Recent trends in the acid-base status of surface waters in Maine,USA

Data from the EPA Long Term Monitoring Program lakes at the Tunk Mountain Watershed, Maine, indicate that decreases of ≤1 Μeq L^?1 yr^?1 in SO₄, and increases of ≤2 Μeq L^?1 yr^?1 in ANC occurred in the 1980s. The sum of base cations also increased. These changes in aquatic chemistry were coincident with decreased concentrations of all solutes in precipitation during the 1980s. Other data on lakes and streams in Maine collected between the 1930s and 1990 generally confirm these trends and further indicate that larger increases in ANC may have occurred in some lowland lakes since 1940. Paleolimnologic studies indicate that decreases of 0.1 to 0.5 pH units occurred in a few small mountain lakes during the past 20 to 70 yr. However, ongoing acidification of lakes is indicated based on available data. Only lakes that were already at least marginally acidic (pH ≤5.8, ANC approximately 0) appear to have acidified.     

Critical loads of acidity for surface waters

The critical load of acidity for surface waters is based on the concept that the inputs of acids to a catchment do not exceed the weathering less a given amount of ANC. The Steady State Water Chemistry (SSWC) Method is used to calculate critical loads, using present water chemistry. To ensure no damage to biological indicators such as fish species a value for ANC_limit of 20 μeq/l has been used to date for calculating critical loads. The SSWC-method is sensitive to the choice of the ANC_limit. In areas with little acid deposition the probability of acid episodes leading to fish kills is small even if the ANC_limit is set to zero, while in areas with high acidic deposition fish kills may occur at this value. Thus, the ANC_limit can be a function of the acidifying deposition to the lake, nearing zero at low deposition and increasing to higher values at higher deposition. A formulation for such an ANC_limit has been worked out, and we have tested the effect of the ANC_limit as a linear function of the deposition, assuming ANC_limit = 0 at zero deposition with a linear increase to 50 ueq/l at a deposition of 200 meq.m^?2.yr^?1. For areas with high deposition the effect of a variable ANC_limit is small, while in areas with low deposition the effect is significant. For Norway the exceeded area decreases from 36 to 30% using a variable ANC_limit instead of a fixed value of 20 μeq/l.     

Critical loads of acidity to surface waters

The critical load of acidity to surface water is based on the condition that the inputs of acids to a catchment do not exceed the weathering rate less a given amount of ANC (Acid Neutralizing Capacity). The Steady State Water Chemistry (SSWC) Method is used to calculate critical loads of acidity, using present water chemistry. To calculate the weathering, the so-called F-factor is used to estimate the part of the base cation flux that is due to soil acidification. The F-factor has been estimated empirically from historical data comparisons from Norway, Sweden, U.S.A. and Canada and is considered to be a function of the base cation concentration by the formula: F=sin(BC^*/S), where BC^* is the present base cation concentration and S the base cation concentration at which F=1. At higher values for BC^* F is set to 1. For Norway, Sweden and Finland S has been set to 400 μeq/l (ca. 8 mg Ca/l), giving F-values in the range 0.05–0.2. The importance of the F-factor in the calculations of the critical loads of acidity for Nordic surface waters was tested by calculating the magnitude of the area where the critical load of acidity is exceeded in Norway for different values of S. Similar calculations were carried out for the Finnish and Swedish lake data. Varying S from 100 μeq/l to 1200 μeq/l, the exceeded area in Norway decreases from 31,9 to 28,3%. For F=0 (S=∞, i.e. assuming no soil acidification), the exceeded area is reduced to 27,2%. For Finland and Sweden the the percent of lakes exceeded are reduced from 16,6 to 12,9% and 30 to 23,6%, respectively. For F = 0 the percent of lakes exceeded are reduced to 11,4 and 16,4, repectively. These results indicate that the F-factor is not of great importance for calculating critical load and critical load exceedances in Norway, Finland and Sweden.     

