Chemical and biological effects of acid, aluminium and lime additions to a Welsh Hill-stream

Chemical and biological responses to simultaneous additions of acid, aluminium and lime were investigated in contiguous 250m-reaches of a chronically acidic stream in Wales. Treatments were applied for 24 h, and from the upstream end were as follows: zone A-untreated, pH 5.0, 0.37 mg litre(-1) filterable Al; zone B-acidified to pH 4.5, 0.40 mg Al litre(-1) (47% of Al attributed to release from the stream bed due to acid additions); zone C-acidified to pH 4.5 and Al dosed to 0.67 mg litre(-1); zone D-dosed with limestone slurry, resulting in pH 7.2, 0.13 mg Al litre(-1). In all reaches, the chemistry of the interstitial water at depths of 0.15 and 0.3 m never fell below pH 5.5, with corresponding decreases in Al and increases in base cation concentrations. Brown trout, Salmo trutta, and crayfish, Austropotamobius pallipes, held in the stream showed decreases in plasma [Na(+)] and haemolymph [Na(+)], respectively, in all acidic zones (A, B, C): these responses were mitigated by liming (zone D). Thus both chronic and simulated episodic levels of pH and dissolved Al were sub-lethally toxic to test species of aquatic fauna. This experiment also demonstrates a stream bed source/sink of Al, and the availability of a possible refuge from acidic surface waters within the substratum.     

Benthic macroinvertebrate community structure in 20 streams of varying pH and humic content

The structure of stream benthic macroinvertebrate communities in relation to pH and humic content was studied in 20 second and third-order forest streams in southern Sweden. Streams varied in pH from 4.2 to 8.0, and in humic content from a colour of 5 to 1200 mg Pt litre(-1). There was a positive relationship between pH and species richness, with a discontinuity occurring at pH approximately 5.7. At pH > 5.7, species richness decreased with increasing colour. At pH < 5.7 there was a positive correlation between species richness and humic concentration up to a colour of about 200-300 mg Pt litre(-1). this may be explained by high concentrations, 0.4-0.9 mg litre(-1), of labile monomeric Al occurring in the low coloured acid streams. In streams with a colour > 200 mg Pt litre(-1) labile monomeric Al was less than 0.2 mg litre(-1). There was no significant change in species richness above this threshold, but a shift in species composition towards a dominance of Plecoptera and Chironomidae. This threshold model seems to explain the observed differences in stream benthic community structure better than a simple linear relationship with pH or humic content.     

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.     

Littoral zooplankton responses to acid and aluminum stress during short-term laboratory bioassays

During autumn 1990, littoral zooplankton were collected from three alkaline lakes in Ohio, USA. Toxicity tests were performed, in which animals were placed into treatments of pH 4.5, with or without 500 microg litre(-1) Al added. Percentage survival after 24 h was determined for each test species, and compared to survival in controls (pH roughly 8.0). Three distinct responses were observed: (1) Four cladocerans, Simocephalus serrulatus, Diaphanosoma birgii, Acantholeberis curvirostris and Chydorus sphaericus, were tolerant of both acid and Al, with no significant reductions in survival in the treatments. (2) The cladoceran Eurycercus lamellatus and the capepod Acanthocyclops vernalis were sensitive to both acid and Al, and suffered 100% mortality in both treatments. (3) The cladocerans Camptocercus rectirostris, Alona costata and Pleuroxus denticulatus, and the copopod Mesocyclops edax showed decreased survival in the acid treatment, and a significantly greater decrease in the acid plus Al treatment. For nine of the ten test species, the results were consistent with previous survey and paleolimnological studies. The results indicate that direct toxic effects of H+ and Al ions largely determine the responses of these common littoral species to acidification.     

