Finnish lake survey: the role of organic and anthropogenic acidity

A lake survey consisting of 987 randomly selected lakes was conducted in Finland in autumn 1987. The survey covered the whole country, and the water quality of the lakes can be considered as representative of the approximately 56 000 lakes larger than 0.01 km² in Finland. The median TOC concentration is 12 mg L^-1 and the median pH 6.3. The proportion of lakes with TOC concentrations > 5 mg L^-1 in the whole country is 91 %. Organic anion is the main anion in the full data set (median 89 μeq L^-1). The high organic matter concentrations in Finnish lakes are associated with catchment areas containing large proportions of peatlands and acid organic soils under coniferous forest. The survey demonstrated that organic matter strongly affects the acidity of lakes in Finland. The decreasing effect of organic matter on the pH values was demonstrated by both regression analysis and ion balances. At current deposition levels of ^*SO₄ the pH of humic lakes in Finland is determined to a greater extent by high TOC concentrations than by ^*SO₄ in most areas. In lakes with pH values lower than 5.5 the average organic anion contribution is 56 % and non-marine sulfate contribution 39 %. However, in the southern parts of the country, where the acidic deposition is highest, the minerogenic acidity commonly exceeds the catchment derived organic acidity.     

Organic vs. minerogenic acidity in headwater streams in Finland

This study provides an assessment of the transport of organic carbon and organic acids from typical Finnish forested catchments since the 1960's. The 21 study catchments (0.69–56 km²) are located over Finland excluding the northernmost regions. The mean annual total organic carbon (TOC) load from the catchments ranges from 2 600 to 8 800 kg/km²/a. Using a total acidity of 9.7 eq/mg DOC this would represent organic acid load of about 25–85 keq/km²/a which is higher than the mean annual deposition of strong acids in the highest deposition areas in southern Finland. The study demonstrates that organic acids dominate stream water acidity over large regions in Finland. In southern Finland minerogenic acidity is, however, more important. Organic acids exceeded mineral acids not only in autumn but also during spring snowmelt in 18 catchments. Moreover, the lowest pH values (25th percentile) were dominated by organic acids in 20 catchments. In most catchments TOC better explained pH than non-marine sulphate. In stepwise multiple regression base cations and TOC explained 67–83 % of the variation in pH for catchments divided into six groups according to season, deposition and peatland percentage; non-marine sulphate had minor contribution.     

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.     

SOURCES OF TRACE METALS IN STREAMS AND HEADWATER LAKES IN FINLAND

Distributions of Mn, Zn, Cu, Ni, Cr, Pb, As, and Cd in Finnish surface waters were studied by comparing two data sets: samples from 154 headwater lakes collected by the Water and Environment Administration in 1992 and samples from 1165 headwater streams collected during the environmental geochemical mapping program of the Geological Survey of Finland in 1990. It was expected that headwater lakes with catchments smaller than 1 km² and high lake percentage (ratio of lake area to catchment size) would be more influenced by atmospheric trace metal deposition than the streams, with average catchment size of 30 km². The lakes with highest arsenic concentrations lie in an area with greenstones and arsenic-rich black schists. The same lakes have high copper concentrations, which evidently are derived from the Cu-rich greenstones of the catchment. The high copper concentrations of streams and lakes in the industrialized region of the southwest coast are due to several anthropogenic sources. The highest concentrations of chromium occur in brown stream and lake waters rich in humic matter, while manganese and zinc concentrations, which are controlled by acidity, tend to be elevated in low-pH waters. The high nickel concentrations in lakes in southwestern Finland probably are due to anthropogenic input, while Ni anomalies in stream and lake water in eastern Finland are correlated with high Ni contents of glacial till. The lead concentrations in lakes are mainly of airborne anthropogenic origin. The pattern of atmospheric deposition is reflected in the concentrations of Cd, As, Cu, Zn, and Ni in headwater lakes, but land-use, the natural distribution of metals in the overburden, water acidity, and the amount of humic substances influence the distribution of trace metals in both lakes and streams. Thus the trace metal distribution in headwater lakes cannot be used alone to estimate the contribution of anthropogenic atmospheric deposition to metal anomalies in Finnish surface waters.     

