Macroinvertebrate Community and Chemistry of the Most Atmospherically Acidified Streams in the Czech Republic

We performed a comparative study of strongly acidified mountain streams covering 10 sites in the Czech Republic in the season 1999/2000. The aim of the study was to determine how acidification influenced macroinvertebrate community structure within a relatively narrow pH range. We focused on strongly acidified, non-humic running waters with low ionic content (pH < 4.6, total organic carbon < 10 mg l^?1, specific conductivity < 100 μS cm^?1) and minimum human influence in the catchment. The actual pH values ranged from 3.98 to 4.65, and concentrations of reactive aluminium ranged from 0.2 to 2.0 mg l^?1. Characteristic macroinvertebrates were the stoneflies Leuctra nigra, Nemurella pictetii, and Protonemura spp.; the chironomids Corynoneura spp.; and the caddisfly Plectrocnemia conspersa – the former two stoneflies formed together 46% of total organisms. The sites were divided into three groups with use of divisive classification. Individual groups reflected similarity in water chemistry, catchment characteristics, and geographical proximity. The largest biotic difference detected by PCA was in the abundance of stoneflies, mainly Diura bicaudata and Leuctra major. The strongest correlation with this gradient was shown by pH (and associated heavy metals), followed by the distance from source. The results show that even in such narrow pH range, the number of taxa is determined by the low pH value and related high concentrations of aluminium and heavy metals.     

Low Success Rate in Re-Establishing European Perch in Some Highly Acidified Lakes in Southernmost Norway

In order to test whether major reductions in acid inputs had improved water quality sufficiently for fish populations to recover, we stocked wild European perch (Perca fluviatilis) in three highly acidified lakes that had previously supported this species, and in one limed lake. The fish, which were introduced from a local lake (donor lake), generally ranged from 12 to 16 cm in total length, and were stocked at densities of 117–177 fish ha^?1. The untreated lakes were highly acid, with minimum pH values and maximum inorganic aluminium concentrations (Al_i) during the spring of 4.6–4.7 and 118–151 µg L^?1 respectively. In the limed lake, the corresponding values for pH and Al_i ranged between 5.8 and 6.6 and 5 and 19 µg L^?1 respectively. Gill-netting in two subsequent years after the introduction yielded only a few recruits (0+) and one adult in one of the three acidified lakes in one year only. However, stocked perch reproduced successfully in both years in the limed lake. There was a significant linear relationship between the catches (CPUE) of juvenile perch (age 0+) in the different lakes in the autumn and the water quality in May (time of hatching), both in terms of Al_i (r ²=0.934, P<0.05) and pH (r ²=0.939, P<0.05). Our data suggest unsuccessful recruitment in waters of pH <5.1 and Al_i>60 µg L^?1.     

Labile inorganic manganese — An overlooked reason for fish mortality in acidified streams?

Acid deposition has caused acid episodes and elevated concentrations of metals like Fe, Al and Mn in streams in mountain regions of Sweden. In streams in the area of Lofsdalen, central Sweden, an episode in 1978 during snow melt caused massive downstream migrations of fish. Acid episodes have occurred yearly since then. pH of 4–4.5 and high concentrations of total Fe, Mn and Al were measured during these spates. Liming measures have been carried out in a number of catchments in order to increase the pH and try to decrease the leaching of metals. The lime has been delivered on wetlands, seepage areas and areas covered by meltwater during the spring. Cage experiments were carried out with yearling brown trout in the springs of 1982, and 1985–86. Fe, Al and Mn were analysed in water samples and on/in the gills of dead and live brown trout. There were no significant correlations between mortality or average survival time and total concentrations of Fe, Al or Mn in the water or on/in the gills. Average survival time was positively correlated to pH (p< 0.01). Metal speciation was carried out in 15 experiments in 1985 and ?86. A canonical discriminant analysis showed that pH and the concentration of labile inorganic manganese in the water explained all the observed mortality (can. corr 0.89, p< 0.001). The rate of accumulation of manganese on/in the gills was correlated to the concentration of labile inorganic manganese in the water (p<0.01, r²=0.54, linear regression).     