Acid and aluminum effects on freshwater zooplankton: an in situ Mesocosm study

An in situ mesocosm experiment was performed to evaluate the role of aluminum toxicity in determining zooplankton community responses to take acidification. Large plastic enclosures were suspended in East Twin Lake, Ohio, USA, and duplicates were either untreated controls (pH 8.8), acidified to pH 4.5 over a 23 day period, or acidified and also spiked with incremental additions of Al, to produce a final inorganic monomeric Al level of 180 microg/liter at pH 4.5. Zooplankton abundance and species richness declined in both acid treatments, relative to the control, as numerous acid-sensitive species were eliminated. All of the acid-sensitive species were also Al-sensitive, declining in abundance more rapidly in the acid plus Al treatment than in the acid-alone treatment. Only two small cladocerans (Bosmina longirostris and Chydorus sphaericus) were acid tolerant. Both were also tolerant of elevated Al levels.     

Artificial acidification of a non-acidic and an acidic headwater stream in Maine, USA

Two headwater streams with low DOC and different pHs (4.5-4.8 and 5-6.5) were acidified with H2SO4 to pH 4.1 and 4.5, respectively, for 24-h periods. Neutralization of the added acid occurred by protonation of ANC (HCO3-dominated in the higher pH stream), desorption of Ca (< 15 microeq litre(-1)) and Mg (<6 microeq litre(-1)), and desorption and dissolution of AL (<250 microg litre(-1)) from the stream bed. The concentrations of dissolved organic carbon (DOC) remained constant within the experimental reaches. The concentrations of Na, K an H4SiO4 also remained constant, indicating no detectable increase in the rate of chemical weathering in the stream bed. After acid addition was stopped, concentrations of Ca, Mg and Al decreased to below background, indicating reversible ion exchange as the principal mechanism for the mobility of Ca and Mg and to a lesser extent for Al. Repeated acidifications indicated that significant regeneration of cations on the exchange surfaces of the stream substrate occurs rapidly.     

Phytoplankton succession during acidification with and without increasing aluminum levels

An in situ mesocosm experiment was performed to investigate the role of aluminum in controlling phytoplankton community succession during lake acidification. Large (2000 liter) mesocosms were suspended in mesotrophic East Twin Lake, Ohio, USA. Duplicates were either untreated controls (pH 8.8), acidified to pH 4.5 over 23 days, or acidified and spiked with 200 microg/liter Al in incremental additions. Filamentous blue greens, diatoms and other chrysophytes became extinct in both acid treatments, but declined most rapidly where Al levels were also increased. The large desmid Closterium and the filamentous chlorophyte Mougoetia became dominant in the Acid treatment. In the Acid + Al treatment, these algae also became dominant, but the species with greatest biomass was the dinoflagellate Peridinium inconspicuum. Acidification (with or without added Al) also resulted in a significant shift in the algal size spectrum to larger (> 20 microm) cells.     

Stability of core/shell quantum dots—role of pH and small organic ligands

The improvement of knowledge about the toxicity and even processability, and stability of quantum dots (QD) requires the understanding of the relationship between the QD binding head group, surface structure, and interligand interaction. The scanned stripping chronopotentiometry and absence of gradients and Nernstian equilibrium stripping techniques were used to determine the concentration of Cd dissolved from a polyacrylate-stabilized CdTe/CdS QD. The effects of various concentrations of small organic ligands such as citric acid, glycine, and histidine and the roles of pH (4.5–8.5) and exposure time (0–48 h) were evaluated. The highest QD dissolution was obtained at the more acidic pH in absence of the ligands (52 %) a result of the CdS shell solubility. At pH 8.5 the largest PAA ability to complex the dissolved Cd leads to a further QD solubility until the equilibrium is reached (24 % of dissolved Cd vs. 4 % at pH 6.0). The citric acid presence resulted in greater QD dissolution, whereas glycine, an amino acid, acts against QD dissolution. Surprisingly, the presence of histidine, an amino acid with an imidazole functional group, leads to the formation of much strong Cd complexes over time, which may be non-labile, inducing variations in the local environment of the QD surface.     

