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.     

Effects of a ski area on the water quality and invertebrates of a mountain stream

Past studies of the Rio en Medio, New Mexico, U.S.A., have shown significant changes in water quality and in invertebrate communities below the Sante Fe Ski Area. The present study was undertaken to determine how far downstream the effects of the ski area extend.. The concentration of every major nutrient except SO₄ was found to increase below the ski area and the only mechanism for recovery seemed to be dilution by downstream tributaries. Increased sediment loads below the ski area were also recorded. Peaks of sediment transport were associated with snow melt and summer rains. Much of the increased sediment below the ski area appeared to settle out in the upper reaches of the Rio en Medio. Composition and diversity of stream insects appeared to be little affected. However numbers and biomass of invertebrates were significantly reduced below the ski area. These reductions were attributed to the effects of increased sediment load. Some recovery of invertebrate production was recorded at distances of 700 to 2200 m below the ski area.     

Biology and chemistry of three Pennsylvania lakes: Responses to acid precipitation

The biology and chemistry of three northeastern Pennsylvania lakes was studied from summer 1981 through summer 1983 to evaluate lakes with different sensitivities to acidification. At the acidified lake (total alkalinity ≤ 0.0 μeq L^?1) there were fewer phytoplankton and zooplankton species than at the moderately sensitive lakes. The most numerous plankton species in all three lakes are reportedly acid tolerant. Among the benthic macro- invertebrates (BMI) there were more acid tolerant Chironomidae at the acidified lake, but more acid intolerant Ephemeroptera and Mollusca and a higher wet weight at the least sensitive lake. There were no differences among the lakes' BMI mean total numbers or mean number of taxa. The fish community at the acidified lake was dominated by stunted Lepomis gibbosus, but L. machrochirous were most abundant in the other lakes. Principal component analysis suggested a shift in all three lakes over the sampling period toward combined lower pH, alkalinity, specific conductance, Ca and Mg and higher Al and Mn. Such chemical changes have been associated with acidification. The rate and extent of acidification appeared to be controlled by geological and hydrological characteristics of the drainage basins.     

Biosorption of lead and uranium by Streptomyces sp.

Both Pb(II) and UO₂ ²⁺ were abstracted from aqueous solution by both living and dead biomasses of Streptomyces sp. The organisms were particularly effective in taking up UO₂ ²⁺ ions. Optimum pH for both metals was pH 5 to 6. For a UO₂ ²⁺ concentrations of 1 mmol L^?1 and a dead biomass concentration of 1 g L^?1, 60% of the UO₂ ²⁺ was removed from solution. If cell wall material of the organism was prepared from a killed biomass an equal weight of the material removed 90% of the UO₂ ²⁺ from solution. in this case accumulated U in the biomass was 0.9 mmol g^?1 of dry biomass. Electron micrographs showed clearly that the Pb abstracted was only in the microorganisms cell surface, but UO₂ ²⁺ uptake was also intracellular.     

The effect of pH,aluminum, and chelator manipulations on the growth of acidic and circumneutral species of Asterionella

The growth rates of two diatoms, acidophilic Asterionella ralfsii and circumneutral A. formosa, were differentially affected by varying pH, Al, and EDTA in chemically defined media. Free Al ion concentration increased as pH and EDTA concentration decreased. Free trace metal ion concentration decreased as EDTA levels increased but increased by orders of magnitude upon addition of Al. pH had an overriding species specific effect on growth rate; at low pH A. ralfsii had higher growth rates than A. formosa and vice versa at high pH. For both species higher EDTA levels depressed growth rates. Moderate additions of Al generally resulted in growth stimulation. The growth rate stimulations, especially at 200 and 400 μg L^?1 Al additions, correlate to increases in free trace metal ion concentrations. The EDTA-AI interaction effects on growth rate were both pH and concentration dependent: at pH 7 both species were stimulated by addition of Al at all EDTA levels (except A. ralfsii at 5.0 mM EDTA and A. formosa at 0.5 mNM EDTA); at pH 6 Al addition either stimulated or had no effect on the growth rates of both species (except at low EDTA and high Al levels); at pH 5 A. formosa did not grow and additions of 200 μg L^?1 Al stimulated growth of A. ralfsii. It is likely that the effect of pH, Al, and EDTA on speciation of essential or toxic trace metals affects growth rates of these diatoms in a species specific manner.     

