (1.5 to 4.7 mol SO _inf4 ^sup2? mol^?1 Fe precipitate) upon mixing Contrary Creek (AMD) and Lake Anna waters. Results of this study suggest that sulfate removal may be more rapid in metal rich AMD systems thans in metal poor systems characteristic of those which receive acidic deposition.     

Long distance transport of anthropogenic lead as measured by lake sediments

Long-term atmospheric deposition of Pb has been measured using lake sediment cores. The average ‘whole-lake’ Pb burden was measured for several lakes in each of four regions located throughout Ontario and Quebec, Canada. Since the regions were remote to any point source of Ph, large scale variation in atmospheric transport could be studied. The results indicate that Pb deposition is highest in South-Central Ontario, where lake burdens ranged from 312 to 432 mg m^?2, and that it decreases in an eastward direction into Quebec. Lowest deposition was at the site farthest north, Schefferville, Quebec, where fallout was 31 to 42 mg m^?2, less than one-tenth of that previously observed in South-Central Ontario. Lead-210 dating of sediment cores from the northern site showed that input to these remote lakes has occurred over the same time period as in the southern sites.     

Modeling organic and inorganic acidity in two Nova Scotia rivers

A watershed acidification model is modified to include organic acids and applied to the colored Moose Pit Brook and Mersey River in Nova Scotia. Comparison with 1983–1985 data confirmed the capability of the model to explain the different levels of organic and inorganic acidity exhibited in these two rivers. Based on the charge balance approach and a triprotic organic acid model, the charge density was found to be about 4 μeq organic anions per mg C of dissolved organic C for these two rivers.     

Influence of pollution and acidification on metal concentrations in Finnish Lapland lake sediments

Fifteen Finnish Lapland lakes have been investigated to study pollution levels and possible acidification effects on nickel (Ni), copper (Cu), cobalt (Co), zinc (Zn), cadmium (Cd), lead (Pb), manganese (Mn), iron (Fe), potassium (K), sodium (Na), calcium (Ca), magnesium (Mg) and aluminium (Al) concentrations in sediments. Four lakes have average water pH lower than 6.0 and alkalinity lower than 0.050 meq/1. Contamination factor (C_f, ratio of metal concentrations in the uppermost to the deepest layers for a given lake sediment core) of Pb is high, particularly for acidic and acidifying lakes (C_f=5.2–10.4). Ni, Cu, Co, Zn and Cd concentrations increase insignificantly towards sediment surface of some lakes (with a neutral pH) with the rare exception. The influence of passible lake acidification consists of decreasing Cu, Cd, Al, Zn concentrations and organic material contents (loss on ignition) towards the sediment surface. The buffer capacity index (BCI), determined as the ratio of the sum of alkaline and alkaline-earth metals (K, Na, Ca, Mg) to Al, is lower for acidic lakes (from 0.12 to 0.36), whereas for the other lakes the BCI values are higher (from 0.42 to 1.34). Thus, BCI-values, decreased contents of Al, Cd, Zn and Cu, as well as organic matter contents (OMC in the upper lake sediment suggest acidification of freshwater environments.     

Québec lake survey: II. Origin and extent of acidification

Over 95% of the province of Québec is located on the Canadian Shield where the bedrock offers a very low acid neutralizing capacity. Some areas of Québec are more vulnerable than others because of shallow soils or soils presenting very low carbonated content. Lakes in these areas tend to be more acidic and more sensitive than elsewhere on the Precambrian Shield. There are two major areas showing high sensitivity (ANC≤100 μeq L^?1): the southwestern portion of Québec and the easternmost part of the province. In the former, lake acidity is mainly driven by SO₄ deposition, while in the latter area, organic acidity appears to be the main controlling factor. The origin of acidification can be related to the pattern of SO₄ deposition, the higher loadings being measured in the southwestern portion of Québec. These depositions follow a west to east decreasing gradient as they are mostly related to sources located west and southwest of Québec.     