Interrelationships between mercury levels in yearling yellow perch,fish condition and water quality

Yearling yellow perch were collected from sixteen Muskoka-Haliburton lakes to determine interrelationships between water quality, Hg residues in fish and fish condition. The lakes studied were Precambrian shield lakes with a pH range of 5.6 to 7.3 and total inflection point alkalinities of 0.4 to 16.0 mg L^?1. Mercury residues in yellow perch ranged from 31 to 233 ng g^?1 and were inversely correlated (p < 0.001; r = 0.84) with lakewater pH. Stepwise linear regression analyses selected lakewater pH as the only significant parameter associated with Hg accumulations. Alkalinities, sulphate, Ca and dissolved organic carbon (DOC) were not selected as significant. Likewise, lakewater pH and Hg residues in yellow perch were inversely (p < 0.001) correlated with fish condition. Lakewater pH, accounted for 74% and Hg in fish a further 11% of the variability in fish condition. Terrestrial drainage size/lake volume ratios were also correlated (p < 0.05; r = 0.78) with Hg accumulations in perch from a subset of nine headwater lakes. No temporal trends in Hg residues were evident in yellow perch over a 9 yr interval (1978–1987).     

Critical loads — A valuable catchment management tool?

Planning advice for forest planting in acid sensitive areas suggests that, where calculated critical loads for acidity are exceeded at a catchment level, new conifer planting may not be appropriate. In south west Scotland, acid waters are currently found in areas where critical loads are not exceeded. The rivers Cree and Bladnoch show a decline in pH of about one unit since 1970, when major afforestation of the headwaters began. No equivalent decline in pH was observed in the adjacent Water of Luce, although it receives similar inputs and has similar geology and soils. Little of the Luce catchment is afforested. Recent surveys of water quality, invertebrate fauna and salmonid fish reveal a picture of widespread acid conditions, impoverished benthos and absence of young salmon. 25 streams (total catchment >150km²) recorded pH <4.5 in high flow conditions. Critical loads for acidity were >1.5keqha^?1yr^?1 for 12 and >2keqha^?1yr^?1 for 6 of the 25 streams. Published deposition data suggested that one stream with pH <4.5 and 7 streams with pH < 5 were in areas where critical load was not exceeded. In 22 catchments, forestry was a major land use. To be effective as planning and management tools, systems must be robust and easy to operate. Critical load exceedance calculations remain research tools at the catchment level where deposition data is generally inadequate. The uncertainties inherent in critical load exceedances render them sources of argument and not beacons of enlightenment.     

Distribution of total mercury in coastal sediments from Jade Bay and its catchment, Lower Saxony, Germany

Purpose

Sediment cores provide a reliable record of mercury (Hg) contamination and can be used to study long-term Hg pollution and relevant environmental change. In the last hundred years, there were several events which may have contributed to the accumulation of Hg in Jade Bay and its catchment. This work was undertaken to assess the record in total Hg (THg) content in sediments of cores from Jade Bay and its catchment.

Materials and methods

A 5-m sediment core from Jade Bay, Lower Saxonian Wadden Sea, southern North Sea and a 12-m core from its catchment area (Wangerland, coastal zone of the Jade Bay) were used to study Hg contents in sediments. Total Hg, grain size distribution, aluminium (Al) and total organic carbon (TOC) were analysed on subsamples of both sediment cores. Total Hg was determined by oxygen combustion-gold amalgamation using DMA-80.

Results and discussion

As THg contents of the Jade Bay core were positively correlated to the sum of TOC and Al contents (r ²?=?0.86, p?<?0.001), the Hg data were interpreted using a regional normalisation function with the sum of Al and TOC as the normalisation parameters. Total Hg contents of the Wangerland core were correlated better to Al contents (r ²?=?0.70, p?<?0.001) than to the sum of TOC and Al contents (r ²?=?0.63, p?<?0.05). Therefore, Hg contents in sediments of the Wangerland core were normalised to Al contents. Comparison between enrichment factors and the background range of the sediment cores suggested that Jade Bay was contaminated about 50 years ago, and that Wangerland, or the catchment area of Jade Bay, was contaminated about 300 years ago, if no diagenetic remobilization occurred.

Conclusions

Total Hg contents of both cores were low and of no concern to the aquatic environment of Jade Bay. The Hg record was in good agreement with the history of industrial development in the region; thus, Hg deposition could have occurred through atmospheric input, ammunition residues of the Second World War and volcanic emanations, as well as through diagenetic remobilization.     