Biomass and compositional changes in the periphytic community of an artificial stream in response to lowered pH

Two artificial streams simulating low-order, softwater streams of the Upper Peninsula of Michigan were employed to examine the effects of lowered pH on periphytic algae. The control stream contained water with a circumneutral pH whereas the pH of the water in the acidified stream was decreased to pH 4 with H₂SO₄. Chlorophyll a concentrations and cell densities in the periphytic algal communities were used to measure differences in biomass accumulations between the 2 streams over a 42-d, spring colonization period. Relative abundances of algal genera and Stander's similarity index (SIMI) were used to examine compositional differences between the control and acidified periphytic algal communities. These algal communities exhibited pronounced differences in their total biomasses and compositions indicating periphytic algal communities inhabiting low-order, softwater streams, such as those of the Upper Peninsula of Michigan, are vulnerable to acidic deposition. Decreased biomass accumulation under acidified conditions was believed to result primarily from decreased nutrient availability, and possibly secondarily from elevated aluminum and/or iron concentrations. The shift in community compositions was interpreted to be a more direct response to the lowered pH as acidophils and acid tolerant genera became favored, and thus more abundant.     

The benthic fauna of 41 acid sensitive headwater lakes in North Central Ontario

The benthic fauna of 41 nonhumic, soft water lakes situated north of lakes Superior and Huron were sampled during 1980. The pH range of the lakes sampled was 4.6 to 7.7. The benthic infauna displayed regional differences in abundance and composition, with large variation within each district. Total abundance, biomass, and number of taxa were not correlated with lake pH or alkalinity. The Chironomidae displayed a slight change in percent composition of the major species (p < 0.2) with lower pH. The Tanytarsini andChironomus salinarius group decreased, whileC. anthracinus group increased in relative abundance in those lakes with lower pH. Other factors appear to control the distribution of the various invertebrate orders, with depth and sediment nature being important variables.     

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.     

Effects of acid,aluminium and lime additions on fish and invertebrates in a chronically acidic welsh stream

A chronically acidic stream, mean pH 5.2, in upland mid-Wales was subjected to an induced episode of acidity, during which acid, Al and limestone were added at different points along the stream length. An upstream reference zone (A), an acid zone (B), an acid plus Al zone (C) and a downstream zone of Al at low pH with added limestone to increase pH (D) were created for a 24 hr period. Four species of fish and 10 species of invertebrates were exposed in each zone and response criteria measured included mortality, metal uptake, feeding and the ability of stressed animals to recover. Fish mortalities were greater in zones B and C than in zone A and were greatly reduced by the addition of lime in zone D. Overall mortality was low amongst the invertebrate species found in acid waters. Greatest mortalities were recorded for Gammarus pulex. G. pulex infected with the acanthocephalan parasite Pomphorhynchus laevis exhibited greater mortality than uninfected animals. The feeding rate of G. pulex was suppressed in all zones during the dosing period; uninfected G. pulex consumed more than infected animals, and the feeding rate of all gammarids increased post-dosing but not to the level of unexposed animals. Aluminium concentrations in fish gills increased with time. Invertebrate body burdens of Al were greatest in zone D, with significant increases over the dosing period for both G. pulex and Isoperla grammatica. No significant patterns were observed in the concentration of Ca, Na or K for either fish or invertebrates.     

Effects of metal pollution on the earthwormdendrobaena rubida (Sav.) in acidified soils

Survival of adultDendrobaena rubida, cocoon production, cocoon viability, and growth of juveniles were examined in laboratory experiments when the worms were reared in acidified and metal polluted soils. Solutions of Cu, Cd and Pb were added to give total concentrations of 10, 100 and 500 μg g^?1 in soils with a pH of 4.5, 5.5 and 6.5. Adult tissues, hatchlings and cocoons were analyzed for metals. D. rubida survived poorly in soils with low pH, especially in combination with Pb or Cu, which accumulated in seminal vesicles and cerebral ganglion. Cocoon production was halved when pH was lowered from 6.5 to 4.5 and metals reduced the cocoon number even more in the most acid soils. Hatching success was lower than 20 % in acidified soils. In contrast, the number of hatchlings increased when pH decreased and peaked in soils polluted with Cd. While low pH reduced the embryonic development time, metals prolonged it. Juveniles grew slowly and died early at low pH.     

