Influence of low-level cadmium and reduced calcium intake on tissue Cd concentrations and behaviour of American black ducks

Populations of American black ducks have declined and it has been hypothesized that wetland acidification, which can alter food quality by increasing availability of cadmium and decreasing that of calcium, may have contributed. We tested whether low-level cadmium and reduced calcium intake affect tissue cadmium concentrations and behaviour of captive black ducks. Adults received diets that mimicked cadmium and calcium concentrations in invertebrate prey from acid and from circumneutral wetlands for three spring and summer months in 1991 and 1992. Behaviours were monitored both when birds were fed experimental diets and control (commercial) diets. Cadmium in kidneys and liver differed significantly among groups and low calcium facilitated cadmium uptake. After two breeding seasons, levels of accumulated Cd were not lethal. However, birds that received Cd were significantly more active than control birds. Increased activity may have implications for survival of birds in the wild.     

Comparison of episodic acidification in Canada, Europe and the United States

Episodic acidification is practically a ubiquitous process in streams and drainage lakes in Canada, Europe and the United States. Depressions of pH are often smaller in systems with low pre-episode pH levels. Studies on European surface waters have reported episodes most frequently with minimum pH levels below 4.5. In Canada and the United States, studies have also reported a number of systems that have had minimum pH levels below 4.5. In all areas, change in water flowpath during hydrological events is a major determinant of episode characteristics. Episodic acidification is also controlled by a combination of other natural and anthropogenic factors. Base cation decreases are an important contributor to episodes in circumneutral streams and lakes. Sulphate pulses are generally important contributors to episodic acidification in Europe and Canada. Nitrate pulses are generally more important to episodic acidification in the Northeast United States. Increases in organic acids contribute to episodes in some streams in all areas. The sea-salt effect is important in near-coastal streams and lakes. In Canada, Europe and the United States, acidic deposition has increased the severity (minimum pH reached) of episodes in some streams and lakes.     

Egg mass and shell thickness in dippers Cinclus cinclus in relation to stream acidity in Wales and Scotland

The shell thickness and mass of eggs of the dipper (Cinclus cinclus) collected on streams of different pH in Wales and Scotland were measured. The aluminium, phosphorus and calcium content of their invertebrate prey were also measured. In a regression analysis, significant at p<0.05, stream pH accounted for up to 7% of the variance in shell thickness, with shells decreasing by 2.5% of the overall mean with each unit of pH decline. In the Welsh sample, differences in shell thickness due to pH were small compared with differences between years across all sites. In data pooled between Scotland and Wales, pH accounted for 17% of the variance in egg mass, but a greater proportion (25%) in Scottish eggs alone. Aluminium concentrations in invertebrates showed no relationship with stream pH, but calcium levels in two insect orders increased significantly with pH. Calcium rich prey, such as Gammarus, were found only in circumneutral streams. The importance of calcium in the diet of dippers before and during egg formation is discussed. No evidence that aluminium in prey adversely affected dipper eggs was found.     

Physiological recovery from episodic acid stress does not mean population recovery of Gammarus fossarum

The physiological responses of the acid-sensitive amphipod Gammarus fossarum exposed in situ to acid stress (pH4.5 and 5.5) and then transferred back to neutral water were investigated. Survival rate and haemolymph [Cl(-)] and [Na(+)] were assessed after 24, 48 and 72h of exposure in acidic streams and after a recovery period of 12, 24, 36, 48 and 60h. After 24h, exposure to slightly acidic (pH5.5) and strongly acidic water (pH4.5) led to a severe and significant depletion in haemolymph [Na(+)] and [Cl(-)] compared to organisms exposed in circumneutral water (pH7.3). However, after only a 12h-period of transfer back in neutral water and whatever the previous exposure time (24, 48 and 72h) in both slightly and strongly acidic water, haemolymph [Na(+)] and [Cl(-)] were equal or superior to the control level without associated mortality. In spite of this fast physiological recovery capacity, populations of G. fossarum living in streams undergoing episodic acid stresses were drastically affected thus, demonstrating the high acid-sensitivity of this species. We discuss the possible reasons of population regression and the absence of population recovery.     

