Avoidance of low pH and elevated Al concentrations by Brook Charr (Salvelinus fontinalis) Alevins in laboratory tests

Laboratory studies were conducted to test the ability of brook charr (Salvelinus fontinalis) alevins, the earliest free-swimming life stage of the species, to detect and avoid toxic levels of H⁺ and inorganic Al. Alevins were tested in steep gradient choice tanks using a range of H⁺ (pH 4.0 to 5.5) and Al (0 to 500 μg L^?1) concentrations in low Ca (2.0 mg L^?1) water. The young brook charr actively avoided acidic water with a pH < 5.0. Aluminum additions of 500 μg L^?l increased the avoidance response. The observed behavioral response of alevins to low pH and elevated levels of Al, may be of significant adaptive advantage in systems undergoing acidification.     

Chemical effects of spring and summer alum additions to a small,Northwestern Ontario Lake

Aluminum was added as aluminum sulfate (alum) to Lake 114, a small, shallow lake of the Experimental Lakes Area, northwestern Ontario, in spring and summer point-source additions. Aluminum and H⁺ gradients were established during the additions, with high Al and low pH (about 1000 μg L^?1 Al, pH 4.7) near the alum sources, and background conditions (< 50 μg L^?1 Al, pH 5.7) further from the sources. Approximately 80% of the added Al was lost from the water column in two weeks. Phosphorus concentrations remained unchanged during the additions, whereas lake alkalinity decreased and sulfate increased close to the sources. Dissolved organic carbon (DOC) concentrations decreased slightly (from 540 μM L^?1 to about 500 μM L^?1) near the alum source during the summer addition.     

Aluminum chemistry in two pristine alpine lakes of the Central Cascades,Washington

A field investigation of the Al chemistry in two adjacent dilute alpine headwater lakes of the Central Washington Cascades was conducted. Quartz Lake is naturally acidic, pH ca. 5.3, due to local geologic sources of S. By contrast, Hi Lo Lake has a pH of ca. 6.0 decreasing to 5.4 during storm episodes in the spring and fall due to cation dilution and increased levels of organic acids. Total Al levels were as high as 156 μg L^?1 in Hi Lo Lake and 127 μg L^?1 in Quartz Lake during high flow spring and fall, whereas summer Al concentrations were 4 and 2 fold lower in Hi Lo and Quartz lakes, respectively. The peak Al concentrations were approximately 4 to 5 times greater than the median total Al levels for Washington Cascade lakes observed by the EPA. Variable flow paths and organic acids are hypothesized to control Al solubility, and the acid-base chemistry of Hi Lo Lake. However, at Quartz Lake sulfate weathering in the groundwater zone appeared most important for Al chemistry controls.     

Localization of aluminum in tissues of fish

The concentrations of Al in fish gills has been used as a measure of fish exposure to this metal in acidified waters. This experiment was designed to determine if other fish tissues also accumulate Al and thus possibly contribute to the cause of death. Rainbow trout (Salmo gairdneri) were exposed to the following fours test conditions for 48 hr or until death: (1) pH 6.8, <0.001 mg.L^?1 Al (n=6); (2) pH 5.2, <0.001 mg₁L^?1 Al (n=2);(3) pH 5.2,1.0 mg.L^?1 Al (n=5); (4) pH 6.8, 1.0 mg.L^?1 Al (n=3). The trout were held in synthetic, low Ca water prior to, and during, experimentation. Esophagus-stomach, gonad, gall bladder, gill (left and right), heart, intestine, kidney, liver, muscle (epaxial), and spleen were digested in a 4:1 mixture of HNO₃:HClO₄ and analyzed by Inductively Coupled Plasma Emission Spectrophotometry. Elevated Al concentrations were found in gill and gastrointestinal tissues. Left and right gills of fish exposed to pH 5.2, 1.0 mg.L^?1 Al were the only tissues found to be significantly different (p<0.01) between the test conditions. The mean total Al concentrations of these test 3 fish, for the left and right gill were 3.61 and 4.33 mg.g^?1 Al dw. The Al concentration in thle gastrointestinal tissues of the fish exposed to pH 6.8 at 1.0 mg.L^?1 Al was greater than that of the control fish, but not statistically significant. These results suggest that the analysis of whole gill remains an effective indicator of Al exposure in fishes at low pH.     