Aluminum speciation in running waters on the Canadian pre-Cambrian Shield: Kinetic aspects

To evaluate the extent to which chemical disequilibrium may exist in stream waters following naturally occurring short-term pH changes, surface water samples were collected from two streams in the Lake Laflamme watershed north of Quebec City, placed in large polyethylene containers and stirred continuously at the in situ temperature; changes in Al speciation were followed with time for up to 24 hr. The original samples were collected during the spring snow-melt period and during summer low flows. In this latter case, a pH depression was induced by artificial acidification (H₂SO₄; pH 4) and changes in Al speciation with time were followed in both the acidified and the unacidified samples. Aluminum speciation as operationally defined did respond to artificial acidification (pH lowered; non-exchangeable and non-extractable Al decreased), and these pH-induced changes occurred rapidly (< 4 hr). During storage of natural water samples at in situ T for up to 24 hr, little change in Al speciation was noted, even in the case of samples collected during spring snow-melt; no clear cases of chemical disequilibrium existed among the studied samples. The distribution of Al among its various physico-chemical forms thus appears to be established within the stream itself; at a given stream sampling point the speciation of A1 will not necessarily reflect its geochemical origins, but rather the prevailing in situ conditions (e.g. pH, ligand concentrations).     

Aluminum speciation in soil solutions: Equilibrium calculations

A computer simulation was done to illustrate how the equilibrium solubility and speciation of Al in well-aerated soil solutions may be affected by pH (from 2.0 to 10.0), organic acids (citric, oxalic, phthalic, and salicylic acid), metal ions (K, Mg, Ca, Al, Fe), inorganic ligands (F, OH, SO₄, PO₄, CO₃, and SiO₃), and type of Al-containing solid [kaolinite, gibbsite, or amorphous Al(OH)₃] thought to be present. The simulation indicated that the type of Al-oxide/hydroxide considered has a substantial influence on the inorganic and organic equilibrium composition of the soil solution, and on the occurrence (or non-occurrence) of other Al-minerals such as KA1₃(SO₄)₂(OH)₆ (alunite) and Al(SO₄)(OH)-5H₂O (jurbanite).     

Effect of simulated acid precipitation on nitrogen mineralization and nitrification in forest soils

After exposure of samples of three forest soils (pH 3.4 to 3.9) from the Adirondacks region of New York to 60, 230, or 400 cm of simulated rain of pH 3.5 or 5.6 in 4, 14, or 24 weeks, respectively, the soil samples were separated into the 0 to 2 and 2 to 5 cm organic layers and further incubated. The rates of N mineralization in Woods soil exposed to the simulated precipitation were less for rain at pH 3.5 than at pH 5.6, but the inhibition decreased with increasing exposure of the 0 to 2 cm layer. In Panther soil, the rates of mineralization were usually not affected by the acidity of the simulated rain. In the upper layer of Sagamore soil, mineralization was not influenced by pH of the simulated rain, but the transformation was faster in the bottom layer of soil after prolonged exposure to simulated rain at pH 3.5 than at pH 5.6. The rate of nitrate formation in Panther and Woods soil amended with ammonium was inhibited by the more acid rain. Studies with ¹⁵NH₄ indicated that ammonium was oxidized to nitrate even though ammonium levels did not decline or declined only slightly after prolonged exposure of Panther or Woods soil to rain at pH 3.5. The growth of orchardgrass in Panther and Woods soil was inhibited by the more acid simulated rain.     