The ecology of acidification and recovery: changes in herbivore-algal food web linkages across a stream pH gradient

We examined the effects of acidification on herbivore-algal food web linkages in headwater streams. We determined the structure and abundance of consumer and benthic algal assemblages, and gauged herbivory, in 10 streams along a pH gradient (mean annual pH 4.6-6.4). Biofilm taxonomic composition changed with pH but total abundance did not vary systematically across the gradient. Mayflies and chironomids dominated under circumneutral conditions but declined with increasing acidity and their consumption of algae was strongly reduced. Contrary to expectations, several putative shredder species consumed algae, maintaining the herbivore-algal linkage where specialist grazers could not persist. These shifts in functioning could render the communities of acidified streams resistant to reinvasion when acidity ameliorates and water chemistry is restored to a pre-acidification condition. This hypothesis is discussed in the light of recent trends in the chemistry and biology of the UK Acid Waters Monitoring Network sites.     

Toxicity of pH,heavy metals and bisulfite to a freshwater green alga

Low pH markedly reduced the growth and photosynthetic activity of an $\text{Ankistrodesmus}$ sp. The alga could not grow at pH 3 and only slight growth occurred at pH 4. The alga grew well above pH 4 with maximum growth occurring at pH 6. The fixation of ¹⁴CO₂ followed a similar pattern with pH. The algal cells were also sensitive to mercury and bisulfite in acidic conditions. Algal growth and photosynthesis were reduced by mercury and bisulfite more at pH 5 than at pH 7. Lead was relatively non-toxic to the algal cells at both pH levels. Bisulfite inhibited the membrane transport of α-amino-¹⁴C-isobutyric acid at pH 5 but not at pH 7. The results suggest that algal growth and activity may be reduced in acidic lakes by low pH and that the toxicity of mercury and bisulfite is enhanced in acidic conditions.     

Restoring acidified streams in upland Wales: a modelling comparison of the chemical and biological effects of liming and reduced sulphate deposition

Increasing emphasis is being placed on the restoration of surface waters which have been affected by acidification. Amongst the possible strategies are management of the causes, by reducing acidic deposition, and management of the symptoms, by treating affected areas with basic material such as limestone. In few cases have there been comparisons of the likely effect of these two strategies on surface water chemistry and ecology, although there is widespread belief that the two are similar in outcome. At present, only a modelling approach permits such a comparison. This paper describes chemical and biological responses of three Welsh streams whose catchments were limed experimentally in 1987-1988 as part of the Llyn Brianne project. Actual changes are compared with simulated changes which occur following reduced acid deposition according to the hydrochemical model, MAGIC (Model of Acidification of Groundwaters in Catchments). The results indicate that liming and 90% reduction in sulphate deposition reduce concentrations of toxic aluminium to similar levels. However, calcium concentrations and pH were increased by liming to values which were high by comparison with conditions simulated at low acid deposition, either in the past or future. Trout density increased in two of the streams following liming to levels similar to those simulated under low acid deposition. By contrast, the aquatic invertebrate fauna changed after liming so that streams acquired species typical of higher calcium concentrations than those simulated under low acid deposition. Species characteristic of 'soft water' communities were apparently lost, although more data are required to separate treatment effects from random change in the longer term. The 'soft water' community also declined in the model as a result of acidification, indicating that both liming and acid deposition resulted in a different faunal community from that prior to acidification. The results support those who conclude that liming is suitable for the restoration or protection of a fishery, but indicate that there may be other ramifications, for example to conservation, which must be considered when liming is implemented. However, the simulation of biological conditions under low acid deposition involves extrapolation from the initial data base. Further data are now required to assess empirically the likely biological character of British streams which have low base cation concentrations unaffected by acid deposition.     