Trends and uncertainties in volatile organic compound emissions from anthropogenic sources

This paper discusses trends and uncertainties in the anthropogenic emission inventory for VOC. EPA's trend analysis indicates that emissions increased almost across the board until about 1970. After 1970, emissions continued to increase for industrial solvents, but declined for transportation, nonindustrial solvents, and combustion and waste disposal. With the current emphasis on using grid models to define NO_x and VOC control strategies, the uncertainty of emission inventories is becoming increasingly important. However, the volume of data in an emissions inventory makes the detailed assessment of uncertainty difficult if not impossible.     

A simple dose-effect model of lake acidity in Québec (Canada)

A simple dose-effect model expressing the relationships between lake acidity, weighted mean annual sulfate concentration in wet deposition, Ca, Mg and true color (as an index of organic anion concentration) is presented. The agreement between observed and estimated pH for more than a 1000 lakes is high according to the Pearson coefficients of correlation (0.81 to 0.90) and the standard error of estimation (0.22 to 0.27 pH unit). Results obtained with this model show that an airborne sulfate target loading of 20 kg ha^?1 yr^?1 would be too high to adequately protect sensitive lake ecosystems. A target loading of 15 kg ha^?1 yr^?1 in wet deposition would be best suited for the protection of the greater portion of sensitive lakes. However, a target loading of 10 kg ha^?1 yr^?1 would be required to protect the most sensitive lake ecosystems.     

The role of sea-salts in enhancing and mitigating surface water acidity

Enhancement of the acidity of fresh waters due to sea-salt “episodes” has been reported in western regions of Scotland, Ireland and Norway and eastern regions of Canada and the United States of America. In all cases these short-term pH depressions have been ascribed to cation-exchange processes in catchment soils whereby sodium ions displace acidic cations (H⁺, Al³⁺) resulting in a lowering of the Na/Cl ratio in run-off water. Studies of sea-salt episodes in different catchment types of similar sensitivity in Scotland show significant variations in chemical responses, especially in terms of acidification status. Catchments with high background salt content, in a low sulphur deposition area, show only a small increase in acidity with negligible aluminium release and most of the sodium retention matched by Ca and Mg release. Catchments in intermediate deposition areas, with low background salt levels, exhibit smaller sodium retention with increased leaching of acidity and labile aluminium. High non-marine S deposition sites, with intermediate background salt levels, reveal high levels of acidity and aluminium leaching associated with some calcium leaching and evidence of Mg retention. Mitigation of acidification occurs at sites with high background sea-salt levels (eg north west Scotland) where acidic deposition is selectively retained in catchment soils. Non-marine sulphate values in run-off are therefore much lower (often producing negative values) than those predicted from current S deposition values. Consequently such sites are presently producing false exceedances of freshwater Critical Loads when current S deposition values are used. Future reductions in S deposition will probably affect the adsorption characteristics at these sites with consequent effects on sulphate leaching.     

Evaluation of two coal-derived organic products in ameliorating surface and subsurface soil acidity

Acidity in the soil surface and subsurface is of major concern in horticulture, cropping and pasture production systems in southern Australia. Broadcast applications of lime to the surface have proved to be ineffective in ameliorating subsurface acidity in the short term. Two calcium-saturated coal-derived organic products, an ‘oxi-product’ (OXPR) and an ‘oxi-fulvate’ (OXFU), were evaluated for use as liming materials with specific consideration given to amelioration of subsurface acidity. The effects of these two organic products and of lime on the chemical composition of the A₁ and A₂ horizons of an acid red podzol were investigated in leaching columns, 20 cm long. OXPR and OXFU supplying 80 or 160 g Ca m^?2 were compared to 160 g Ca m^?2 applied as CaCO₃ and a control receiving no amendments. The effects of CaCO₃ on exchangeable Al and pH were limited to the surface 2 cm. In contrast, the two organic amendments were effective in decreasing exchangeable Al and increasing pH and exchangeable Ca to depth, the extent being a function of amendment and rate applied. The formation of inorganic and organic complexes were assumed to be responsible for the movement of Al out of the column in the leachate, although significant quantities of Al were precipitated in the column. Significant linear regressions were observed between the ionic strength and Al in the leachate. Significant quantities of Mg and K were displaced by Ca and leached from the column; consequently, this loss must be considered against the benefits of decreased exchangeable Al when assessing fertility for plant production.     

