Chronic effects of low ph and elevated aluminum on survival,maturation, spawning and embryo-larval development of the fathead minnow in soft water

Fathead minnows (Pimephales promelas) were exposed to a range of pH and A1 concentrations in soft water (8 mg Ca L^?1) to determine effect levels at various life stages. The tested pH levels ranged from 8.0 through 5.2 and inorganic monomeric Al from 15 through 60 μg L^?1. Reproductive processes including spawning, embryogenesis and early larval survival were more sensitive to acid stress than were juvenile growth and survival. Juvenile survival was significantly reduced at pH 5.2 + 60 μg Al L^?1 (P <0.05). Spawning success was reduced at pH 6.0 and 5.5 (P <0.10) and failed completely at pH 5.2, regardless of Al concentration. An apparant beneficial effect of added Al was observed during spawning at pH 7.5 + 35 μg Al L^?1, but this effect was not significantly greater than at pH 7.5 + 15 μg Al L^?1. A significant (P <0.05) decrease in larval survival occurred at pH 6.0 + 15 μg Al L^?1 and lower compared to the survival at pH 7.5 + 15 μg Al L^?1. Aluminum at 30 μg L^?1 provided protection resulting in short term increased embryo-larval survival at pH 5.5. The effect of parental exposure on progeny survival was assessed by an interchange of embryos from the spawning treatment to all tested exposure conditions. When reared at pH 8.0 + 15 μg Al L^?1 through 6.0 + 15 μg Al L^?1 or at pH 5.5 + 30 μg Al L^?1, parental exposure did not significantly influence progeny survival. However, survival was significantly reduced among progeny from brood fish reared at pH 5.5 + 15 μg Al L^?1 as compared to those spawned at pH 6.0 + 15 μg Al L^?1 and above, or at pH 5.5 + 30 μg Al L^?1 (P <0.05). Juvenile or 14 d larval growth effects were not detected under any exposure condition (P >0.05). Ultimately, fathead minnow young-of-the-year recruitment and production potential can be expected to diminish when environmental pH falls to 6.0, and to fail completely at 5.5 and lower.     

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.     

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 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.     

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.     

Acidification of Lake Annie,Highlands Co., FL

Lake Annie, a clear-water seepage lake in south-central Florida remote from significant pollution sources, was sampled by the USGS from 1966 until 1978, and by Battoe and others from 1978 until present. Since 1966, pH and bicarbonate alkalinity have decreased (pH from above 6.0 to about 5.1; bicarbonate from 5.0 to less than 0.5 mg L^?1), while specific conductivity and sulfate concentration have increased (cond. from 30 to 55 μS; sulfate from 3.0 to 8.0 mg L^?1). The chemical changes are apparently due to acidification from atmospheric deposition. There are no proximate sources of acidity and the stability of lake level indicates there has been no significant concentration or dilution of solutes. It is suggested that Lake Annie's acidification was a threshold phenomenon wherein, following depletion of the watershed's buffering capacity, acidification of the lake was rapid.     

Effects of liming on nutrient limitation of epilithic algae in an acid lake

The processes of lake acidification and lake restoration frequently involve major changes in DIC and DIN, both of which may potentially limit algal growth. We evaluate nutrient limitation of benthic algal biomass and species abundances during summers 1987 and 1989, before and after the liming of Lake Earnest (NE Pennsylvania) in November 1988. Limestone addition caused immediate increases in pH from 4.7 to 7.2. Alkalinity was ?34 μeq L^?1 in summer 1987, but rose to 620 μeq L^?1 in summer 1989, whereas DIN declined from 10.7 μmol L^?1 to 1.1 μmol L^?1 The algae were sampled after 45 to 46 d from clay flower pot substrates diffusing combinations of N, P and C. Algal biomass was strongly C-limited in 1987, but NP-limited in 1989. Mougeotia sp., which comprised >99% of total algal biovolume prior to liming, declined to < 1% of the community on control substrates, while Oedogonium sp. increased to 43% of total biovolume in 1989. The stimulation of chlorophyll-a accrual with C-enrichment during 1987 was consistent with the later increase in chlorophyll-a on control substrates following liming. Species enhanced by the diffused nutrients, however, generally differed from those which dominated the natural community.     