A test of fluctuating asymmetry in Bluegills (Lepomis macrochirus Rafinesque) as a measure of pH-related stress

Fluctuating asymmetry of bilateral anatomical characters, previously proposed as an indicator of stress induced by agents affecting the calcium metabolism of fishes, was measured in bluegills (Lepomis macrochirus) from eleven Wisconsin lakes. The fluctuating asymmetries of three meristic characters-numbers of pored lateral line scales, pectoral fin rays and gill rakers on the outer arch-were either unrelated or only marginally related to either lake pH or waterborne calcium concentration. The asymmetry variance of gill raker counts was negatively correlated with both lake pH and waterborne calcium concentration; however, the overall asymmetry mean of gill raker counts in bluegills from five low pH lakes only slightly exceeded that in bluegills from six lakes with circumneutral pH. Fluctuating asymmetry in adult fishes was judged to be insensitive as a potential measure of pH-related stress.     

Calcium-lead interactions involving earthworms. Part 1: The effect of exogenous calcium on lead accumulation by earthworms under field and laboratory conditions

Earthworms (Lumbricus rubellus and Dendrodrilus rubidus) were collected from several acidic and calcareous abandoned ferrous metalliferous mine sites. Tissue lead concentrations were substantially lower than the total soil lead concentrations, except at one site (Cwmystwyth) where the tissue lead concentrations of both species were approximately 5 to 10 times higher than that of the soil. Soil lead was the major factor in determining the tissue lead concentration, although it was demonstrated that both soil pH and soil calcium concentration could markedly increase the % variance in tissue lead concentration. These findings help explain the apparent anomaly in tissue lead concentrations of earthworms from Cwmystwyth, where the soil is acidic and has exceptionally low calcium concentrations. Soil-liming experiments provided supportive evidence that soil pH, coupled with soil calcium, influences lead accumulation by earthworms, but a filter paper feeding experiment provided unequivocal evidence that soil calcium concentration alone can influence lead accumulation by earthworms. It is concluded that, although lead accumulation by earthworms is influenced by both physico-chemical and biochemical mechanisms, the latter over-rides the former, i.e. soil calcium is more important factor in determining the accumulation of lead earthworms than is soil pH.     

Reproductive status, blood chemistry, gill histology and growth of perch (Perca fluviatilis) in three acidic lakes

Perch (Perca fluviatilis L.) were sampled soon after spawning in three small acidic lakes (pH 4.3-6.1, Al(lab) 5-106 microg litre(-1), Ca2+ 0.01-0.08 mmol litre(-1)) and in one circumneutral lake (pH 5.9-6.4, Al(lab) 4-12 microg litre(-1), Ca2+ 0.06-0.07 mmol litre(-1)) in southern Finland. Due to the delayed spawning of perch in the acidic lakes, sampling in those lakes was performed later than in the reference lake. In spite of that, the gonadosomatic index (GSI) of males in all the acidic lakes was significantly greater than in the reference lake. Of the two lakes with similar low water pH, the effects on reproduction were more prominent in the lake with higher water Al content. The plasma Ca2+ concentrations of females in the acidic lakes were significantly smaller than in the females of the reference lake. The low female:male plasma Ca2+ ratio (1.0-1.32) depicted delay of spawning. Stress in perch in acidic water was also seen in elevated blood haematocrit values, especially in females. On the other hand, a low plasma Cl- level, a common response to acidic water in salmonids, was not detected in perch in the most acidic lakes. The amount of Al accumulated in the gill epithelium was highest in the most acidified lake with high Al concentration, but was also pronounced in a lake with low pH and low Al concentration.     

The impact of acidification on macroinvertebrate assemblages in welsh streams: towards an empirical model

The acidification of surface waters has profound ecological consequences. There is a need to predict the effects of possible future patterns of acid deposition on the biological components of fresh waters. This paper describes a model of the relationships between water chemistry and macroinvertebrate assemblages in eighteen streams in the upper Tywi whose catchments are subject to different land uses. Using established statistical techniques on data sets derived from riffle and margin samples taken in spring and summer, the macroinvertebrate assemblages were classified into three groups, which corresponded with streams draining conifer afforested catchments, acidic moorland streams and circumneutral moorland streams. Following principal components analysis to select key environmental variables, the application of multiple discriminant analysis generated two discriminant functions which were related most strongly to mean filterable aluminium concentration and mean total hardness, respectively. The discriminant functions were used to assign site-group membership with 100% success in the case of the spring data set with combined habitats. In addition, multiple regression of the primary ordination axis of each data set on mean aluminium concentration and mean hardness or pH, produced equations which explained 62.0%-87.2% of the variance. We conclude that the methods used here provide an effective analytical and potentially predictive tool for use in the understanding and management of the impact of acidification on freshwater ecosystems.     