Temporal chemical variability in acid sensitive high elevation lakes

Chemical indicators suggest that slight, but discernable acidification occurs during smowmelt in some highly sensitive Cascade Mountain Lakes (mean alkalinity 20 ueq L^?1). Although some SO₄ in the lakes (mean 13 μeq L^?1 ) comes from local geologic sources, several considerations suggest that some also comes from atmospheric deposition and anthropogenic sources. If sampling is stratified, the relatively low lake-to-lake and year-to-year variability in chemical constituents demonstrates that these highly sensitive lakes represent excellent indicators of acidification. The contention that precipitation pH >4.6 is needed for protection of sensitive lakes is supported. However, the slight but temporary acidification effect currently detectable during snowmelt, suggests that for adequate protection of these highly sensitive lakes, precipitation pH should be >4.7 to 4.8.     

Boron content in freshwaters of Northern Italy

The B concentration was determined in bulk deposition and in surface freshwaters (lakes and rivers) of the river Po watershed in Northern Italy. The curcumin photometric method was used to determine B content for all analyses. The B concentrations were under detection limits (0.06 mg B L^?1) in bulk deposition and below 0.09 mg B L^?1 in lake waters. Approximately 65 % of river samples measured had B concentrations close to natural background levels for natural waters (0.1 mg B L^?1). There was a strong correlation (r < 0.85) between B concentration and those of both total dissolved P and anionic detergents. The elevated B concentrations may be related to anthropogenic sources.     

Acid deposition and lake chemistry in southwest China

A water quality survey has been performed on selected lakes and streams in southwest China. The purpose of the study was to measure the concentrations of acidic deposition and surface water chemistry in a region of severe air pollution, forest decline, and relatively sensitive geology to acidic deposition. We show that, although there are some high elevation lakes of low acid neutralizing capacity (ANC<150μeq L^?1, acidification of lakes has not occurred in southwest China due to production of base cations in soil and dry deposition of dust that serves to neutralize acidic deposition. Water chemistry is buffered by high base cation concentrations (Ca²⁺, Mg²⁺, Na⁺, and K⁺ greater than 300μeq L^?1, and pH values are always greater than 6.5.     

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.     

RAIN project: Role of organic acids in moderating ph change following reduction in acid deposition

The RAIN project (Reversing Acidification In Norway) entails catchment-scale experimental manipulations to investigate the effect on water and soil chemistry of drastic changes in precipitation chemistry. At Risdalsheia in southernmost Norway wet deposition of acid is excluded from a 860-m² headwater catchment by means of a roof and “clean” precipitation is added beneath. Four years of acid exclusion (through June 1988) have resulted in lower concentrations of the strong acid anions NO₃ (from 35 to 7 ueq L^-1) and SO₄ (from 110 to 53 ueq L^-1) in runoff. The decline in strong acid anion concentrations has been compensated partially by a decrease in concentrations of base cations (55%) and partially by an increase in alkalinity (45%). pH has increased only slightly from 4.0 to 4.1. Organic acids have become increasingly important for the pH of runoff. Runoff from the shallow organic soils contains 10 to 20 mg C L^-1 total organic carbon (TOC). The concentration of organic anions (estimated from the ionic balance) has increased from about 22 ueq L^-1 in 1984 to 49 ueq L^-1 in 1987. This increase is due to increased dissociation of organic acids and not to change in TOC concentrations. The organic C in these acid samples apparently has a maximum charge density of about 4.5 ueq mg C^-1 and pK of about 4.     

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.     