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.     

种植花生、施用尿素对红壤酸化作用及有机物料的改良效果

通过连续2年盆栽试验,比较研究了种植花生和施用尿素对红壤pH和交换性Al含量的影响,以及施用几种有机物料(稻草、紫云英、猪粪)对土壤酸化的改良效果,为花生种植地区合理施用有机物料缓解土壤酸化、提高产量提供参考依据。结果表明,与同一季中相同施肥处理不种花生的土壤相比,种植花生1季和2季后土壤pH分别降低了0.06～0.28和0.08～0.27,土壤交换性Al则分别增加了7.69%～72.94%和8.49%～46.20%;施用尿素增加了花生产量,但同时也加剧了土壤酸化,同一季中有机物料施用相同情况下,与低尿素水平处理的土壤相比,高尿素水平处理1季和2季后土壤pH分别下降了0.02～0.10和0.01～0.16;不同有机物料对土壤酸化的改良效果:猪粪稻草紫云英,且有机物料施用量越大,土壤pH升幅越大,土壤交换性Al含量则越低;几种有机物料中,猪粪处理显著增加了花生产量,2季中花生秸秆干重平均增加了11.12%～59.28%,花生籽粒干重平均增加了12.42%～68.20%;紫云英效果次之,稻草增产效果不明显。     

Influence of organic acids on model projections of lake acidification

We employed three mathematical models to make quantitative estimates of the pH of 33 statistically-selected lakes in the Adirondack mountains, New York (USA) prior to the Industrial Revolution (1840). The models included 1) the MAGIC watershed acidification model, 2) a paleolimnological model of diatom-inferred pH, and 3) the MAGIC model modified to incorporate an empirically-based model of natural organic acidity. Application of approaches 2) and 3) yielded consistent estimates of pre-industrial Adirondack lakewater pH. However, when the organic acid model was not included, MAGIC calculations and diatom-inferred values showed poor agreement. MAGIC projections of lakewater pH 50 years into the future, under differing atmospheric deposition scenarios, were also sensitive to inclusion of the organic acid model. MAGIC predicted greater recovery in response to reduced deposition when organic acids were not considered. These results suggest that failure to consider the pH buffering of naturally-occurring organic acidity will often result in biased projections which overemphasize the response of lakewater pH to changes in atmospheric inputs of strong acid.     

pH and solubility of aluminium in acidic forest soils: a consequence of reactions between organic acidity and aluminium alkalinity

Data from two Podzol O and E horizons, sampled in 1-cm layers at 13 points within 2 m × 2 m plots, were used to test the hypothesis that the composition of hydrogen ions (H) and aluminium (Al) adsorbed to the solid-phase soil organic matter (SOM) determines pH and Al solubility in organic-rich acidic forest soils. Organically adsorbed Al was extracted sequentially with 0.5 m CuCl₂ and organically adsorbed H was determined as the difference between total acidity titrated to pH 8.2 and Al extracted in 0.5 m CuCl₂. The quotient between fractions of SOM sites binding Al and H (N_Al/N_H) is shown to determine the variation in pH and Al solubility. It is furthermore shown that models in which pH and Al solubility are linked via a pH-dependent solubility of an Al hydroxide and in which cation exchange between Al³⁺ and Ca²⁺, rather than cation exchange between Al³⁺ and H⁺, is the main pH-buffering process cannot be used to simulate pH or Al solubility in O and E horizons. The fraction of SOM sites adsorbing Al increased by depth in the lower O and throughout the E horizon at the same magnitude as sites adsorbing H decreased. The fraction of sites binding the cations Ca²⁺ + Mg²⁺ + K⁺ + Na⁺ remained constant. It is suggested that a net reaction between Al silicates (proton acceptors) and protonated functional groups in SOM (proton donors) is the long-term chemical process determining the composition of organically adsorbed H and Al in the lower part of the O and in the E horizon of Podzols. Thus, in the long term, pH and Al solubility are determined by the interaction between organic acidity and Al alkalinity.     