Acid generation upon thermal concentration of natural water: The critical water content and the effects of ionic composition

Thermal evaporation of a variety of simulated pore waters from the region of Yucca Mountain, Nevada, produced acidic liquids and gases during the final stages of evaporation. Several simulated pore waters were prepared and then thermally distilled in order to collect and analyze fractions of the evolved vapor. In some cases, distillates collected towards the end of the distillation were highly acidic; in other cases the pH of the distillate remained comparatively unchanged during the course of the distillation. The results suggest that the pH values of the later fractions are determined by the initial composition of the water. Acid production stems from the hydrolysis of magnesium ions, especially at near dryness. Near the end of the distillation, magnesium nitrate and magnesium chloride begin to lose water of hydration, greatly accelerating their thermal decomposition to form acid. Acid formation is promoted further when precipitated calcium carbonate is removed. Specifically, calcium chloride-rich pore waters containing moderate (10–20 ppm) levels of magnesium and nitrate and low levels of bicarbonate produced mixtures of nitric and hydrochloric acid, resulting in a precipitous drop in pH to values of 1 or lower after about 95% of the original volume was distilled. Waters with either low or moderate magnesium content coupled with high levels of bicarbonate produced slightly basic fractions (pH 7–9). If calcium was present in excess of bicarbonate, waters containing moderate levels of magnesium produced acid even in the presence of bicarbonate, due to the precipitation of calcium carbonate. Other salts such as halite and anhydrite promote the segregation of acidic vapors from residual basic solids. The concomitant release of wet acid gas has implications for the integrity of the alloys under consideration for containers at the Yucca Mountain nuclear waste repository. Condensed acid gases at very low pH, especially mixtures of nitric and hydrochloric acid, are capable of corroding even alloys, such as nickel-based Alloy 22, which are considered to be corrosion-resistant under milder conditions.     

Effects of aluminium in acid streams on growth and sporulation of aquatic hyphomycetes

We investigated, by field and laboratory experiments, the effects of aluminium in an acid stream (pH 5.0) on the growth and sporulation of aquatic hyphomycete fungi which degrade organic litter. The stream water had monomeric aluminium (Al(m)) concentrations of 9.1-13.4 microm - fifty times higher than a nearby circumneutral stream. Alder leaves submersed in the stream accumulated Al, most of which was tightly bound. Growth rates of four species of aquatic hyphomycetes were altered by inclusion of Al(m) in the culture medium. On a polypectate substrate, and on low-phosphate medium with glucose, growth rates increased significantly. On a low-nutrient substrate of homogenized alder leaves, growth rates were inhibited by aluminium. The pattern of mycelial growth was found to be different on a polypectate medium including Al(m), compared with a control without aluminium. There was a significant increase in hyphal radial growth and a decrease in the hyphal growth unit. The effect resembled the growth of a starved fungal colony. Treatment with Al(m) decreased pectinase production by the four fungal species tested. The capacity of these species to sporulate was reduced by flooding culture plates with Al(m) solution. These deleterious metabolic effects were most severe in isolates taken from circumneutral streams and less marked, though significant, in species originating from acid streams.     

Relationships between lake chemistry and calcium and trace metal concentrations of aquatic invertebrates eaten by breeding insectivorous waterfowl