The effects of low pH,low calcium concentrations and elevated aluminium concentrations on sodium fluxes in brown trout,Salmo Trutta L.

The effects of pH (c. 7.0, 5.4, 4.5 and 4.0), nominal Al levels (0 and 8 μmol L^?1) and Ca levels (10 and 50 μmol L^?1) on Na influx, efflux and netflux of brown trout have been investigated using artificial lake water of known composition. Low pH had little effect on influx, but tended to increase efflux, particularly in the low Ca treatments. A nominal addition of 8 μmol Al L^?1 at pH 4.5 and 4.0 reduced influx significantly. Efflux was unaffected. Aluminium addition at pH c. 7.0 and 5.4 had no such effect. The measured Al concentrations at the end of the static 8 hr flux measuring experiments were markedly lower than the nominal amount of A1 added to the start.     

Aluminum retention in a man-made Sphagnum wetland

Runoff from a highway interchange in western Maryland had Al concentrations averaging about 50 mg L^?1, with a maximum of 206 mg L^?1. As an alternative to expensive chemical treatment of this Al-rich water, in August 1984, the drainage was diverted through a 500 m² man-made wetland, constructed from organic peat. For a 10 week period, Al concentrations in water leaving the wetland averaged 1.5 mg L^?1. as compared to Al concentrations at the two major inflows to the wetland of 35.3 and 6.6 mg L^?1. However, effective treatment of the drainage by the wetland was not observed over the entire 27 mo sampling period. Peat chemical analysis indicated that over the 27 mo, total Al concentration in the peat increased from 2375 μg g^?1 to 13 634 μg g^?1. Of this increase 5.5 % was contributed by exchangeable Al, 4.3% by adsorbed Al, 39.8% by organically bound Al, 33.1% by oxide bound Al, and 17.2% by precipitated and residual Al. Changes in Fe, Mn, Ca, Mg, K, and Na chemistry in the peat associated with Al retention are discussed.     

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.     

Can Phosphate Help Acidified Lakes to Recover?

Experimental addition of phosphate to enclosures in an acidified lake in Southern Norway was performed to study the effect on nitrate, pH and labile aluminium along a gradient of phosphate from 4–19 µg P L^?1. Nitrate decreased from 180 µg L^?1 to below detection limit after three weeks at P-concentrations > 17 µg L^?1, due to phytoplankton uptake. pH increased from 4.9 to 5.2, corresponding to a 50% decrease of H⁺-equivalents from 12 to 6 µg P L^?1 due to algal uptake of H⁺-ions when assimilating NO₃ ^?-ions. Due to the increased pH and probably also precipitation with phosphate, concentrations of labile aluminium decreased from 150 to 100 µg L^?1 within the P-interval 4–19 µg L^?1. Algal biomass increased from 0.5 to 6 µg chlorophyll a L^?1 along the same P-gradient. The results suggest that moderate P-addition (< 15 µg P L^?1 to avoid eutrophication problems) can improve water quality in moderately acidified lakes, and also increase nitrate retention in strongly acidified lakes. In humic lakes, the treatment will be less efficient due to light limitation of primary production and the presence of organic acids.     