Increasing contributions of nitrogen to the acidity of surface waters in Norway

The acidification of lakes in southern Norway is largely due to sulfate. Recent data from regional surveys of lakes and from monitoring stations indicates that nitrate concentrations have increased in many lakes and rivers in southernmost Norway. The ratio of NO₃ to NO₃ + SO₄ is still low for most areas, but is 0.54 on an equivalent basis in lakes and rivers in the area of high runoff in southwestern Norway. Here, concentrations of nitrate in the runoff are lower than for sites in Central Europe, but are higher than those in North America. The sites showing increases in NO₃ also increased in Al. Further increases in nitrate as a mobile anion which may be due to decreased uptake in the watershed, will contribute to acidification in the same manner as sulfate.     

Acid-base analysis of dissolved organic matter in surface waters

A mono-protic multi-site model is developed to obtain a pK(acid) — concentration distribution. Dense and equal interval pH data are required for an accurate characterization. A computer driven titrimetric system is used to obtain the data. The technique is applied to dissolved organic carbon (> 15 mg C L^-1) samples from the Kejimkujik region, Nova Scotia. A calculation shows that the acidic (pH=4.6) dystrophic waters can result from mixing 15 mg C L^-1 of the organic acids with an initial inorganic system of about 75 peq L^-1 alkalinity.     

Soil-solution chemistry in a low-elevation spruce-fir ecosystem,Howland, Maine

Soil solutions were collected monthly by tension and zero-tension lysimeters in a low-elevation red spruce stand in east-central Maine from May 1987 through December 1992. Soil solutions collected by Oa tension lysimeters had higher concentrations of most constituents than the Oa zero-tension lysimeters. In Oa horizon soil solutions growing season concentrations for SO₄, Ca, and Mg averaged 57, 43, and 30 μmol L^?1 in tension lysimeters, and 43, 28, and 19 μmol L^?1 in zero-tension lysimeters, respectively. Because tension lysimeters remove water held by the soil at tensions up to 10 kPa, solutions are assumed to have more time to react with the soil compared to freely draining solutions collected by zero-tension lysimeters. Solutions collected in the Bs horizon by both types of collectors were similar which was attributed to the frequency of time periods when the water table was above the Bs lysimeters. Concentrations of SO₄ and NO₃ at this site were lower than concentrations reported for most other eastern U.S. spruce-fir sites, but base cation concentrations fell in the same range. Aluminum concentrations in this study were also lower than reported for other sites in the eastern U.S. and Ca/Al ratios did not suggest inhibition of Ca uptake by roots. Concentrations of SO₄, Ca, K, and Cl decreased significantly in both the Oa and Bs horizons over the 56-month sampling period, which could reflect decreasing deposition rates for sulfur and base cations, climatic influences, or natural variation. A longer record of measured fluxes will be needed to adequately define temporal trends in solution chemistry and their causes.     

Critical loads of acidity to surface waters in the Vosges massif (north-east of France)

Acid clearwater fishless streams have been identified in the Vosges mountains. In order to evaluate the relatipnships between acidifying factors (such as atmospheric deposition), buffering factors (such as bedrock and soil type), and surface water acidity, an exhaustive survey of streamwater acidity in the Vosges mountains (N-E France) was performed. A network of 11 measurement stations of atmospheric deposition was used to estimate and map deposition over the whole massif (total area 5000 km²). Data on bedrock, soil, superficial deposits, and vegetation were collected from published studies. Sensitive areas as well as acidifying environment factors were derived from the corresponding maps. Over the whole massif, 19% of streams showed baseflow alkalinity below 30 eq.r¹ and 7.5 % were identified as acid (pH < 5.4).=" acid=" streams=" occur=" on=" the=" north-western=" side=" of=" the=" massif=" on=" quartzrich=" sandstone=" and=" acid=" granites.=" in=" each=" of=" these=" areas,=" we=" could=" clearly=" point=" out=" on=" one=" hand,=" the=" negative=" influence=" of=" conifer=" vegetation=" and=" glacial=" soil=" abrasion=" or=" induration,=" and=" on=" the=" other=" hand=" the=" buffering=" effect=" of=" moraine=" deposits.=" a=" corresponding=" range=" of=" critical=" loads=">< 0.2=" to=" 2.0=" keq.=">¹ yr¹) for surface water was calculated using the Steady State Water, Chemistry method (SSWC).     