Ca, P, Al, and trace metal (Cu, Ni, Zn, Cd, and Pb) concentrations were measured in several aquatic invertebrate taxa used as food by breeding insectivorous waterfowl, sampled from three sites in eastern Canada with widely varying water chemistry. Ca concentrations were highest in molluscs (snails and clams), averaging 200-300 mg g(-1) (shells included). Aquatic insects of varying sizes, life stages and habits (caddisfly larvae, dragonfly larvae, adult backswimmers, waterstriders, and whirligig beetles) had much lower mean Ca concentrations, ranging from about 0.6 mg g(-1) (beetles) to 1.8 mg g(-1) (caddisflies). Invertebrate-Ca concentrations decreased with increasing body mass for several taxa, with smaller and larger individuals providing similar absolute amounts of Ca. Ca concentrations in most aquatic insects (but not molluscs) were reduced under acidic, low Ca, high Al, low dissolved organic carbon (DOC) and/or low total phosphorus (TP) conditions. In stepwise multiple regressions, pH was consistently the main factor explaining variability in invertebrate-Ca, after controlling for the negative relationship between invertebrate-Ca and body mass for some taxa. Molluscs were absent from lakes below pH 5.3. In general, concentrations of P and metals in invertebrate taxa were not significantly correlated with lake pH. Levels of Al, Cd, or Pb were not sufficiently high to be considered toxic to potential consumers of these organisms. For waterfowl and other birds breeding in acid-stressed habitats and relying on aquatic invertebrates as a source of food, a reduced availability of dietary Ca is more likely than an increased exposure to toxic metals to negatively affect reproductive success, especially when other adverse effects of acidification (lower diversity of prey) are considered.     

Effects of acidification on the availability of toxic metals and calcium to wild birds and mammals

The effects of acidification on wildlife inhabiting aquatic or semi-aquatic environments are reviewed, with particular reference to the possibility for increased dietary exposure to Hg, Cd, Pb and/or Al, and decreased availability of essential dietary minerals such as Ca. It is concluded that: (1) piscivores risk increased exposure to dietary methyl-Hg in acidified habitats, and Hg concentrations in prey may reach levels known to cause reproductive impairment in birds and mammals; (2) piscivores do not risk increased exposure to dietary Cd, Pb or Al because these metals are either not increased in fish due to acidification, or increase are trivial from a toxicological perspective; (3) insectivores and omnivores may, under certain conditions, experience increased exposure to toxic metals in some acidified environments. Exposure levels are likely to be sufficiently low, however, that significant risks to health or reproduction are unlikely. More importantly, these wildlife species may experience a drastic decrease in the availability of dietary Ca due to the pH-related extinction of high-Ca aquatic invertebrate taxa (molluscs, crustaceans). Decreased availability of dietary Ca is known to adversely affect egg laying and eggshell integrity in birds, and the growth of hatchling birds and neonatal mammals. Acidification-related changes in the dietary availability of other essential elements, such as Mg, Se and P, have not been established and require further investigation; (4) herbivores may risk increased exposure to Al and Pb, and perhaps Cd, in acidified environments because certain macrophytes can accumulate high concentrations of these metals under acidic conditions. The relative importance of pH in determining the metal concentrations of major browse species, and the toxicological consequences for herbivores wildlife, is not well established and requires further study. A decreased availability of dietary Ca is also likely for herbivores inhabiting acidified environments.     

New perspectives on the passive treatment of ferruginous circumneutral mine waters in the UK

This paper examines major physico-chemical processes during the passive treatment of ferruginous circumneutral drainage from abandoned coal mines in the UK. Data collected over several years of studies on mine water treatment systems shed new light on the relative importance of hydraulics, settling velocity, Fe(II) oxidation rates and cascade aeration, which, in turn, informs the design of future systems. This paper demonstrates that (1) the complex settling behaviour of Fe(III) precipitates may be described by a first-order volumetric process and that settling rate is different for different mine waters; (2) the hydraulic efficiency (ratio of time to peak tracer concentration to nominal residence time) of the settling ponds studied was widely variable at low flow rates in comparison to constructed wetlands; (3) aeration cascades contribute dissolved oxygen and lead to a rise in pH due to CO₂ degassing, which are very important in reducing the required time for iron oxidation and removal; (4) for at least 10 of the 30 sites examined, modelling of the rates of Fe(II) oxidation and particulate settling reveals that removal of iron is primarily dependent on settling rate; and (5) that substantial increases in pH can be brought about by forced aeration of mine water over several hours. Findings of this study apply to the majority of coal mine water treatment sites in the UK and may have broader application to other ferruginous waters with circumneutral pH or after treatment to increase pH.     