Reutilization of granite powder as an amendment and fertilizer for acid soils

The properties of granite powders--a granite manufacturing waste product-were analyzed to assess their potential use as amendments and fertilizers on acid soils. Two types of powders were characterized: one produced during cutting of granite with a diamond-edged disc saw, comprising only rock powder, the other produced during cutting with a multi-blade bandsaw, containing calcium hydroxide and metal filings added during the cutting procedure. The acid neutralizing capacity of the granite powders was assessed in short- (2-3 h) and medium-term (1-30 d) experiments. The powders showed a buffering capacity at around pH 8, which corresponded to the rapid dissolution of basic cations, and another buffering effect at pH<4.5, attributable to the dissolution of Fe and Al. The acid neutralizing capacity (ANC) determined in the short-term experiments, to a final pH of 4.5, varied between 5 and 61 cmol H+kg(-1) powder. The ANC to pH 4.5 obtained in the medium-term experiments was much higher than that obtained in the short-term experiments, reaching a maximum ANC value of 200 cmol H+kg(-1) powder. There was no great difference in the neutralizing capacity determined at between 1 and 30 d. The most abundant elements in acid solutions obtained at the end of medium-term experiments were Mg and Ca for disc saw powders, whereas Ca and Fe (at pH<5) were the most soluble elements in the bandsaw powders. The rapid release of these cations suggests the possible effective use of the granite powders as a source of nutrients on being added to acid soils.     

Toxicity and bioaccumulation of thallium in Hyalella azteca, with comparison to other metals and prediction of environmental impact

Thallium (Tl) is an extremely toxic but little studied metal. For Hyalella azteca exposed in Lake Ontario water, a 25% reduction in survival (the LC25) occurred at about 48 nmol litre(-1) after 4 weeks. Body concentrations of Tl, which were proportional to water concentrations, averaged 290 nmol g(-1) dry mass at the LC25. Growth was reduced at slightly lower concentrations. Concentrations affecting reproduction were variable at < 50% of the LC25. On a water-concentration basis Tl was more toxic than Ni, Cu or Zn, but less toxic than Cd or Hg to Hyalella; toxicity to Pb was similar. On a body-concentration basis, the toxicities of Tl, Cd, Hg and Pb were all similar. Unlike Cd, Tl toxicity and uptake was affected by K concentrations in the water, and not by Ca, Mg, Na or other ions. Toxicity was proportional to uptake, and body concentrations were better predictors of toxicity than water concentrations in media with varying K concentrations. Preliminary measurements of Tl and Cd uptake by Hyalella from Hamilton Harbour and Lake Ontario sediments suggested that total bioavailable metal concentrations were greater in deep-water sediments from Lake Ontario than in sediments from the harbour. The ratio of bioavailable metal to the toxic threshold was slightly higher for Cd than for Tl, but well below 1 for both metals.     

Changes in gill morphology of Atlantic salmon (Salmo salar) smolts due to addition of acid and aluminum to stream water

One-year-old Atlantic salmon smolts were held in three artificial channels adjacent to a softwater (mean sp. cond. 30 microS cm(-1), circumneutral stream. Water in one channel was untreated (mean pH 6.25); the others received additions of acid (to mean pH 5.6), or acid plus aluminum (to mean pH 5.5; mean exchangeable Al 158 microg litre(-1)). Gills were sampled after 16 and 23 days of exposure for morphometric examination. On primary lamellae, chloride cells were more numerous in both experimental treatments than in controls. In contrast, numbers of chloride cells on secondary lamellae were elevated only in fish exposed to acid without added Al. Chloride cell size and shape also varied with time and treatment. Fewer gill mucous cells were found in fish exposed to acid plus Al than in controls. Chloride cell proliferation and structural changes may represent an attempt to compensate for increased ionic effluxes with low pH stress by increasing uptake. However, if Al concentrations are high, chloride cells do not proliferate along the secondary lamellae, or proliferating cells are damaged and lost. This may limit the potential to increase ionic uptake.     