Relationship of ryegrass growth to extractable phosphorus in acidic soil amended with phosphate rock,coal combustion by‐product,limestone, and cellulose

Abstract

An improved management of phosphorus (P) is crucial for increasing crop production and improving environmental quality of acid infertile soils. Laboratory analyses and greenhouse experiments were conducted to evaluate effects of phosphate rock (PR), coal combustion by‐product (BP), limestone, and cellulose application on the relationship between soil test P and crop growth in acidic soil. Application of PR, BP, limestone, and cellulose increased soil pH, exchangeable calcium (Ca) and magnesium (Mg), and extractable P, and decreased free aluminum (Al) ion in the acid soil. Addition of BP or limestone increased P availability efficiency [PAE, mg dry matter yield (DMY) of plant per mg soil extractable P by Olsen‐P procedure] and P utilization efficiency (PUE, mg DMY of plant per mg P in the plant). There was significant positive correlation between the PAE and BP rates applied alone (r²=O.979, p<0.01) or with either PR (r²=0.972, p<0.01) or PR plus cellulose (r²=0.985, p<0.01). The PUE of ryegrass was significantly correlated with BP rates alone (r²=O.957, p<0.01) or with either PR (r²=0.906, p<0.01) or PR plus limestone (r²=O.699). The increase in PAE and PUE of ryegrass caused by BP and limestone reflected more plant root growth from increased availability of Ca and Mg and higher soil pH.     

Extreme acidification of a lake in southern Norway caused by weathering of sulphide-containing bedrock

In 1986 Lake Langedalstjenn in southern Norway was a weakly acidified lake with a pH of 5.2–5.6, and an average concentration of SO₄ of 330 μeq L^?1. The total Al concentration varied between 10 and 20 μeq L^?1 (expressed as Al³⁺). The lake supported populations of brown trout and perch and had supplied about 100 people with drinking water until the late 1980's. During 1986–1989, a dramatic change in the water chemistry occurred because of blasting of and weathering of sulphidic gneisses in the watershed. The oxidation of sulphide to sulphate (sulphuric acid) caused an increase in the SO₄ concentration of the draining stream of up to ≈ 4800 μeq L^?1. Weathering and/or cation exchange of Ca and Mg neutralized approximately 52% of the protons from the sulphuric acid production, while about 46% were consumed by mobilization of aluminium and iron. Nevertheless, about 2% of the hydrogen ions from the sulfuric acid were still present, which resulted in a stream pH of 4.0. In the lake, the pH was 4.4, and the concentrations of all major cations and anions were significantly lower than in the heavily affected stream. Mixing of the stream water with lake water, formation of aluminium-sulphate complexes and coprecipitation of Ca may explain the resulting concentrations of major ions in the lake.     

Regional Patterns of Streamwater Acidity and Catchment Afforestation in Galloway,SW Scotland

This paper investigates the regional relationships between highflow water chemistry and conifer forest cover in 95 streamsspread over an area of approximately 2000 km² in Galloway,south-west Scotland, paying particular attention to the use ofdetailed catchment area data. Catchment forest data areextracted from a 30 m resolution tree height map derived fromsatellite imagery; geology data from a digital geology map; andaltitude and slope data from a 50 m resolution Digital TerrainModel (DTM). The results show that over the entire region pHlevels are lower with increasing catchment afforestation whilstaluminium concentrations are higher. Concentrations of sulphate arealso higher with increasing afforestation, which suggests thatconifers play a primary role in increasing the acidity levels ofstreams by exacerbating aerial acid deposition in the entireregion.     

Annual Variations of Needle Surface Characteristics of Pinus Sylvestris Growing Near the Emission Source

In present study, pollutant effects on needle surface characteristics of Pinus sylvestris in the area affected by a nitrogen fertilizer plant have been investigated over 1994–1997 year period. Near the factory, sites with 15–25-year-old trees on a 0.5–22 km interval were chosen. Mean monthly concentrations of NO₂ and NH₃ varied across the transect in the range of 1.8–8.8 µg m^?3 and 1.8 – 69.3 µg m^?3, respectively. NH₃ concentrations exceeded the critical level (>23 µg m^?3) only in the 0.5 km vicinity. Assessment of needle surface wettability by measuring contact angles (CA) of water droplets and surface quality by measuring stomatal area covered by structural wax (SW) revealed significant (p<0.05) needle age, site, and year of sampling related differences. Comparison of SW between sites showed reliably (p<0.05) higher surface wax erosion on one-year-old needles sampled in the area, where ammonia concentration exceeds critical level. Significant correlations between site SW on one-year-old needles and distance from the pollution source, NO₂ and NH₃ concentrations were detected (r = 0.539; r = ? 0.495; r = ? 0.426; p<0.001, respectively). Correlations between CA and factors mentioned were lower.     