A hematoxylin staining technique to locate sites of aluminum binding in aquatic plants and animals

This paper describes a modified hematoxylin staining technique that can be used to locate sites of A1 binding in freshwater plants and animals. This technique is fast, simple, and inexpensive to use. It is more reliable for organisms raised under controlled conditions, although it can be used on organisms isolated from the field. In the presence of Al, a purple stain appears which absorbs between 560 and 570 nm. This stain can be used as a live stain over the pH range of 3 to 9. The stain remains stable for at least 12 mo in alcohol-preserved specimens. Low concentrations of Fe (reddish-brown) and high concentrations of Pb (grey) and Cu (pink) can mask the reaction with Al (purple). Fluoride (10:1 molar ratio to Al), EDTA (1:1 ratio to Al), humic acid and PO₄ (1:10 ratio to Al) can prevent A1 uptake or interfere with Al-hematein binding. Based on the technique described in this paper, sites of Al binding in aquatic plants and animals include: nucleus and cell wall of the green alga Mougeotia; cell wall of the aquatic moss Leptodictyum riparium; chloride cells, tip of the penis, and hind gut of the fairy shrimp, Branchinecta paludosa; and the anal papillae of the phantom midge, Chaoborus.     

Aluminum solubility of strongly acidified allophanic Andosols from Kagoshima Prefecture,southern Japan

Abstract

The aluminum solubility of acidified soils both from furrows and under tree canopies of a tea garden was studied using equilibrium experiments in 0.01 mol L^?1 CaCl₂ solution systems. The soils were originally classified as allophanic Andosols. The furrow soils were more severely acidified because of the heavy application of nitrogen fertilizer, especially in the upper soil horizons (pH[H₂O] of 3.6–3.8 in the A1 and 2A2 horizons). These acidified soils were characterized by the dissolution of allophanic materials (allophane, imogolite and allophane-like materials) and by an increase in Al–humus complexes. Ion activity product (IAP) values of the strongly acidified soil horizons were largely undersaturated with respect to imogolite (allophanic clay) or gibbsite. Plots of p(Al³⁺) as a function of pH strongly indicated that Al solubility of the soils was largely controlled by Al–humus complexes, especially in the A1 horizon. In the canopy soils, which were more weakly acidified (pH[H₂O] 4.9–5.0), Al solubility was close to that of gibbsite and allophanic materials, indicating that the solubility is partly controlled by these minerals.     

The short and medium term effects of organic Amendments on lead availability

The effect of six organic amendments on Pb solubility and availability was studied from May to September 1978 in a sandy soil low in organic matter. Three extractants were used to essay the Pb solubility: BaCl₂ 0.5M, AcNH₄ 2.5% at pH 7.0 and EDTA 0.05M at pH 7.0. During the aging process both increases and decreases of Pb solubility were observed in manured soils with respect to the control. Only in the soil treated with cow manure was a decrease of Pb solubility in ammonium acetate always noted. From regression lines of Pb concentration on soil/solution ratio it was possible to observe that only the soil treated with cow manure showed a significant decrease of slope of regression line when it was dispersed in ammonium acetate solution. The regression lines of Pb concentration on organic matter extracted by ammonium acetate and, especially, EDTA showed that these reagents extract mainly Pb complexed with organic compounds. A physiological test on Pb availability showed that only in the presence of cow manure was the Pb assimilation greatly decreased.     

The effects of acid perturbation on a controlled ecosystem

Duplicate, 8-compartment, continuous-flow microcosms were used to study the effects of acid addition on community function, algal community structure, and degradation of a plasticizer, diethyl phthalate. Inputs of HCl decreased the alkalinity (measured as CaC0₃) from 25 to 8 mg 1^?1, creating diurnal H⁺ activity curves that indicated that the ecosystem was being severely stressed. Removal of excess acid was accompanied by a return to a normal diurnal pH cycle. Nutrient concentrations and O₂ production did not give a definite indication of stress resulting from the addition of acid. Algal community structure and total biomass were not affected by acid inputs. Also, degradation rates of diethyl phtalate by the aquatic bacteria were similar for the control and the acid-stressed systems. These studies indicate that acid inputs can significantly disrupt normal ecosystem function, such as diurnal pH cycling, without having a measurable impact on other parameters usually monitored in aquatic ecosystems.     