Counteractions Against Acidification in Forests Ecosystems. Effects on stream water quality after dolomite application to forest soil in Gjerstad,Norway

The deposition of strong acids is one of many threats to forest ecosystems and viable forestry. Several counteractions against acidification have been launched, e.g. changes in forestry management and the introduction of chemicals. The inter-institutional programme “Counteractions Against Acidification in Forest Ecosystems” was established in 1993 to evaluate existing knowledge and run experimental and fullscale field experiments. A total of 240 metric tons of coarse dolomite powder was spread by helicopter in September 1994 on 84 ha forest catchment dominated by pine (Pinus sylvestris) and Norway spruce (Picea abies). Potential desirable and undesirable effects after this carbonate application may be less pronounced than recorded at other sites due to the relatively moderate dose (3 tons ha^?1). Pre-liming stream water quality (mean values for May 1993-September 1994) was as follows: pH 4.8; Ca 1.13 mg L^?1; reactive Al (RAl) 248 μg L^?1; inorganic monomeric Al (Al) 72 μg L^?1. The reference station was slightly higher in Ca and slightly lower in both RAl and Al. Dolomite application resulted in a significant increase in pH to 5.7 as mean value for the post-liming period (September 1994-April 1995). Both Ca and Mg increased significantly after liming, and both RAl and Al, declined significantly. The rapid detoxification of stream-water may be explained by dissolution of dolomite particles in both streams and catchment, a resulting pH increase and change in Al species composition. Retention of Al in the catchment probably explains the reduction in RAl. No increase in NO₃, total N, total P or TOC was recorded the first seven months.     

Time and Ph-Dependent Detoxification of Aluminum in Mixing Zones between Acid and Non-Acid Rivers

Liming detoxifies aluminum in a time-dependent process following the increase in pH. Transformation of Ali into non-reactive or colloidal forms of Al reduces toxicity. To investigate the effects of pH on the detoxification rate, Atlantic salmon (Salmo salar) parr were exposed in four identical channel-tank setups differing only in mixing ratio (30:70, 16:84 or 6:94) between acid (pH 5.6, total Ali 90 µg Al·L^?1) and non-acid water (pH 6.3, total Ali 3 µg Al·L^?1). Two channels had identical mixing ratio (30:70), but differed with respect to pH (6.0 or >6.4) due to addition of lime. Fish were exposed for 140 hrs. in waters aged from 1 minute and up to 4 hours after mixing. Ali decreased within minutes after mixing at pH 6.4. The detoxification process required hours at pH 6.0. Al accumulation onto fish gills and fish homeostasis was related to Ali. The data suggest that the detoxification process, and therefore the water body affected by ongoing polymerization, was strongly influenced by pH, where a pH target for liming set at pH 6.4 detoxified water faster than a pH target of pH 6.0.     

Toxicity of heavy metals (Zn,Cu, Cd,Pb) to vascular plants

The literature on heavy metal toxicity to vascular plants is reviewed. Special attention is given to forest plant species, especially trees, and effects at low metal concentrations, including growth, physiological, biochemical and cytological responses. Interactions between the metals in toxicity are considered and the role of mycorrhizal infection as well. Of the metals reviewed, Zn is the least toxic. Generally plant growth is affected at 1000 μg Zn L^?1 or more in a nutrient solution, though 100 to 200 µg L^?1 may give cytological disorders. At concentrations of 100 to 200 μg L^?1, Cu and Cd disturb metabolic processes and growth, whereas the phytotoxicity of Pb generally is lower. Although a great variation between plant species, critical leaf tissue concentrations affecting growth in most species being 200 to 300 μg Zn g^?1 dry weight, 15 to 20 μg Cu g^?1 and 8–12 μg Cd g^?1. With our present knowledge it is difficult to propose a limit for toxic concentrations of Zn, Cu, Cd and Pb in soils. Besides time of exposure, the degree of toxicity is influenced by biological availability of the metals and interactions with other metals in the soil, nutritional status, age and mycorrhizal infection of the plant.     