Formiate and acetate in wet deposition at Pallanza (NW Italy) in relation to major ion concentrations

Weekly samples of wet deposition were collected at Pallanza (NW Italy) from January 1987 to December 1988. Their chemistry is characterized by high mineral acidity, with a median pH value of 4.26; only in 2 out of 62 samples was pH higher than 6.0. Sulphate, nitrate and ammonium are the main ions. Formiate and acetate showed a volume weighted average of 7 and 4 μeq L^?1, respectively; the values for the dissociated forms are 5 and 1 μeq L^?1, respectively. The contribution of formiate and acetate (dissociated form) to the total ionic concentration is about 2%, while the contribution to free hydrogenion is about 13%, mainly deriving from formic acid. Seasonal variations in concentration and the relationships between organic acid and other ions indicate that the photolysis of isoprenoid compounds released into the atmosphere from vegetation is a significant source for formic acid. In the case of acetic acid there is a contribution from anthropogenic emissions, more marked during the winter period.     

Measurement of methylmercury and mercury in run-off,lake and rain waters

During one year, samples from eight drainage lakes, seven run-off stations and three deposition sites from various geographical areas in Sweden were collected and analyzed for methyl Hg (MeHg) and total Hg (Hg-tot). The MeHg concentrations ranged from 0.04 to 0.64 ng L^?1, 0.04 to 0.8 ng L^?1, and <0.05 to 0.6 ng L^?1 in run-off, lake water and rain water, respectively. The corresponding Hg-tot concentrations were found in the range 2 to 12 ng L^?1, 1.35 to 15 ng L^?1, and 7 to 90 ng L^?1, respectively. A Hg-tot level of about 60 ng Hg L^?1 was found in throughfall water. The MeHg and Hg-tot concentrations are positively correlated in both run-off and lake water, but not in rain and throughfall water. A strong positive correlation between the MeHg, as well as the Hg-tot concentration, and the water color is observed in both run-off and lake waters, which suggests that the transport of MeHg and other Hg fractions from soil via run-off water to the lake is closely related to the transport of organic substances; and is a consequence of the biogeochemical processes and the water flow pathway. The ratio between the mean values of MeHg and Hg-tot seems to be an important parameter, with an indicated negative coupling to the mean value of pH for run-off water, but a strong positive correlation to Hg-content in fish, the ratio between the area of the catchment and the lake, as well as to the retention time of lake.     

Atmospheric Deposition in a Rural Area in India - Net and Potential Acidity

Atmospheric deposition in India is generally described as alkaline and well buffered against an increase of acidifying components. Such conclusion has been based on measurements usually performed in urban or suburban areas. Our data on deposition in NE India (in the countryside N of Bhubaneswar) obtained with wet-only and bulk collectors show that: 1) the weighted mean concentrations (and wet deposition) of H⁺ and HCO₃ ^? are almost equal, with dustfall contributing a negligible amount of HCO₃ ^?, 2) the deposition of potential acidity, defined as the acidity that would give the same acidity contribution to the receiving surface as the actual deposition provided that all ammonium was converted to nitrate in the soil, could be as high as 40 mmol H⁺ m^?2 a^?1 corresponding to a pH of 4.3 in precipitation. The low buffer capacity against acidification and high potential acidity were discovered from long- term measurements in a vegetation covered rural area. Similar measurements in a nearby suburban area gave a much higher input of HCO₃ ^? both in wet deposition and dustfall. Further increase of the emission of acidifying components in the region will increase the acid deposition.     

Recovery Pattern from Acidification of Headwater Lakes in Finland

Acid sensitive headwater lakes (n=163) throughout Finland have been monitored during autumn overturn between 1987–1998. Statistically significant decline in sulphate concentration is detected in 60 to 80 percent of the lakes, depending on the region. Median slope estimates are from ?1.1 µeq L^?1 in North Finland to ?3.3 µeq L^?1 in South Finland. The base cation (BC) concentrations are still declining especially in southern Finland (slope ?2.5 µeq L^?1), where every second lake exhibits a significant downward trend. The BC slope is steeper for lakes with less peatlands, more exposed bedrock, longer retention time and southerly location, but these factors are inter correlated. Gran alkalinity slope medians for the three regions range from 1.4 to 1.8 µeq L^?1 yr^?1. No significant negative alkalinity trends were detected. The similarity in the slopes of SO₄, BC and alkalinity in this data compared to seasonal sampling data from Nordic Countries can be regarded as indirect evidence that autumnal sampling is representative for long term monitoring for these ions. There are no indications of increased organic carbon in lakes, as found in some recent trend analyses of similar regional data sets. Although the processes behind the positive development in these lakes have to be revealed with site- specific intensive studies, this data suggests, that the initial recovery from lake acidification in Finland is a regional phenomenon.     