Soluble organic acids and their chelating influence on Al and other metal dissolution from forest soils

The effects of mineral acid deposition on chemical properties of leachates of three granitic forest soils and pine O₁-litter were investigated under controlled laboratory conditions. Of the array of organic acids released from litter and SOM as detected by HPLC analysis, nine compounds were identified and six compounds have been quantified. Organic acids possessing certain functional group arrangements, such as di- and tri-carboxylic acids containing β-hydroxyl groups, and phenolic acids with ortho-hydroxyls were about three to ten times faster in dissolving Al than similar organics with other functional group combinations or mineral acids at comparable pH and concentration levels. There was little correlation between the initial pH of chelating organic acid input solution and rate of metal dissolution. On a mole metal-leached per gram basis, dissolution of metals from Shaver soil followed the order Al>Mn>Fe in both organic and mineral acids.     

Effects of fertilization practices on aluminum fractions and species in a wheat soil

Purpose

To better understand the effect of fertilizer practices on soil acidification and soil organic matter (SOM) stocks in a rice-wheat system, a field experiment was conducted to (i) investigate the influence of fertilizer practices on the Al forms in solid phases and the distribution of Al species in water extracts and (ii) explore the relationship between the Al forms, the quantity and composition of SOM, and soil acidity.

Materials and methods

Seven fertilizer treatments including CL (no fertilizer), NK, PK, NPK, N₂PK (PK and 125 % of N), NP₂K (NK and 125 % of P), and organic fertilizer (OF) were applied to induce various changes in pH and SOM composition (i.e., total C and N contents, C/N ratio, and SOM recalcitrant indices) in a rice-wheat system. After 6-year cultivation, different pools of Al forms (i.e., amorphous Al; organically bound Al of varying stability; exchangeable Al; water-soluble inorganic Al³⁺, Al-OH, Al-F, Al-SiO₃, and Al-SO₄; and organic Al monomers) were quantified and related with SOM composition and soil pH during the wheat phase.

Results and discussion

Fertilizer types significantly changed soil pH and SOM composition and which explained 84 % of the variance of Al forms using redundancy analysis. An interaction between soil pH and SOM quality on Al forms also existed but only accounted for a very small (6 %) portion of the variation. Compared to CL and chemical fertilizer, OF practice with relative low SOM stabilization is likely to favor the formation of amorphous Al in order to bind more SOM. The decrease in exchangeable acidity and water-extractable Al via hydroxyl-Al precipitation but not in the form of organo-aluminum complexes evidenced this phenomenon. In contrast, chemical fertilizer input increased exchangeable Al and water extract Al (especially Al³⁺), partly at the expense of organically bound Al. The destabilization of organic-aluminum complexes was a mechanism of pH buffering evidenced by the increased soluble Al-dissolved organic matter (DOM) as soil pH decreases. Further, the magnitude of this trend was much greater for elevated N input compared with P input.

Conclusions

Chemical fertilizer with relative high SOM stabilization favored the formation of exchangeable Al and soluble Al resulting in soil acidification, whereas OF with relative low SOM stabilization tended to transform exchangeable Al and soluble Al to amorphous Al, thereby alleviating soil acidification and enhancing C stocks in a rice-wheat system.

     

Titanium oxide nanoparticle effects on composition of soil microbial communities and plant performance

We examined the effect of TiO₂ nanoparticles (NPs) on the growth of maize and soybean plants and associated soil microbial communities. Plants were grown in a greenhouse, and low levels of undoped or nitrogen-doped TiO₂ NPs were applied. Plant growth and nutrient content were determined, and effects of NPs on composition of soil microbial communities were examined using terminal restriction fragment length polymorphism analysis (TRFLP) of rDNA. We found no significant effects of TiO₂ NPs on plant growth, nutrient content, or the composition of bacterial communities within the rhizosphere. However, arbuscular mycorrhizal fungal communities were affected by application of undoped and nitrogen-doped TiO₂ NPs. This observation may be partially attributed to the small but significant TiO₂ NP uptake levels in the root tissues of both plants. Our results suggest that even low concentrations of TiO₂ NPs may influence some important groups of soil microbes, such as mycorrhizal fungi, but changes in the composition of microbial communities may not affect plant growth under conditions of adequate moisture and nutrients.