Sources of Nitrate in Snowmelt Discharge: Evidence From Water Chemistry and Stable Isotopes of Nitrate

To determine whether NO₃ ^? concentration pulses in surface water in early spring snowmelt discharge are due to atmospheric NO₃ ^?, we analyzed stream δ¹⁵N-NO₃ ^? and δ¹⁸O-NO₃ ^? values between February and June of 2001 and 2002 and compared them to those of throughfall, bulk precipitation, snow, and groundwater. Stream total Al, DOC and Si concentrations were used to indicate preferential water flow through the forest floor, mineral soil, and ground water. The study was conducted in a 135-ha subcatchment of the Arbutus Watershed in the Huntington Wildlife Forest in the Adirondack Region of New York State, U.S.A. Stream discharge in 2001 increased from 0.6 before to 32.4 mm day^?1 during snowmelt, and element concentrations increased from 33 to 71 μmol L^?1 for NO₃ ^?, 3 to 9 μmol L^?1 for total Al, and 330 to 570 μmol L^?1 for DOC. Discharge in 2002 was variable, with a maximum of 30 mm day^?1 during snowmelt. The highest NO₃ ^?, Al, and DOC concentrations were 52, 10, and 630 μmol L^?1, respectively, and dissolved Si decreased from 148 μmol L^?1 before to 96 μmol L^?1 during snowmelt. Values of δ¹⁵N and δ¹⁸O of NO₃ ^? in stream water were similar in both years. Stream water, atmospherically-derived solutions, and groundwaters had overlapping δ¹⁵N-NO₃ ^? values. In stream and ground water, δ¹⁸O-NO₃ ^? values ranged from +5.9 to +12.9‰ and were significantly lower than the +58.3 to +78.7‰ values in atmospheric solutions. Values of δ¹⁸O-NO₃ ^? indicating nitrification, increase in Al and DOC, and decrease in dissolved Si concentrations indicating water flow through the soil suggested a dilution of groundwater NO₃ ^? by increasing contributions of forest floor and mineral soil NO₃ ^? during snowmelt.     

Selenium Behavior in Open Bulk Precipitation, Soil Solution and Groundwater in Alluvial Fan Area in Tsukui, Central Japan

A monitoring study was carried out in an alluvial fan area in Tsukui, Central Japan during the study period of 1999–2003, in order to explain selenium (Se) behaviors in ecosystem combined with air, soil and groundwater. Monthly Se concentrations in open bulk precipitation (rainfall+aerosol, gaseous deposition and etc.), soil solution (collected by porous ceramic-cup) and groundwater ranged from 0.1 to 1.4 μg L^?1 (volume-weighted average: 0.34 μg L^?1), 0.21 to 1.0 μg L^?1 (0.48 μg L^?1) and 1.6 to 2.4 μg L^?1 (2.2 μg L^?1), respectively. Se concentration in open bulk precipitation was negatively correlated with the rainfall amount. Se concentration in soil solution significantly increased with DOC concentration in soil solution. Besides, despite atmospheric Se input and rainfall to the grassland study area, Se concentration in soil solution and groundwater received no significant effect from the rainfall amount, pH, Se, DOC, SO₄ ^2?, NO₃ ^? and EC in rainfall. Even though Se concentrations in groundwater were significantly correlated with soil solution volume, Se, DOC and NO₃ ^? and groundwater level, the result of multiple regression analyses (MRA) indicated that the groundwater Se was negatively influenced by groundwater level, which depended on groundwater recharge. Se was transported into the groundwater through the groundwater recharge that largely increased in this alluvial fan study area after heavy rain.     