Total cadmium concentrations in the water and littoral sediments of Central Ontario Lakes

Lakes within 20 km of Sudbury, Ontario, have significantly higher Cd concentrations in surface waters (geometric mean 122 ng L^?1; n = 7) than lakes elsewhere in central Ontario (10.8 ng L^?1; n = 57). Cadmium concentrations in water from lakes beyond the Sudbury halo were negatively correlated (r = 0.797; p < 0.001) with pH. A weak correlation between fluoride and Cd concentrations leads to speculation that some Cd may be mobilized from watersheds with Al. Cadmium concentrations in littoral sediments are not elevated near Sudbury. The geometric mean Cd concentration of littoral sediments in central Ontario lakes is 0.08 mg Cd kg^?1 dry mass (n = 75). Cadmium concentrations in littoral sediments are strongly correlated with sediment loss on ignition (r = 0.860; p < 0.001). After correction for differences in organic content, littoral sediments are less enriched with Cd than profundal sediments, as reported in the literature. The difference between littoral and profundal sediments, and the sensitivity of Cd concentrations in water to pH, may be due to the importance of Cd binding by Fe/Mn hydrous oxides in the profundal zone, while organic matter binds Cd in the littoral zone. The lack of sensitivity of Cd concentrations in littoral sediments to acidification may be due to the incorporation of much of the Cd in those sediments into organic particulates.     

Factors affecting snowmelt streamwater chemistry in the black forest (West Germany)

Site conditions such as parent material, soils, but also vegetation cover and elevation explain the varying snowmelt streamwater chemistry in the Black Forest. The results are derived from multiple statistical analysis of a regional survey of 104 small mountain streams in the first phase of snowmelt in spring 1984. Cluster analysis classifies the snowmelt streams into three groups which are clearly linked to bedrock geology. Factor analysis finds podsolization, weathering and mineralization processes in the soils of the catchments to have most impact even under snowmelt conditions. There is no evidence that acidic atmospheric deposition directly affects the acidity of the investigated streams. However, the deposition rates are low compared to certain other regions in Central Europe. In areas with podsolic soils the organic soil layer plays a key role in the acidity and mobilization of Al and heavy metals. This is shown in the high correlations between pH, DOC, UV-extinction, color and metal concentrations. Because the concentrations of DOC are low (<10 mg.L^?1) and an anion deficit cannot be found, it is assumed that water acidity is not caused by dissolved humic acids, but by cations exchanged in the organic layer of acidic soils. Streamwater chemistry in areas with brown earth soil types is mainly affected by leaching of basic cations in the mineral soil horizons and mineral weathering.     

Determination of organic acid anions in precipitation by ion chromatography exclusion

A method for the determination of organic acid anions in precipitation samples is described. The technique of ion chromatography exclusion (ICE) is used to identify and quantify the more commonly found anions of the acids citric, formic and acetic in central Illinois rainwater. By using a two column system consisting of a separator and suppressor, method detection limits (MDL) of 0.03 mg L^?1 for each of the three anions are obtained. The total analysis time for quantitation is 24 min. Samples collected from early spring rains contained primarily formate and acetate ions with levels of concentration ranging from 0.03 to 0.44 mg L^?1. The organic acids formic and acetic contributed approximately 8% to the total acidity in the precipitation samples analyzed. Precision averaged 5% as the relative standard deviation (RSD) and analyte spikes of natural precipitation samples revealed a mean recovery of greater than 99%. A preservation technique using chloroform (CHCl₃) addition is discussed with results indicating its necessity in maintaining original organic anion concentrations.     