Photochemically induced formation of the "Al13" tridecameric polycation in the presence of Fe(III) and organic acids

We found that light-induced Fe(III) reduction associated with the oxidation of a simple hydroxy-carboxylic acid (lactate) caused the formation of the AlO4Al12(OH)24(H2O)12 polycation ("Al13"). Initial conditions were a lactate:Al:Fe ratio of 1:0.76:0.11 in a partially neutralized solution. Base was added rapidly and no Al13 was detected in samples kept in the dark. With exposure to light, Fe(III) reduction was rapid and Fe(II) reached a maximum within 1 day. After the maximum, steady-state Fe(II) declined from 54% to 43% over eight days. During this same time period, the lactate concentration fell to 2% of the original, pH rose from 4.05 to 4.46, and the Al13 detectable by 27Al NMR increased to 2.3 mmol l(-1) (51% of the total solution Al). The formation of Al13 is attributed to the pH rise resulting from the removal of the organic acid buffer. Similar photo-induced chemical changes occur in natural waters and may promote the formation of Al13, conditions permitting.     

Effective uptake of decontaminating agent (citric acid) from aqueous solution by mesoporous and microporous materials: an adsorption process

The presence of citric acid in decontamination waste can cause complexation of the radioactive cations resulting in interferences in their removal by various treatment processes such as chemical precipitation, ion-exchange, etc., which are employed for the removal of radioactivity and may cause potential danger to the environment. Mesoporous Al-MCM-41 (Si/Al=30, 51, 72 and 97) and Si-MCM-41 molecular sieves were synthesized hydrothermally and characterized by XRD, BET (surface area) and FT-IR to evaluate the removal of citric acid through an adsorption process. Adsorption of citric acid over Al-MCM-41 shows the applicability of Freundlich and Langmuir isotherm and follows first order kinetics. The effects of contact time, concentration of citric acid, adsorbents (various Si/Al ratios of Al-MCM-41, Si-MCM-41, Hbeta zeolite and commercial carbon) and pH have been investigated. It has been found that the amount of citric acid adsorbed per unit gram of catalyst followed the order Al-MCM-41 (Si/Al=30)>Al-MCM-41 (Si/Al=51)>activated charcoal>Al-MCM-41 (Si/Al=72)>Al-MCM-41 (Si/Al=97)>Si-MCM-41>Hbeta zeolite.     

Influence of pH and aluminum on developing brook trout in a low calcium water

Eyed embryos of brook trout (Salvelinus fontinalis) were exposed to nominal pHs of 4.5, 5.5 and 7.5 with and without aluminum (300 microg liter(-1)) in extremely soft water (hardness <9mg liter (-1)) at 12 degrees C. Embryo mortality exceeded 80% at pH 4.5, averaged 15 to 18% in the pH 5.5 treatments and was less than 2% in the pH 7.5 treatments. Aluminum significantly reduced embryo mortality (85.3% vs 99.5%) at pH 4.5 but did not affect mortality at pH 5.5 or pH 7.5. Percent hatch and poor hatch were pH dependent and were not significantly influenced by aluminum. Brook trout larvae cumulative mortalities were 100% within 30 days at pH 4.5, with or without aluminum; 69% after 60 days at pH 5.5; 100% in 15 days at pH 5.5 with aluminum and 20% after 60 days at pH 7.5 with or without aluminum. Fish that survived the pH 5.5 treatment showed decreased growth and behavioral impairments compared to the controls (pH 7.5 without aluminum).     

污泥中重金属的去除及回收试验

论述了利用离子交换技术循环使用柠檬酸去除污泥中重金属,并置换回收重金属的适宜工艺条件.经柠檬酸处理后,污泥中90%以上的重金属被去除;柠檬酸处理液中的重金属用离子交换法回收,考察了树脂种类、流速、操作方式等因素对离子交换、再生效果的影响;在适宜工艺条件下,重金属的交换率均为100%,而洗脱率均接近90%;柠檬酸及离子交换树脂循环使用,重金属也得到回收,降低了处理成本.     