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.     

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.     

Effects of organic and inorganic calcium compounds on soil-solution pH and aluminium concentration

The reactions of two organic (citrate and fulvate) and two inorganic (chloride and phosphogypsum) calcium compounds were studied during leaching of columns of unsaturated acidic soil. The potential of these compounds to decrease the aluminium concentration in the soil solution and remove exchangeable aluminium, and their effects on soil acidity are described. The calcium citrate solution increased the soil solution pH from 5 to a maximum value of 7 in the upper portion of the column. In contrast, the fulvate, calcium chloride and phosphogypsum solutions had little effect on soil-solution pH. Treatment with calcium citrate, or fulvate solution that contained 51 mm Na, removed most of the exchangeable aluminium from the column. The cation exchange sites in the upper portion of the column were saturated with calcium, and the cation exchange capacity of the soil was increased from 35 to c. 80 mmol_c kg^?1 in the calcium citrate treatment. Leachate from this treatment contained low (< 2 mm ) calcium concentrations and high aluminium concentrations. In contrast, the above changes were not shown by the calcium chloride and phosphogypsum treatments. In these treatments the calcium concentration in the leachate was equal to that in the inflowing solution, which indicated that calcium was transported through the entire column. These results suggest that calcium alone was ineffective in displacing aluminium from the cation exchange sites and a strong complexing agent such as citrate or fulvate is needed to mobilize the exchangeable aluminium.     

Solubility of a proto-imogolite sol in oxalate solutions

The amounts of aluminium liberated from a proto-imogolite (P-I) sol by 1–3 mM oxalate at pH 4·8–7·1 are found to be in excellent agreement with those calculated on the basis of the solubility product of the P-I sol, and the stability constants for aluminium oxalate complexes established earlier. Calculated solubility curves are presented for proto-imogolite sols in the presence of 10^?3, 10^?4 and 10^?5 M total oxalate over the pH range 4–8, and also for the case where oxalate concentrations are controlled by solid calcium oxalate in the presence of 0·05, 0·5 and 5 mM calcium ion. We conclude that the presence of a proto-imogolite allophane in podzol B horizons of pH 5·0 requires oxalate concentrations less than 10^?5 M. For fertile agricultural soils with typical calcium concentrations (approximately 5 mM) in the soil solution, aluminium oxalate concentrations would be limited by calcium oxalate solubility to less than 10^?6 M in the presence of proto-imogolite allophane at pH values exceeding 5·5. In leached podzolic soils calcium concentrations are generally less than 0·05 mM, and would not limit the formation of aluminium oxalate complexes.     

Effects of aluminium ions on uptake of calcium,magnesium and nitrogen in Betula pendula seedlings growing at high and low nutrient supply rates

The effects of aluminium on plant nutrition in small birch plants (Betula pendula Roth) were investigated. By using relative addition rate (r _A, g g^?1 d^?1) of nutrients as the growth-controlling variable, it was possible to grow the plants at very low external nutrient concentrations and to simulate plant requirements at two different fertility levels. Before aluminium addition the plants were at steady-state relative growth rate, (R _G, g g^?1 d^?1). The two addition rates were free access of nutrients with R _G ≈ 0.215 d^?1, or nutrient-limited, R _Aand R _G=0.10 d^?1. Internal concentrations of calcium and magnesium decreased with increasing Al³⁺ conncentration in the nutrient solution while nitrogen concentrations in the plants remained unchanged or increased. It was demonstrated in both nutrition treatments that calcium and magnesium decrease per se does not reduce plant growth and that uptake has to be considered in relation to plant requirement at different growth rates. The interpretation of the effects of aluminium on Ca and Mg uptake and plant biomass development suggested that processes other than disturbances in Ca and Mg uptake are the cause of the decrease in growth.     