Analysis and assessment of precipitation chemistry at Caribou,Maine

Over the last 30 yr, Caribou, Maine has been the only U.S. collection site which has been a part of all four national precipitation chemistry networks. Due to its remote but strategically important location, the data from this site are very useful in evaluating transboundary transport of the major ions present in precipitation. This paper assesses the reliability of the Caribou data base and looks at the more recent data with the aid of the GAMBIT (Gridded Atmospheric Multilevel Backward Isobaric Trajectory) model. An examination of the historical data base indicates serious contamination problems in pre-1980 samples, particularly with S0₄ measurements. The trajectory climatology shows that the largest number of precipitation events track along the U.S. coast. Preliminary chemistry measurements indicate highest concentrations of H+ and S0₄ occur from events associated with trajectories passing through southern Canada.     

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 organic acids in the acidification of surface waters in the Eastern U.S.

There is considerable uncertainty concerning the role of naturally occurring organic solutes in the acidification of surface waters. To provide a preliminary assessment of this process, we evaluated water chemistry data obtained from the US EPA Eastern Lake Survey (ELS). A wide range of dissolved organic carbon (DOC) and organic anion concentrations were evident across acid-sensitive lake districts in the Eastern US. In particular, lakes in Maine, the Upper Midwest and Florida contained high concentrations (greater than 1000 gmol C · L^?1) of DOC. High concentrations of organic anions, estimated by discrepancy in charge balance in several subregions, suggest that dissociation of naturally occurring organic acids could significantly reduce the ANC of dilute surface waters. Unfortunately, analysis of acidification by organic solutes is complicated by uncertainty in H⁺ dissociation characteristics. Input of organic acids with weakly acidic pK _a values do not alter acid neutralizing capacity (ANC), while strongly acidic organic functional groups dissociate completely and decrease ANC. As a first step to assess the acid/base characteristics of naturally occurring organic solutes, we calibrated the Oliver et al. (1983) model, using a reduced version of the ELS data set. This model explained 94% of the observed variability in organic anion concentration in this data set. However, model parameters obtained from the ELS calibration were somewhat different than values provided by Oliver et al. (1983), based on potentiometric titrations of pre-concentrated organic acids. The discrepancy in model parameters has implications for estimating organic anion concentrations in water using the Oliver et al. (1983) model. Finally, data from the ELS indicates that across glaciated regions of the eastern US, concentrations of DOC and organic ions were negatively correlated with SO _inf2? ^p4 . This trend would appear to be consistent with the hypothesis that inputs of strong acids immobilize organic acids, resulting in a shift of surface water acidification by organic acids to strong acids.     

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.     

Factors affecting streamwater chemistry in The Great Smoky Mountains,USA

The Great Smoky Mountains in the southeastern U.S. receive high total atmospheric deposition of sulphur and nitrogen (N) and contain large areas of shallow, poorly buffered soils. Results from extensive surveys conducted in October 1993 and March 1994 showed mat stream pH values were near or below 5.5 and Acid Neutralizing Capacity (ANC) was below SO μeq·L^?1 at high elevations. Mechanisms of acidification varies among stream systems in the study. We classified each study catchment into one of five water quality districts based upon within-basin elevational gradients of streamwater quality. Geologic factors, cf. the presence of calcareous or pyritic bedrock types exhibited a major influence on water quality and within-basin elevational gradients. Atmospheric deposition is an important factor affecting water quality at high elevations in all districts. Nitrate was the dominant strong acid anion in streamwater in many catchments, particularly at high elevation and especially in basins draining old growth forests. Most high elevation catchments appear to be N saturated. Continued high atmospheric loadings of N will likely spread N saturation of catchments downslope into areas where second growth forests are now maturing. Stream sulphate concentrations were lower than expected at higher elevations and may be related to the N saturation status of fliese systems.     

A method for evaluating the acid-base balance in natural waters

As is well known the acid-base content of lake water is composed of strong base or acid, weak acids (mainly fulvic acid) and carbonic acid. Recently Lee (1980) has calculated the acidity constants and the concentrations of the weak acids in a number of lake water samples. In this paper a method for the evaluation of the remaining concentration of strong base or acid and of carbonic acid has been described. Applied to the previously mentioned lake water samples it has given the following results: The concentration of strong base or acid has been obtained with good accuracy (calculated slope of Grant's plot: ?100 ± 0.02, ?r = 0.9999). Values of [H₂CO₃] obtained from pH-values measured in connection with sampling, correspond, in most cases, to supersaturation which for samples with about the same pH seems to increase with alkalinity and also possibly with the concentration of fulvic acid. However, the method of calculation applied may not give quite reliable results for [H₂CO₃] in originally very acid samples.     

Litterfall Mercury in Two Forested Watersheds at Acadia National Park, Maine, USA

Litterfall can be an important flux of mercury (Hg) to soils in forested landscapes, yet typically the only available data to evaluate Hg deposition is from precipitation Hg monitoring. Litterfall was collected at 39 sampling sites in two small research watersheds, in 2003 and 2004, and analyzed for total Hg. Four vegetation classes were designated in this study as hardwoods, softwoods, mixed and scrub. The mean litter Hg concentration in softwoods (58.8 ± 3.3 ng Hg g^?1 was significantly greater than in mixed (41.7 ± 2.8 ng Hg g^?1 and scrub (40.6 ± 2.7 ng Hg g^?1, and significantly lower than in hardwoods (31.6 ± 2.6 ng Hg g^?1. In contrast, the mean weighted litter Hg flux was not significantly different among vegetation classes. The lack of a significant difference in litter Hg flux between hardwoods and softwoods was attributable to the large autumnal hardwood litter Hg flux being balanced by the higher softwood litter Hg concentrations, along with the higher chronic litterfall flux throughout the winter and spring in softwoods. The estimated annual deposition of Hg via litterfall in Hadlock Brook watershed (10.1 μg m^?2 and Cadillac Brook watershed (10.0 μg m^?2 was greater than precipitation Hg deposition and similar to or greater than the magnitude of Hg deposition via throughfall. These results demonstrate that litterfall Hg flux to forested landscapes can be at least as important as precipitation Hg inputs.     

Sources of acidity in running waters in central northern Sweden

Factors controlling the acidity of running waters between the coast of the Gulf of Bothnia and the Caledonian mountain range in central-northern Sweden were studied intensively in 8 large streams and in two synoptic surveys of 179 small streams. The bulk deposition of SO₄ ^2? was between 11–22 μeq m^?2 y^?1, of which 93% was nonmarine, with the highest values in the coastal region. Organic anions were the most frequent acid anions in the whole investigation area followed by sulfate. The major portion of SO₄ ^2? was from natural sources in the whole investigation area. The most acidic streams occurred in the hilly wave-washed terrain of the coastal region, because of a high terrestrial export of organic acids and very low neutralizing capacity. It is concluded that most of the acidity in the investigated streams is due to natural sources.     

Population decline of northern dusky salamanders at Acadia National Park, Maine, USA

We investigated and reviewed the current and historic distribution of northern dusky salamanders (Desmognathus fuscus fuscus) in Acadia National Park (ANP), Maine, USA during 1938-2003. Historical data indicate that northern dusky salamanders were once widespread and common in ANP. We conducted intensive surveys for stream salamanders during 2000-2003 and observed only two adult northern dusky salamanders on one stream. No eggs or larvae were observed. Although the cause of the observed population decline is unknown, we identify multiple potential stressors including stocking of predatory fishes, fungal pathogens, substrate embeddedness, and widespread pollution (i.e., from atmospheric pollutants) of surface waters at ANP. Our data suggest that ANP streams may no longer be suitable for northern dusky salamanders. This investigation is the first to document the decline of a stream dwelling amphibian species in a national park (i.e., areas that are not subject to obvious habitat loss or major changes in land use) with widespread mercury contamination of its surface waters.     

Ameliorating subsoil acidity by surface application of calcium fulvates derived from common organic materials

Subsoil acidity is a serious constraint to crop production, and is difficult to correct by conventional liming practices. Thus, a different approach to ameliorating acid subsoils was evaluated. Subsoil material of an acid Ultisol (pH 4.4) was packed into 50-cm long columns, then leached with solutions of CaCl₂, CaCO₃ (suspension) or Ca fulvates prepared from chicken manure, cowpea green manure, or sewage sludge. The total water applied was 30.26 cm (or 800 ml) in 2 days. Thereafter, the columns were dismantled and cut into 5-cm segments for chemical analysis. The results indicated that only 2% of the added Ca from CaCO₃ moved past the 15-cm depth, compared to 68% from CaCl₂ and 35–75% from Ca fulvates. Correspondingly, CaCO₃ precipitated all KCl-extractable Al in the top 5 cm, but had no effect beyond the 10-cm depth. The CaCl₂ displaced a small but significant portion of extractable Al from the top 15 cm and redeposited some of that Al in lower depths. Similar to CaCO₃, Ca fulvates from chicken manure and green mamure only decreased extractable Al significantly in the top 10-cm layers, but had little effect beyond that depth. By contrast, the Ca fulvate from sewage sludge decreased Al down to the 45-cm depth. In terms of reducing Al saturation as a percentage of total extractable cations (effective cation exchange capacity), the Ca fulvates were as effective as CaCO₃ in the 0-to 5-cm layer, and more effective than CaCl₂ in any soil layer because of the increased exchangeable Ca and/or decreased Al. In general, surface application of common organic material-derived Ca fulvates can increase subsoil Ca and decrease the Al saturation percentage. However, Mg depletion and enrichment of unwanted metals (e.g., Na or heavy metals) may be a problem when leaching with these organic sources.     

Effects of Acidity and Aluminum on the Physiology and Migratory Behavior of Atlantic Salmon Smolts in Maine, USA

Atlantic salmon, Salmo salar, smolts of hatchery origin were held for 5 to 16 days in ambient (pH 6.35, labile Al = 60 µg L^?1), limed (pH 6.72, labile Al = 58.4 µg L^?1), or acidified (pH 5.47, labile Al=96 µg L^?1) water from the Narraguagus River in Maine, USA. Wild smolts were captured in the same river in rotary traps and held for up to two days in ambient river water. Osmoregulatory ability was assessed by measuring Na⁺/K⁺ ATPase activity, hematocrit, and blood Cl concentration in freshwater, and after 24-hr exposure to seawater. Hatchery smolts exposed to acidic water and wild smolts displayed sub-lethal ionoregulatory stress both in fresh and seawater, with mortalities of wild smolts in seawater. Using ultrasonic telemetry, hatchery-reared ambient and acid-exposed, and wild smolts were tracked as they migrated through freshwater and estuarine sections of the river. The proportion of wild smolts migrating during daylight hours was higher than for hatchery-reared smolts. Wild smolts remained in the freshwater portions of the river longer than either group of hatchery smolts, although survival during migration to seawater was similar for all three treatments. Acid-exposed hatchery-origin and wild Narraguagus River smolts were both under ionoregulatory stress that may have affected their migratory behavior, but not their survival for the time and area in which we tracked them.