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).     

The influence of organic acidity on the acid-base chemistry of surface waters in Maine,USA

Results from surveys of low-ANC lakes (high elevation, and seepage lakes), and of surface waters in dystrophic, acidic bogs, indicate that acidic precipitation and organic acidity are each generally necessary, but not solely sufficient, for chronically acidic status in Maine lakes. Acidic, low DOC (ANC < 0; DOC < 5 mg L^-1) lakes of all hydrologic types are acidic due largely to acidic deposition; high DOC (DOC > 30 mg L^-1) acidic seepage lakes are acidic due largely to organic acidity, and high DOC drainage lakes are acidic due to a combination of both factors. No low DOC drainage lakes are known with pH less than about 5.0, suggesting that organic acidity is necessary to depress lake pH values to below 5 in Maine at current deposition loadings,The dominant anion of low DOC, acidic waters is sulfate. Acidic waters with intermediate concentrations of DOC (5 to 30 mg L^-1), may be dominated by S04 and/or organic acidity. Seepage-input lakes were the only group to include both organically-dominated (37% of the acidic lakes) and S0₄-dominated members (63% of the acidic lakes). High DOC systems are typically low pH bogs, and are all organic acid-dominated.     

Water-soluble organic matter and soil solution acidity in the main soil types of the central forest state biosphere reserve

The dynamics of the soluble organic carbon (C_WSO) and pH in soil solutions of the main soil types of the Central Forest State Biosphere Reserve were described. Possible reasons for the pH variation were considered. It was found that different soils are characterized by specific levels of pH and C_WSO. The structure of the soil solution acidity and its changes with depth were analyzed, and the relationship between the acidity and the content of water-soluble organics substances (WSOs) was determined. The predominantly hydrophilic nature and polydispersity of WSOs in soil solutions were revealed, as well as a decrease in the proportion of high-molecular soil fractions with depth. It was found that the mobility of metals in soils depends on the amphiphilic properties of WSOs to which they are bound, the metal features, and the soil type. The possibility of selective absorption of metals bound to the hydrophobic WSO fraction was shown.     

Potential for biodegradation of anthropogenic organic compounds at low temperature in boreal soils

The effect of temperatures of −2.5 to +20 °C on the biodegradation of concentrations 0.2-50 μg cm⁻³ of pentachlorophenol (PCP), phenanthrene, pyrene and 2,4,5-trichlorophenol (TCP) was studied in soils sampled from an agricultural field and a relatively pristine forest in Helsinki, Finland. At the temperatures simulating seasonal variation of boreal soil temperatures [Heikinheimo, M., Fougstedt, B., 1992. Statistic of Soil Temperature in Finland. Meteorological Publications 22. Finnish Meteorological Institute, Helsinki, Finland], the response of mineralization of PCP, phenanthrene and 2,4,5-TCP was the most effective in the rhizosphere fraction of the forest humus soil at the substrate concentrations of ?5 μg cm⁻³. In the control incubation, performed at constant temperature of +20 °C, the mineralization yields of the model pollutants were highest in the agricultural soil with the highest applied substrate concentration (50 μg cm⁻³). The results suggest that the high level of pollutant mineralization at +20 °C resulted from the apparent adaptation of the soil microbial community to the high substrate concentration. No such adaptation occurred when the soils were incubated at temperatures simulating the actual boreal soil temperatures. The present results stress the role of adjusting the incubation conditions to environmentally relevant values, when assessing biodegradation of anthropogenic organic compound in boreal soils.