Dissolved Organic Nitrogen Concentrations and Ratios of Dissolved Organic Carbon to Dissolved Organic Nitrogen in Throughfall and Soil Waters in Norway Spruce and Scots Pine Forest Stands Throughout Norway

Dissolved organic nitrogen (DON) plays an important ecological role in forest ecosystems, and its concentration is related to that of dissolved organic carbon (DOC). We investigated DON concentrations and ratios of DOC to DON in throughfall and soil waters in 16 Norway spruce and two Scots pine forest stands sampled at weekly intervals between 1996 and 2006. The stands are all included in the ICP Forests Level II monitoring program and are located throughout Norway. DON concentrations were significantly and positively related to DOC concentrations in throughfall (r ²?=?0.72, p?<?0.0001) and soil water at 5, 15, and 40 cm (r ²?=?0.86, 0.32, and 0.84 and p?<?0.0001, 0.04, and <0.0001, respectively). At most sites, the annual median DOC/DON ratio in throughfall ranged from 20.3 to 55.5, which is lower than values in soil water, which ranged from 24.5 to 81.3, gradually decreasing with soil depth. DON concentrations varied seasonally in throughfall at many plots and in soil water at 5-cm depth at one plot only, with higher values in the growing season, but there was no noticeable seasonality at greater depth. The ratios of DOC/DON in soil water were significantly positively related to the C/N ratio in soil at the same depth. Above-ground litter input was the main factor having a significant, negative relationship to DOC/DON in soil water at all depths studied. This might reflect the effect of site conditions on both DOC/DON ratios and litter quantity.     

Chemical and Biochemical Characteristics of Alpine Soils in the Tatra Mountains and their Correlation with Lake Water Quality

Soils and lakes were sampled in fifteen catchments in the alpinezone of the Tatra Mountains (Slovak-Polish border) to evaluate the dependence of lake water chemistry on soil properties. The amount of soil in alpine meadows varied from 38 to 255 kg m^-2 (dry weight soil <2 mm; average of 121 kg m^-2). The average cation exchange capacity (CEC) was 12 eq m^-2, average base saturation was 12%, and average ${\text{pH}}_{{\text{CaCl}}_{\text{2}} } $ was 4.0. Moraine areas had, on average, 13 kg m^-2 of <2 mm soil in small deposits between stones. Their chemical properties were similar to mineral horizons of alpine soils but had higher concentrations of P forms. Soil composition was spatially uniform, having coefficientsof variation of all parameters between 5 and 115%, and did not exhibit significant differences between the catchments or along the elevation gradient. Variation in pools of soil constituents was ～2-fold higher. Soil organic matter concentration was theparameter that most strongly and positively correlated with N, P, S, CEC, exchangeable base cations, exchangeable acidity, and all biochemical parameters (C, N, and P in microbial biomass and C and N mineralisation rates). Lake water concentrations of organic C, N, and total P were positively correlated (P < 0.01) with the pool of soil organic matter in the catchments, while NO₃ ^- concentrations were negatively correlated (P < 0.001). No correlations were found between C, N, and P concentrations in lakes and soil chemistry, indicating the dominant role of soil quantity over quality for surface water composition in the Tatra lakes. Relatively high concentrations of Ca²⁺, Na⁺, SO₄ ^2-, reactive Si, and acid neutralising capacity in some lakes were not explained by soil characteristics, and were more probably related to bedrock composition and structure.     

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.     

Relating Tree Ring Chemistry of Pinus densiflora to Precipitation Acidity in an Industrial Area of South Korea

To test the possible use of tree ring chemical properties as proxies for precipitation acidity ([H⁺]), we investigated the relationships between tree ring chemistry (δ¹³C, δ¹⁵N, Ca-to-Al ratio, and N concentration) of Pinus densiflora and precipitation [H⁺] between 1992 and 2005 in an industrial area in the southwest region of South Korea. Statistical analyses showed that all tree ring chemistry parameters were significantly correlated with precipitation [H⁺]. Tree ring δ¹³C was negatively correlated with precipitation acidity (r?=??0.67, P?<?0.01), reflecting the photosynthetic fixation of ¹³C-depleted CO₂ from fossil fuel combustion that would be the primary source of precipitation acidity. A positive correlation of N concentration (r?=?0.89, P?<?0.001) and a negative correlation of δ¹⁵N (r?=??0.63, P?<?0.05) in tree rings with precipitation acidity most likely reflected the influence of ¹⁵N-depleted N compounds deposited via precipitation. The Ca-to-Al ratio was negatively (r?=??0.58, P?<?0.05) correlated with precipitation acidity, indicating that soil acidification caused the loss of Ca from the soil and solubilization of Al resulting from acid precipitation. Such relationships suggest that δ¹³C, δ¹⁵N, N concentration, and Ca-to-Al ratio in tree rings can be reliably used to evaluate the impact of acid precipitation on the studied P. densiflora stands.