Partitioning of Hg Between Solid and Dissolved Organic Matter in the Humus Layer of Boreal Forests

The mobility of mercury (Hg) deposited on soils controls the concentration and toxicity of Hg within soils and in nearby streams and lakes, but has rarely been quantified under field conditions. We studied the in situ partitioning of Hg in the organic top layer (mor) of podsols at two boreal forest sites differing in Hg deposition and climatic regime (S. and N. Sweden, with pollution declining to the north). Soil solution leaching from the mor layer was repeatedly sampled using zero-tension lysimeters over 2 years, partly in parallel with tension lysimeters. Concentrations of Hg and dissolved organic carbon (DOC) were higher while pH was lower at the southern site (means ± SD: Hg?=?44?±?15 ng L^?1, DOC?=?63.0?±?31.3 mg L^?1, pH?=?4.05?±?0.53) than at the northern site (Hg?=?22?±?6 ng L^?1, DOC?=?41.8?±?12.1 mg L^?1, pH?=?4.28?±?0.43). There was a positive correlation over time between dissolved Hg and DOC at both sites, even though the DOC concentration peaked during autumn at both sites, while the Hg concentration remained more constant. This correlation is consistent with the expected strong association of Hg with organic matter and supports the use of Hg/C ratios in assessments of Hg mobility. In the solid phase of the overlying O_f layer, both Hg concentrations and Hg/C ratios were higher at the southern site (means ± SD: 0.34?±?0.06 μg g^?1 dw and 0.76?±?0.14 μg g^?1 C, respectively) than at the northern site (0.31?±?0.05 μg g^?1 dw and 0.70?±?0.12 μg g^?1 C, respectively). However, concentrations in the solid phase differed less than might be expected from the difference in current atmospheric input, suggesting that the fraction of natural Hg is still substantial. At both sites, Hg/C ratios in the upper half of the mor layer were only about two thirds of those in the lower half, suggesting that the recent decrease in anthropogenic Hg deposition onto the soil is offset by a natural downward enrichment of Hg due to soil decomposition or other processes. Most interestingly, comparison with soil leachate showed that the average Hg/C ratios in the dissolved phase of the mor layers at both sites did not differ from the average Hg/C ratios in the overlying solid organic matter. These results indicate a simple mobilisation with negligible fractionation, despite differences in Hg deposition patterns, soil chemistry and climatic regimes. Such a straight-forward linkage between Hg and organic matter greatly facilitates the parameterisation of watershed models for assessing the biogeochemical fate, toxic effect and critical level of atmospheric Hg input to forest soils.     

Brook Water Quality and Background Leaching from Unmanaged Forested Catchments in Finland

The water chemistry of 21 outlet brooks in undisturbed, forested catchments (0.074–38 km²) in Finland was monitored during three years (1997–1999) in order to estimate the background levels and leaching of total organic carbon (TOC), iron, nitrogen and phosphorus, and examine the relationships between catchment characteristics and brook water quality in pristine forested areas. The studied catchments are located throughout Finland except the northernmost parts of the country. The concentrations of TOC were relatively high, on average 20 mg L^-1. Annual leaching of TOC ranged from 3000 to 10 000 kg km^-2. The average total nitrogen concentration and annual leaching were 430 μg L^-1 and 140 kg km^-2, respectively. The average total phosphorus concentration and annual leaching were 15 μg L^-1 and 5.4 kg km^-2, respectively. On a national level temperature and discharge conditions were the most important variables for predicting total phosphorus, total nitrogen and TOC concentrations. Both total nitrogen and total phosphorus concentrationsdisplayed positive correlation with temperature, and thus the concentrations were higher in the south than in the north. Nitrogen was mainly organic and showed strong correlation with TOC. On the catchment level, both TOC and total nitrogen concentrations and export had a strongpositive correlation with the abundance of Norway spruce (Piceaabies Karsten) and a strong negative correlation with the abundance of Scots pine (Pinus sylvestris L.). Nitrate concentrations and leaching were related to average site type. The more fertile the average site type was in the catchment, the higher the nitrate concentrations and export were.     

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.