Influence of Natural Organic Matter (NOM) on the Speciation of Aluminum during Water Treatment

Natural organic matter (NOM) is a term collectively used to describe the complex matrix of organic material present in natural waters. The impact of NOM on the speciation of aluminum at Buffalo Pound water treatment plant was evaluated in the present study using fulvic acid. The first stage of the study was to conduct aluminum (Al) speciation experiments (using background dissolved organic carbon levels present in the raw water) at the pilot scale water treatment plant located within the main plant changing the aluminum sulfate (alum) dose from 68 mg L^-1 (yearly average dose of the main plant) to 34 mg L^-1. The second stage of the study was to conduct jar tests at various alum/DOC ratios. Pilot scale speciation study showed that when the alum/DOC ratio was 5.3, most of the total aluminum in the filtered water was in the form of particulate aluminum. Such an increased particulate aluminum level did not increase the finished water turbidity. Soluble organic aluminum also increased compared to the level in raw water when the alum/DOC ratio was 5.3. Al speciation study conducted during jar testing showed that organically bound aluminum increased from 8 μg L^-1 (raw water) to 15 μg L^-1 in the finishedwater when the alum/DOC = 1.37. Jar test results also showed that an alum/DOC of at least 7.3 should be maintained in the main plant in order to meet the proposed operating guidelines of 100 μg L^-1 of total aluminum by Health Canada given the conditions that finished water soluble aluminum levels may be in the range of 35–40 μg L^-1.     

Adsorption of dissolved organic carbon and sulfate by acid forest soils in the Fichtelgebirge,FRG

The adsorption of dissolved organic carbon (DOC) and sulfate was examined in mineral horizons of acid soils from damaged (Oberwarmensteinach) and healthy (Wülfersreuth) Norway spruce forested sites in the Fichtelgebirge (NE-Bavaria). The A horizons of both sites desorbed DOC at all levels added, whereas the B horizons (Bs and Bv) retained added DOC at levels > 5 mmol C kg^?1. An initial mass isotherm used on the B horizon data indicated that these soils have a greater affinity for DOC than B horizons from Spodosols in the northeastern U.S. Sulfate was only retained at high solution levels, and retention was pH dependent. Nitrate and sulfate additions (1000 μeq L^?1 anion) had minor effects on DOC adsorption. Overall, there was little difference in DOC or sulfate retention at the two sites, indicating atmospheric deposition inputs have not affected these processes.     

Seasonal,annual and long-term variability in the water chemistry of a remote high mountain lake: Acid rain versus natural changes

Seasonal fluctuations as well as long-term trends in water chemistry were studied in Schwarzsee ob Sölden (Tyrol, Austria), an oligotrophic softwater lake situated at 2796 m a.s.l. The catchement is composed of granite, plagioclase and micaschists containing considerable amounts of sulphur, with little soil cover. The lake is ice covered for about nine months, during this time the deepest layers (>16m) become anoxic. During summer overturn, alkalinity (ALK) is lowest (?8 μeq l^?1) in the whole water column, whereas pH reaches its minimum (4.88) at the surface during snowmelt. A decrease of pH from 5.8 to 5.4 during winter is caused by CO₂ oversaturation, but deep water ALK increases to up to 130 μeq l^?1 due to in-lake ALK generation by reductive processes and base cation (BC) release. The seasonal pattern of ALK in SOS is driven by in-lake processes in winter, the snowmelting in spring and watershed processes and precipitation during summer. Since 1989 summer sulfate concentrations in SOS, originating mainly from the catchment, show a tendency to increase presumably caused by enhanced weathering. In contrast, SO₄ ^2? concentrations in other high mountain lakes which are dominated by atmospheric depositions show a decreasing trend. SOS is a good example for the complexity of interactions between catchment and in-lake processes which act at different time scales and depend on climate changes and atmospheric inputs.     

Seasonal variations of oil residues in water of Shatt al-Arab river,Iraq

The distribution and seasonal variations of petroleum residues in the Shatt al-Arab water column have been determined spectrofluorometrically. Their concentrations were found to vary between 1.7 to 35.4 μg L^?1 Kuwait crude oil equivalents. The results suggested that petroleum hydrocarbons present in this river originated from diverse sources. Hydrocarbon amounts tend to be highest in winter (averaged 17.4 μg L^?1) and lowest in summer (averaged 3.1 μg L^?1).     