Rapid regional recovery from sulfate and nitrate pollution in streams of the western Czech Republic--comparison to other recovering areas

Hydrochemical changes between 1991 and 2001 were assessed based on two synoptic stream surveys from the 820-km2 region of the Slavkov Forest and surrounding area, western Czech Republic. Marked declines of sulfate, nitrate, chloride, calcium and magnesium in surface waters were compared with other areas of Europe and North America recovering from acidification. Declines of sulfate concentration in the Slavkov Forest (-30 microeq L(-1) yr(-1)) were more dramatic than declines reported from other sites. However, these dramatic declines of strong acid anions did not generate a widespread increase of stream water pH in the Slavkov Forest. Only the most acidic streams experienced a slight increase of pH by 0.5 unit. An unexpected decline of stream water pH occurred in slightly alkaline streams.     

Diet shifts during egg laying: Implications for measuring contaminants in bird eggs

We combined stable isotope tracers of blood plasma, blood cells and egg contents with faecal analysis during pre-breeding and egg laying phases in two dipper species Cinclus cinclus and Cinclus mexicanus to determine the occurrence of dietary shifts during egg production and to assess consequences for egg contaminant loads. In both species, changes in δ¹³C (C. cinclus) or δ¹⁵N (C. mexicanus) in female plasma relative to red blood cells indicated a dietary shift during laying that was not observed in males. Eurasian dippers increased prey consumption as breeding approached, shifting from primarily trichopteran insect larvae to ephemeropterans and plecopterans. In American dippers, egg-laying females switched to feeding at a higher trophic level by consuming more fish. Eggs derived from higher trophic level diets contained more mercury (American dipper), polychlorinated biphenyls and some organochlorines, especially DDT metabolites. The results demonstrate how dietary changes during egg laying accompany the demands for egg production with consequences for contaminant deposition in avian eggs.     

Effects of tri-o-cresyl phosphate on serum estrogen and progesterone concentration and ATPase activity in the shell gland of adult hens

The activities of calcium-activated ATPase (Ca2+-ATPase) and calcium magnesium-activated ATPase (Ca2+-Mg2+-ATPase) in the shell gland, and concentrations of 17beta-estradiol (E2) and progesterone in serum were monitored, respectively, from hens orally dosed with tri-o-cresyl phosphate (TOCP) (750 mg/kg). Treated birds were monitored daily for laying and development of delayed neurotoxicity, and activities of Ca2+-ATPase and Ca2+-Mg2+-ATPase were measured at 7 and 10 days after dosing. TOCP-treated birds manifested motor deficit by 7-9 days postdosing, while hens administered vehicle exhibited no signs of delayed neurotoxicity. Ca2+-ATPase and Ca2+-Mg2+-ATPase activities of shell glands from TOCP-dosed hens were not significantly affected (P > 0.05). The serum E2 concentration was significantly reduced in TOCP-treated hens (P < 0.01); however, progesterone levels were unaffected.     

Heterogeneous response of central European streams to decreased acidic atmospheric deposition

We investigated the relations between mountain streamwater chemistry and atmospheric pollution in an arca of 1611 km2 of the Czech Republic by comparing concentrations of SO4. NO3, Cl, Ca and the pH at 432 localities at the time of high (1984-1986) and relatively low (1996-2000) acidic atmospheric deposition. Medians of Cl. SO4, and NO3 decreased by 17, 96 and 60 microeq l(-1), or by 23, 17 and 49%, respectively, during 12 +/- 2 years. The decreased Cl corresponds to decreased emission of industrial Cl (as HCl). The decreased stream SO4 was proportionally lower than the 71% decrease in S-emissions due to leaching of previously accumulated SO4 from soils and non-zero background concentrations. Decreases of NO3 up to 60% in streamwaters with pH < or = 6 was greater than the decrease of N emission in central Europe, about 35%. Extensive regional decrease of NO3 is surprising and is probably described for the first time. The difference in NO3 concentrations between the two periods was probably enhanced by (a) an increase of mineralisation of forest floor in the mid-1980s and (b) by higher uptake of N in the late-1990s. The median pH of the 432 streams did not change but the pH of the sub-population with pH < 6 in the mid-1980s recovered substantially. The pH of circum-neutral streams (pH > 6.5) decreased even as acidic atmospheric deposition decreased.