Oxidative stress is an early symptom triggered by aluminum in Al-sensitive potato plantlets

The objective of this study was to evaluate whether the oxidative stress caused by aluminum (Al) toxicity is an early symptom that can trigger root growth inhibition in Macaca (Al-sensitive) and SMIC148-A (Al-tolerant) potato clones. Plantlets were grown in a nutrient solution (pH 4.00) with 0, 100 and 200 mg Al L⁻¹. At 24, 72, 120 and 168 h after Al addition, root length and biochemical parameters were determined. Regardless of exposure time, root length of the Macaca clone was significantly lower at 200 mg Al L⁻¹. For the SMIC148-A clone, root length did not decrease with any Al treatments. Al supply caused lipid peroxidation only in Macaca, in both roots (at 24, 72, 120 and 168 h) and shoot (at 120 and 168 h). In roots of the Macaca, catalase (CAT) and ascorbate peroxidase (APX) activity decreased at 72 and 120 h, and at 24, 72 and 120 h, respectively. At 168 h, both activities increased upon addition of Al. In roots of the SMIC148-A, CAT activity increased at 72 and 168 h, whereas APX activity decreased at 72 h and increased at 24, 12 and 168 h. The Macaca showed lower root non-protein thiol group (NPSH) concentration at 200 mg Al L⁻¹ in all evaluations, but the SMIC148-A either did not demonstrate any alterations at 24 and 72 h or presented higher levels at 120 h. This pattern was also observed in root ascorbic acid (AsA) concentration at 24 and 120 h. The cellular redox status of these potato clones seems to be affected by Al. Therefore, oxidative stress may be an important mechanism for Al toxicity, mainly in the Al-sensitive Macaca clone.     

Observations on the influence of water and soil pH on the persistence of insecticides

Abstract

The pH‐disappearance rate profiles were determined at ca. 25°C for 24 insecticides at 4 or 5 pH values over the range 4.5 to 8.0 in sterile phosphate buffers prepared in water‐ethanol (99: 1 v/v). Half‐lives measured at pH 8 were generally smaller than at lower pH values. Changes in half lives between pH 8.0 and 4.5 were largest (>1000x) for the aryl carbamates, carbofuran and carbaryl, the oxime carbamate, oxamyl, and the organophosphorus insecticide, trichlorfon. In contrast, half lives of phorate, terbufos, heptachlor, fensulfothion and aldicarb were affected only slightly by pH changes. Under the experimental conditions described half lives at pH8 varied from 1–2 days for trichlorfon and oxamyl to >1 year for fensulfothion and cyper‐methrin. Insecticide persistence on alumina (acid, neutral and basic), mineral soils amended with aluminum sulfate or calcium hydroxide to different pH values and four natural soils of different pH was examined. No correlation was observed between the measured pH of these solids and the rate of disappearance of selected insecticides applied to them. These observations demonstrate the difficulty of extrapolating the pH dependent disappearance behaviour observed in homogeneous solution to partially solid heterogeneous systems such as soil.     

The impact of aluminium on green algae isolated from two hydrochemically different headwater streams, Bavaria, Germany

Two strains of green algae (Scenedesmus sp. and Chlorella sp.) have been isolated from two headwater streams differing in stream chemistry (Eger river: acidic, low alkalinity; Püttlach river: slightly alkaline, high alkalinity). In this study the growth response of these indigenous algae to increased concentrations of aluminium (Al) is investigated. A semi-continuous culture technique was used for Al-toxicity studies. Algal response was determined by calculating growth rates from turbidity and cell counts. Those Al-species which are well known to be toxic were estimated by equilibrium calculations using the WATEQ computer program (Truesdall & