Can forest-soil liming mitigate acidification of surface waters in Sweden?

Acidification of surface waters and forest soils is severe in large parts of southern Sweden. The shallow groundwaters are also affected. Large scale liming of surface waters and streams is in operation, often combined with wetland liming to limit the effects of acid episodes, e.g. at snow melt. Acid episodes are perhaps the most severe problem in limed surface waters and in many as yet well buffered waters, because of temperature-layered acid inflow, often superficial. As a result of some investigations, a large scale forest liming programme covering 6.500–10.000 km² was recently suggested. The main objectives of this forest liming programme are to retard cation depletion and to prevent nutrient imbalance and forest decline in acidified areas. This paper deals with the effects of forest soil liming on streams and surface waters. The response of water chemistry is very dependent on hydrological and soil properties. Although pH itself may be little affected by liming, the acidity (or negative ANC) decreases, inorganic Al-species decrease and the Al/BC-ratio increases in the runoff water. Especially interesting is that this is also true during acid episodes. This means that toxicity for acid sensitive biota decreases. These results indicate that large scale liming may have beneficial effects on surface water chemistry. Furthermore, as surface waters are expected to respond to smaller decreases in acid deposition than do forests soils, forest soil liming may allow less frequent liming of lakes. Consequently, forest soil liming in combination with the anticipated emission reductions may have very beneficial results on surface waters in certain areas of Sweden.     

Cooperative federal-state liming research on surface waters impacted by acidic deposition

In the eastern and north-central United States, lakes and streams with low acid neutralizing capacity are at risk from acidity. Resource management agencies are interested in developing mitigation strategies that protect or restore fisheries in these waters. Addition of limestone (calcium carbonate) to improve water quality and prevent episodic depressions of pH during precipitation events and spring runoff is one mitigation technique being used. The ecological changes that accompany such treatment of streams and lakes are being investigated in a cooperative program between the U.S. Fish and Wildlife Service and individual states. Streams in Massachusetts, West Virginia and Tennessee, and a lake in Minnesota are included in this 5-yr research program. Intensive monitoring during pre- and post-liming tracks a suite of physical, chemical and biological parameters that influence the re-establishment or maintenance of healthy fisheries. Supporting studies on liming being conducted at Adirondack lakes in New York focus on fisheries management. A model on the influence of liming on light attenuation and thermal stratification is also being developed. Management guidelines are to be generated from the program results.     

Estimation of background sulphate concentrations in natural surface waters in Sweden

In order to measure the extent of acidification the background, ‘preindustrial’ conditions must be known. An equation for the estimation of background concentrations of sulphate in surface water in Norway was proposed by Henriksen. When applied on data from the Swedish lake survey in 1990 it was found that the calculated background concentrations exceeded those measured for about one-third of the lakes. The proposed revision is based on a background concentration in precipitation and an estimated contribution from weathering, the latter associated with base cations. Three different approaches were tested to establish the contribution from weathering; geochemical ratios or groundwater chemistry data as a basis, and historical data on denudification. The weathering calculated from groundwater chemistry data seems to give the best estimate of the background sulphate concentration in surface water. Organic matter as source or sink of sulphur is discussed and considered negligible.     

Effects of liming on crayfish and fish in Sweden

The effects of lime treatment on crayfish (Astacus astacus and Pacifastacus leniusculus) populations in 17 lakes and fish populations in 47 lakes and 7 rivers within the trial period 1976–82 have been evaluated. An increase in the catch of crayfish per unit effort was observed in 7 lakes, although significantly in one lake only. The varying results in the other lakes indicate that factors other than pH may be of greater importance for the development of crayfish populations after liming. Recruitment of fish improved in waters where liming resulted in pH >5.5. In lakes with pH <5.5 before and pH >5.5 after treatment, there was a significant increase in the number of fish caught, from 12 to 34 per unit effort. Due to improved recruitment the individual average weight was smaller and hence the catch in weight per unit effort was about the same as before liming. After lime treatment in streams which resulted in a stable pH of >5.5, the abundance of juvenile salmonids increased to numbers found in non-acidified streams. In other streams acid spates reduced the positive influence of liming on the abundance of juvenile salmonids.     

Relations between organic carbon and methylmercury in humic rich surface waters from Svartberget catchment in northern Sweden

Monthly sampling of a mire outlet and two tributaries, one of them originating in the mire, on the Svartberget catchment in northern Sweden was performed during one year. The concentration of total organic carbon (TOC) in the three waters was fairly high (10–40 mg/l). Methylmercury (MeHg) was analysed in the original water sample (MeHg-whl) and in the humic fraction (MeHg-hum). The MeHg-hum increased with increasing concentration of humic substances (HS; measured as absorbance at 254 nm) in the water. A seasonal variation of the MeHg-hum/TOC ratio was superimposed on a negative relationship to the water flow, which indicates that the methylation is a slow process which results in a rapid drainage of the storage during periods of high flow. A minimum of the MeHg-whl/TOC ratio observed during the spring flood was followed by a slow increase during the rest of the year.     

Integrated studies of the effects of liming acidified waters (ISELAW-programme)

To assess the long-term (>15 years) effects of liming, an integrated programme for studies of the effects of liming in acidified waters (ISELAW) was initiated in 1989. At present, 14 lakes and 14 streams are included in the programme. Although on average of 14 years have passed since the first lime treatment, and the chemical goal of liming have been achieved in all lakes, i.e. to raise pH over 6.0 and alkalinity over 0.1 meq 1–1, changes in biota could still be observed in several of the lakes. Species richness and species diversity was in general not different in the limed lakes as compared to circumneutral reference lakes, although the composition of the fauna did not resembled that of neutral lakes. Among zooplankton, rotifers were still more abundant than expected in limed lakes. The fish communities appeared unstable and the species proportions as well as population structures are changing, partly as a result of re-colonisation of acid-sensitive species after liming. The results indicate that the long-term changes may persist for more than 15 years after liming and emphasise the importance of comparable time series in non-limed lakes.     

Water chemistry in forested catchments after topsoil treatment with liming agents in South Sweden

Critical loads of sulphur and nitrogen are exceeded in South Sweden, and nutritional imbalances are expected to appear with time in forests. During 1984 paired catchments were established in a northwestern-southeastern gradient in South Sweden. The aim was to study long-term liming effects on throughfall, soil water, groundwater and runoff. Dolomitic limestone and wood ash were tested at one locality, Hagfors (59° N). Three adjacent catchments were used; one reference area, one treated with dolomitic lime (0.5 kg/m²) in 1985, and one with wood fly ash (0.22 kg/m²) in 1988. The lime and the fly ash was granulated and applied by a helicopter in the end of May. Measurements concerning chemistry of the precipitation, throughfall, soil water and runoff has been conducted since spring 1984. The results showed that top-soil spreading of liming agents, besides the desired effects on soil chemistry, after some years also affected the quality of the recipient water. In the dolomitic lime treated catchment the positive effects were most obvious, with raised pH-, Ca-, and Mg-values and lowered Al-, Fe- and Mn-values. A positive trend regarding lower nitrogen (NO₃ ^?) leaching could also be calculated. Wood ash in the used amount affected only slowly, but after six years the runoff water indicated increased pH-values as well as increased Ca- and K-values and Ca/Al-ratios. Dolomitic lime in the amounts of 0.5 kg/m² was concluded to be sufficient to achieve positive effects in catchments of the present type. Wood ash in the amount of 0.22 kg/m² although enough for recycling purposes, was not sufficient enough in increasing pH in runoff to prevent acid leaching from the forest soils.     

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.     

Pools and fluxes of carbon and nitrogen in 40-year-old forest liming experiments in Southern Sweden

Soil samples were collected from litter, humus and mineral soil layers to a depth of 50 cm in 37–42 year-old limed and unlimed plots in one beech and three spruce stands in S Sweden for determination of carbon (C) and nitrogen (N) pools, C and N mineralization rates and nitrification rates. The samples were sifted while still fresh and incubated at a constant temperature (15°C) and soil moisture (50 % WHC) for 110–180 days with periodic subsamplings. The C and N pools in the uppermost soil layers were significantly lower in plots limed with 9–10 t CaCO₃ ha^?1 than in unlimed plots, whereas the pools in the deeper mineral soil did not differ markedly between the treatments. In the whole soil profile, the C and N pools had, on average, decreased by 16% (P<0.05) and 11% (P>0.05), respectively, after 40 yrs. The smaller reduction in N pools resulted in significantly lower C:N ratios and increased N immobilization in the limed spruce plots but not in the limed beech plot. C and net N mineralization rates were increased in some of the limed plots and decreased in others. This indicates that liming can still have a stimulatory effect after 40 yrs in some soils. The nitrification potential was increased in the limed plots. Liming did not increase tree growth in the stands investigated. We conclude that liming with high doses of CaCO₃ is likely to reduce pools of soil C and possibly even soil N in relation to unlimed areas in spruce and beech forests in S Sweden. If trees in limed stands do not respond with better growth, the treatment will thus result in a net ecosystem loss of C and N in relation to unlimed areas. It was not possible to conclude whether the effects of low doses of lime would be similar to those of high doses.     

Influence of wetland liming on water chemistry of acidified mountain streams in Lofsdalen,Central Sweden

Acidic precipitation has caused damage to the populations of fish and invertebrates in numerous streams in the southern part of the Swedish mountain range. In the middle of the 70's, the pH of precipitation decreased and has since then frequently been lower than 4.5. Many of the streamwaters were well buffered during most time of the year, but during periods with high discharge, the buffering capacity was completely exhausted, pH frequently decreased to around 4.5 and very high levels of Fe, Mn and Al occurred. In general, base cations (BC) and organic anions decreased during periods of high flow, while SO₄ increased or was relatively independent of flow. On an average, the ratio SO₄/BC was negatively correlated to pH, while organic anions/BC showed a weaker correlation to pH. In order to investigate if wetland liming could be used as a remedial measure in such areas, lime treatments were started in 1983 in the Lofsdalen area, province of Härjedalen. The liming stabilized the alkalinity and pH of the streams at circum-neutral levels, and reduced the leaching of Fe, Mn, and Al. The average levels of these elements decreased and the seasonal fluctuation decreased considerably.     

Acidity status of surface waters in Massachusetts

The Massachusetts Acid Rain Monitoring project surveyed 80.5% of the state's 5294 named water bodies between 1983 and 1985. PH and acid neutralizing capacity (ANC) were measured monthly the first 14 mo and semi-annually afterwards. Sample collection and analysis were performed by volunteers. The majority of surface waters in Massachusetts were found to be sensitive to possible long term acidification, with 63% exhibiting ANC less than 200 μeq L^?1 and 22% with ANC less than 40 μeq L^?1. Seasonal patterns in ANC were observed, the median ANC being 384 μeq L^?1 in summer/fall and 134 μeq L^?1 in winter/spring. Geographical differences were also found across the state: the streams and lakes with lowest pH and ANC were located in the southeastern and north-central parts of the state, while the most alkaline surface waters were found in the western-most part of the state, which is the only area of the state with significant limestone deposits.     

Effects of acidification on the concentrations of heavy metals in running waters in Sweden

Heavy metals in running water are analysed within the Swedish Surface Water Monitoring Programme at about 80 stations. Data for selected rivers and brooks has been used to assess the effect of soil acidification on the concentrations of metals in waters. In southern Sweden, acidification shows a significant effect on Zn and Cd. In the upper parts of the drainage areas, there is an marked increased leakage of these metals from soils to waters indicated by elevated concentrations of Zn and Cd in brooks and also by high maxima during periods of low pH values. The increased leaching from forest soils also influences the concentrations in rivers in southern Sweden. During periods of high water flow, the pH values of the rivers decreases and the concentrations of Zn and Cd increases. At pH levels of 6.2–6.5 the concentrations of these metals are mostly 2–5 times higher as compared to pH levels of about 7.0. Since high concentrations of Zn and Cd coincides with high water flow, the transport of these metals has most certainly increased several times compared to the pre-industrial period. Hence, the by far most important human impact on the loading of Zn and Cd on the marine areas, surrounding southern Sweden is the increased leakage of these metals due to acidification. In northern Sweden the effects of acidification on Zn and Cd are less evident. In general, the concentrations of these metals are lower and the connection between pH and these metals are much less significant in the rivers. The links between acidification and the concentrations of Pb and Cu in the watercourses are comparatively much weaker. These two metals are more related to the content of organic matter in the waters and a possible effect of acidification is overshadowed by natural transport processes in soils and waters.     

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.     

Effects of liming and acid surface water on the mayfly Leptophlebia vespertina in Lake Hovvatn

The acidified Lake Hovvatn have been limed in 1981, 1987, 1989 and 1991. After the first liming the lake reacidified close to the prelimed condition. The reliming, which started in 1987, was planned to maintain the pH at a relatively high level for the lake. A detailed monitoring of pH and temperature was performed at depth 0.5, 1, 1,5 and 5 m since spring 1993. Quantitative samples of benthic invertebrates were taken in spring and fall in 1977 and regularly at the same seasons from 1981 at depth 0.5, 2, 5 and 10 m. A reference lake, Lille Hovvatn have been sampled with the same procedure since 1988. The acid tolerant mayfly Leptophlebia vespertina responded quickly to the first liming with a 20 times increase in density after a few months. However, the densities rapidly decreased during the first years of reacidification. The lime treatments in 1987 and 1989, resulted in a second peak in density in 1990. After this, the densities have been reduced in spite of generally good water quality in Hovvatn. During fall the density increase was significant at 0.5 m depth in 1990, at 2 m depth in 1989, 1990 and 1992 and at 5 m depth in 1988 to 1990. No significant increase was observed in the limed localities during spring. It is concluded that acid surface water, prior to ice break, affect the food resources to L. vespenina and reduce the population at all depths during spring and in the littoral zone in fall.     

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.     

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.     