Water Quality Dependent Recovery from Aluminum Stress in Atlantic Salmon Smolt

In Norway, a variable pH target (pH 6.2–6.4 during most of the year, but 6.4 during the smoltification period) is used to reduce the cost of liming salmon rivers. Here we test the adequacy of this liming strategy. Atlantic salmon presmolts exposed to sublethal acidic water (pH 5.9, <25 µg Ali·L^?1) for more than 3 months showed impaired sewater tolerance, elevated gill-Al concentrations, severe gill tissue changes, elevated blood plasma glucose concentrations, but no effect on blood plasma chloride. It is usually assumed that smolt will recover from prior aluminum (Al) exposure if water quality is restored. Recovery rate is here used as an indirect measure of water quality improvements achieved after treating acid water (pH 5.8, 85 µg Ali·L^?1) with lime to reach pH-target levels of 6.0 – 6.3. Fish were exposed in a channel-tank set-up for >210 hrs in water aged from 1 minute up to 2 hours after treatment (in a flow through system). More Al was eliminated from the gills when the fish were exposed to pH 6.3 than to pH 5.8 or 6.0, and when water was aged after pH increase. Recovery, defined as return of normal gill morphology, blood homeostasis and establishment of seawater tolerance was achieved within 210 hrs in channels treated with lime to pH 6.3, while a similar recovery was not obvious at lower pH values. Liming to pH 6.3 detoxified Al better than pH 6.1.     

Hydrogen and aluminum inhibition of soybean root extension from limed soil into acid subsurface solutions

Soybean [Glycine max (L.) Merr. cv. ‘Ransom'] root elongation under varying concentrations of solution hydrogen (H) and aluminum (Al) was investigated in a vertical split‐root system. Roots extending from a limed and fertilized soil compartment grew for 12 days into a subsurface compartment with solutions adjusted to either different pH values from 3.7 to 5.5 or a factorial combination of pH (4.0,4.6, and 5.2) and Al (0,7.5, 15, and 30 μM) levels. Ionic forms of Al were estimated with GEOCHEM and solution Al was determined with ferron. Boron (B) (18.5 μM) and zinc (Zn) (0.5 μM) were supplied to all solution treatments, in addition to 2000 μM Ca, after preliminary studies at pH 5.2 without Al indicated that their omission inhibited length of tap roots and their laterals in the subsurface compartment. Both H⁺ and Al inhibited the length of lateral roots more than tap roots. Lateral roots failed to develop on tap roots at pH<4.3 or in treatments with 30 μM Al. Relative tap root length (RRL) among treatments receiving Al correlated with Al as measured by reaction with ferron for 30s. Ferron‐reactive Al was correlated to GEOCHEM‐predicted Al³⁺ activity (r=0.99). A 50% reduction in RRL occurred with either 2.1 μM Al³⁺ activity or 4.9 uM ferron‐reactive Al. The absence of shoot and soil‐root biomass differences among solution treatments in the split‐root system indicated that differences in root growth in the subsurface compartment were not directly confounded with differences in top growth.     

Physiological response of brown trout (Salmo trutta) spawners and postspawners to acidic alminum-rich stream water

High immediate postspawning mortality due to inferior autumn water quality has been hypothesized to cause juvenilization in some brown trout populations in acidified areas. We exposed male and female spawners and female postspawners from a juvenile-dominated brown trout population to acidic streamwater (pH = 4.83, Al_i = 240 μg L^?1) and a limed control (pH = 5.70, Al_i = 55 μg L^?1) for 28 days in November and December, 1984. Water chemistry was monitored at least bi-daily, and physiological stress was assessed by analysis of plasma chloride, osmolality and haematocrit. Neither pronounced physiological stress nor mortality was observed at the control site. At the exposure site trout showed significant but moderate stress responses and 15 % died. The results are discussed in terms of potential population effects and physiological mechanisms, e.g., plasma volume reduction.     

Fish species distribution and water chemistry in Nova Scotia lakes

During the summers of 1981-1984, 19,714 fish (23 species) were netted in 234 Nova Scotian lakes. Surface and mid-depth water samples were also analyzed for major ions, metals, and DOC. Lakewater pH varied from 4.4 to 7.7, including eight lakes which produced no fish in standard 23-hr net sets. Fish data were partitioned into 6 pH groupings for analysis. Stepwise multiple regressions of fish species vs. H+, S0₄,A1, Fe, and Mn showed little predictive power. Productive lakes ranged up to 530 μg L^?1 Al, 1680 pg L^?1 Fe, and 836 μg L^?1 Mn. Apart from pH, fish distribution and abundance showed no significant relationships with water chemistry data. We note, however, that the more acidic lakes had fewer species of fish.     