Effects of phosphogypsum or calcium sulfate on aluminon reactive aluminum in solutions at varying pH

Abstract

Growing evidence of positive crop responses to gypsum or phosphogypsum (PG) application in acid soils strongly support the use of these amendments as an ameliorant of subsoil acidity. Although gypsum improves Ca availability in subsoils, its role in alleviation of Al toxicity needs careful attention. In the current study, either PG, CaSO₄.2H₂O or CaCl₂.2H₂O was added (to supply 12 mM Ca) to solutions containing 40 μM Al at pH 4.1 + 0.1. Solution pH was gradually raised to 4.5, 4.8 and then to 5.3 at various time intervals during 25 d aging of the solutions at 25 + 1^OC.

Concentration of Al measured by aluminon method without preacidification and preheating, referred to as “reactive Al”; in this paper, was 16 μM in 2 g L^‐1PG solution without added Al. This accounted 38% of total soluble Al in PG solution. Addition of 2 g L^‐1PG to solution containing 40 μM Al, resulted in only 42% of total Al in solution present in forms reactive with aluminon. According to MINTEQ speciation model, Al in solution was present as an entirely complexed form with F^‐. An increase in solution pH up to 5.3 had no effect on measured concentration of reactive Al or predicted distribution of Al species.

Addition of CaSO₄.2H₂O to 40 μMAl solutions had no effect on the concentration of reactive Al within pH 4.1 ‐4.8, however, up to 62% of total Al was in a form complexed with SO₄ ^2‐, as predicted by MINTEQ model. The concentration of reactive Al decreased by 60% at pH 5.3. Addition of CaCl₂.2H₂O also had no effect on the concentration of reactive Al within pH 4.1 ‐ 4.8. Nearly 73 ‐ 94% of total Al was present in Al³⁺form. An increase in pH to 5.3, decreased the concentration of reactive Al by 27%. The results suggest that ion‐pairing of Al with F^‐would appear to be a possible mechanism for alleviation of Al toxicity by PG at pH range 4.1 ‐ 5.3. With regard to CaSO₄.2H₂O, at pH 4.1 ‐ 4.8 ion‐pairing with SO.₄ ^2‐appears to be possible mechanism for the alleviation of Al toxicity. In addition, at pH 5.3 a considerable decrease in reactive Al was evident which would further alleviate Al toxicity.     

Response to a smelter closure in Cascade mountain lakes

A statistically significant decrease in sulfate was observed in high elevation Cascade lakes during 1983 through 1988. The total decrease averaged 2.2 μeq L^?1 in two slow-flush lakes and 4.2 μeq L^?1 in three fast-flush lakes for 1983–1985 vs 1986–1988, respectively. Coincident with these changes in sulfate concentrations were a sharp decrease of SO₂ emissions from the ASARCO smelter (100 km SE of the lakes), from 87 to 70 kt yr^?1 during 1983–1984 to 12 in 1985, the year of its closure, and a gradual change in SO₂ emissions from Mt. St. Helens, from 39 to 27 during 1983–1984 to 5 in 1988. The sharpest decreases occurred in non-marine sulfate in fast-flush lakes from 1984 to 1985 (about 2 μeq L^?1) and in slow-flush lakes from 1985 to 1986 (1 μeq L^?1, which point to the ASARCO closure as the sole cause. However, some of the more gradual decline in non-marine sulfate observed during 1983 through the 1988 sampling periods may have been due to a slow washout of sulfate enriched ash from the 1980 Mt. St. Helens' eruption. Sulfate concentrations in precipitation also declined significantly by about 2 μeq L^?1, but changes in volume-weighted sulfate content were not significant. Lake alkalinity did not show a consistent increase in response to decreased sulfate. This was probably due to either watershed neutralization of acidic deposition or the greater variability in alkalinity measurements caused by small changes in acidic deposition making it difficult to detect changes.     

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.     