Sensitive surface waters — A UK perspective

This overview of sensitive surface waters in the United Kingdom has focused on palaeolimnological studies, the estimation of acidification values according the Henriksen, and correlation with non-marine sulphate values of available chemical data and trends in salmonid populations. The palaeolimnological studies of lakes with unafforested catchments in Galloway led to the conclusion that changes in water acidity, since the 1800's, have been caused by acid deposition. Significant differences in stream chemistry between mature conifer forests and adjacent moorland catchments, in both Wales and Scotland, suggest that afforestation as well as acid deposition have contributed to the decline and, in some areas, the elimination of the salmonid population.     

Background concentrations and loadings of nitrogen in Danish surface waters

Quantitative knowledge of background nitrogen (N) concentrations and loadings is essential for as it determines the minimally disturbed conditions for N in surface waters as a near reference condition. To determine background N concentrations, a total of 39 smaller Danish streams draining relatively undisturbed catchments in different regions were selected and screened for N concentrations and discharge during a 1-year period (2004–2005). Only 19 of the streams fulfilled the threshold set for least disturbed conditions (LDC) in their catchments (proportion of agricultural land <10%). Within the five sampled dominant landscape types in Denmark, the concentrations of ammonium N and total organic N in the LDC streams were found to be nearly constant: 0.05 ± 0.01 mg N L^?1 and 0.53 ± 0.07 mg N L^?1, respectively. In contrast, the concentration of nitrate N differed significantly (P < 0.05) between the five landscape types, with variations between 0.06 and 0.83 mg N L^?1. An analysis of all the 39 streams sampled demonstrated significantly different relationships between the proportion of land use and the flow-weighted annual concentration of nitrate N for two dominant soil types with a Y-axis intercept equal to 0.12 mg N L^?1 for streams draining coarse textural soils and 0.76 mg N L^?1 for streams draining finer textural soils. A significant (P < 0.05) downward trend (18–41%) emerged for flow-weighted annual total N concentrations in four of the five streams that were sampled during the period 1990–2011. A 5 × 5 km grid map of Denmark showing nitrate N and total N background concentrations was produced and used for estimating background N losses to Danish surface waters. Based on the grid map, the average annual background loss of total N was calculated to be 13,000 tonnes N or 19% of the total N loading to Danish coastal waters during the period 2004–2005.     

Soil organic matter pools and carbon-protection mechanisms in aggregate classes influenced by surface liming in a no-till system

The stabilisation of soil organic matter (SOM) is the result of the simultaneous action of three mechanisms: chemical stabilisation, biochemical stabilisation and physical protection. The objectives of this study were (i) to evaluate carbon-protection mechanisms in different SOM pools in soil aggregates and (ii) to identify the association of Ca^2 + with total organic carbon (TOC) under the influence of surface liming in a medium-textured Oxisol in a long-term experiment under no-till system (NTS) in southern Brazil (25° 10′ S, 50° 05′ W). The treatments consisted of application of zero or 6 tons ha^? 1 of dolomitic lime on the soil surface in 1993 and a reapplication of zero or 3 tons ha^? 1 of dolomitic lime in 2000 to plots with or without previous lime application. Soil samples collected at depths of 0–2.5, 2.5–5, 5–10 and 10–20 cm were separated into seven aggregate classes. In each of these classes, TOC, particulate organic carbon (POC) and mineral-associated organic carbon (MAOC) were analysed. The 8–19 mm sized aggregates from the 0–2.5 cm layer were assessed by energy-dispersive X-ray spectroscopy (EDS) for the elemental analysis of carbon (C) and calcium (Ca). The liming caused an accumulation of TOC in the aggregates, mainly at a depth of 0–2.5 cm. The aggregates from soils treated with lime had a higher mean weight diameter (MWD) that resulted in the accumulation of TOC, especially in the 8–19 mm aggregate class, that was linear and closely related with C input (R² = 0.99). The proportion of large aggregates in the treatments with lime was closely correlated with the TOC content of the whole sample. The largest dose of lime (9 tons ha^? 1) resulted in higher TOC, POC and MAOC values, mainly in the 8–19 mm aggregate class. The elemental analyses for C and Ca revealed similar spectra between them for the surface-liming treatments in the clay fraction found in the centres of the 8–19 mm aggregates. The surface application of lime to NT fields provided greater stability and protection of the intra-aggregate C, presumably due to Ca^2 + acting as a cationic bridge between OC and the kaolinite in the clay fraction.     

Acidification of surface waters in two areas of the Eastern United States

Acidification by precipitation of undisturbed, upland surface waters was examined in the White Mountains of New Hampshire and the Blue Ridge Mountains of North Carolina. The pH and alkalinity of samples taken in the summer of 1979 were compared to those taken in North Carolina in the early 1960s and in New Hampshire in the late 1930s. These parameters had declined significantly over the sampling intervals. Results were confirmed by comparing recent measurements of Ca, Mg, Na, and K to those of bicarbonate alkalinity. This comparison confirmed the hypothesis that some acidification has occurred in both areas and that acidification was more pronounced in the New Hampshire waters.