Influence of thermal power station effluents on hydrobiology of seawater

The hydrobiological parameters of the waters in the vicinity of ash slurry and cooling water outfall from Ennore Thermal Power Station located on the shore of Bay of Bengal, Madras were determined. In the outfall site, an increase in mean temperature (35 °C), salinity (3.5%), nitrite ? N (25 μg L^?1), ammonia ? N (185 μg L^?1), phosphate ? P (1 mg L^?1), silicate ? SiO₂ (1.65 mg L^?1), chlorophyll a (21.1 mg m^?3), respiration (76% of gross production), suspended solids (3.84 g L^?1), BOD (3.65 mg O₂) and decrease in pH (8.1), dissolved oxygen (DO) (5.5 mg L^?1), nitrate ? N (15 jig L^?1), gross production (16.6 Mg C m^?3 hr^?1) were recorded. Phaeopigment and respiration were inversely related with chlorophyll a and net productivity, respectively. Microbial biomass varied spatially, but was generally low (114.5 jig L^?1), at the outfall site. The hydrobiological characteristics of water with high turbidity indicate that the ash slurry and coolant water play a crucial role in a localized area resulting in environmental disturbance. The effect was profoundly influenced by an initial dilution, dispersion, wave mixing and current direction. The ecological relationships between these parameters and their implications in coastal pollution are discussed.     

Chemistry differences in two streams entering an acidic lake in the Adirondack Mountains,New York (U.S.A.)

Solution chemistry was measured in two major inlets, lake water column, lake outlet, and soils of the South Lake watershed in the Adirondack Mountains, New York. The east inlet had greater concentrations of H⁺, sulfate-S, and Al and smaller concentrations of base cations and silica than the west inlet (70, 116, 25, 90, 64 and 4, 99, 8, 228, 148 μeq L^?1 of H⁺ and sulfate-S, μmol L^?1 Al, μeq L^?1 total base cations and μmol L^?1 silica in east and west inlets, respectively). Concentrations of base cations in C horizon soil solutions (157 μeq L^?1 total base cations) were smaller and greater than west and east inlets, respectively. This suggests that water flowing into the west inlet contacted deeper mineral layers, whereas water reaching the east inlet did not. Lake and lake outlet concentrations were also intermediate between the two inlets, and the lake was acidic (pH 4.9 to 5.1) with relatively high total monomeric Al concentrations (8 to 9 μmol Al L^?1). The east inlet also had greater DOC concentrations than the west (0.38 and 0.24 μmol C L^?1, respectively), again indicating that soil solutions entering the east inlet passed through the forest floor but had more limited contact with deeper mineral layers in comparison with the west inlet. Differences between the streams are hypothesized to be related to contact of percolating solutions with mineral soil horizons and underlying glacial till, which provides neutralization of acidic solutions and releases base cations. This work indicates that processes controlling surface water acidification can be spatially quite variable over a small watershed.     

Field and laboratory studies of exposures of brown trout to acid waters

Some recent work on the effects of acid waters on brown trout are presented. Laboratory bioassay experiments have demonstrated that yearling trout are relatively insensitive to pH >4.3. Aluminium is demonstrated to be extremely toxic with suppression of growth occurring at concentrations above 20 μg L^?1 at pH 4.4 to 5.2. Aluminium toxicity is reduced at high pH (5.9 and 6.3). Field studies carried out on 61 acidic and circumneutral streams in upland areas of England and Wales showed a strong relationship between water quality and standing crop of 1+ brown trout. Measured pH levels per se were too high to be directly toxic. On the other hand, heavy metal and Al concentrations could account for low or zero brown trout biomass in the more acidic streams. A mobile bioassay laboratory has been developed to allow controlled bioassay experiments to be carried out in the field. Natural and synthesised waters can be tested concurrently in multi-factorial experiments with in situ determinations of pH, Ca, Al (total and monomeric) and other water quality characteristics.