Aluminum toxicity to fish in acidic waters

An important consequence of acidification is the mobilization of Al from the edaphic to the aquatic environment. Elevated Al levels in acidic waters may be toxic to fish. Eggs, larvae, and postlarvae of white suckers (Catostomus commersoni) and brook trout (Salvelinus fontinalis) were exposed in laboratory bioassays to pH levels 4.2 to 5.6 and inorganic Al concentrations of 0 to 0.5 mg l^?1. Aluminum toxicity varied with both pH and life history stage. At low pH levels (4.2 to 4.8), the presence of Al (up 0.2 mg l^?1 for white suckers; 0.5 mg l^?1 for brook trout) was beneficial to egg survival through the eyed stage. In contrast, Al concentrations of 0.1 mg l^?1 (for white suckers) or 0.2 mg l^?1 (for brook trout) and greater resulted in measurable reductions in survival and growth of larvae and postlarvae at all pH levels (4.2 to 5.6). Aluminum was most toxic in over-saturated solutions at pH levels 5.2 to 5.4. The simultaneous increase in Al concentration with elevated acidity must be considered to accurately assess the potential effect of acidification of surface waters on survival of fish populations.     

Chemical composition of hoarfrost,rime and snow during a winter inversion in Utah,U.S.A.

We present data on the chemical composition of hoarfrost, rime, and snow grains that accumulated during an eighteen-day long temperature inversion event in Salt Lake City, Utah in December 1985 and January 1986. Chemical analyses show that the precipitation formed during this inversion event was acidic (as low as pH 3.85) and had nitrate and sulfate contents up to 1680 and 1290 μeq · L^?1, respectively. Ammonia, nitrate, and sulfate deposition of 361, 615, and 792 μeq · m^?2, respectively, occurred in a six-day period due to the accumulation of snow grains during this inversion.     

Respiration of Louisiana Freshwater Floating Marsh Soils Amended with Ammonium,Phosphate, and Sulfate

Wetland soils of the freshwater coastal deltaic regions of Louisiana have developed under decreasing influence from the Mississippi River, which has resulted in lower available nutrient conditions and sediment input relative to other coastal marshes. A laboratory soil respiration experiment was conducted to measure cumulative carbon dioxide (CO₂) and methane (CH₄) production in soils from a floating freshwater marsh in response to additions of added ammonium (N), phosphate (P), ammonium (N) + phosphate (P), and sulfate (S). CO₂ respiration was significantly greater over a 28-day period than controls following ammonium N, phosphorus, and sulfate addition at 10 mg L^?1. Nitrogen and phosphorus addition at 10 mg L^?1 also increased methane production. The lower sulfate amendment (10 mg L^?1) did not significantly increase CH₄ production. In contrast, the greatest sulfate treatment (100 m l^?1) significantly reduced total carbon (C) production by inhibiting CH₄ production. The fact that soil C/N (20.2) and C/P (355) ratios were both relatively low may partially explain why both N and P colimited microbial activity and respiration. While microbial activity of freshwater floating marsh soils was stimulated over the short term with increased ammonium, nitrogen, phosphorus, and sulfate exposure, it is unclear whether the increase would be the same over extended periods or would increase in plant productivity from nutrient additions compensate for any loss in soil carbon.     

Reversibility of soil solution acidity and of sulfate retention in acid forest soils

To quantify the effects of reduced sulfate input on the chemistry of soil solution and soil S storage in acid forest soils, an experiment with undisturbed soil columns from two different sites was implemented. The acid cambisol of the Solling is subjected to a high sulfate input and especially the B-horizon has a high sulfate content. On the contrary, the podzol of the Fuhrberg site is subjected to low input and has low sulfate content. Undisturbed soil columns were taken from both sites and were irrigated at 6 °C with a precipitation rate of 3 mm d^?1 over 10 mo. In treatment No. 1, an artificial throughfall with pH 5.2 and reduced sulfate load (45 μmol L^?1) was applied. In treatment No. 2, an artificial througfall representing a high sulfate deposition (427 μmol L^?1, pH 3.2) was used. In case of the Solling soil, the pH of soil solution was unaffected by treatments during the entire experiment. Alkalinity of the soil solution was slightly increased in treatment No. 1 at a depth of 20 cm. While treatment No. 1 resulted in a reduction of the sulfate concentrations of the soil solution in the top soil, sulfate concentrations were unaffected at a depth of 40 cm. The B-horizon of the Solling soil prevented deacidification of the soil solution by desorption of previously stored sulfate. In case of the Fuhrberg soil, treatment No. 1 resulted in reduced sulfate concentrations of the soil solution even in deeper soil layers with concentrations approaching input levels. The pH of the solution was slightly elevated and the alkalinity of the solution increased. Organic S compounds in the soil seemed to have no influence on sulfate release in either soils.     

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.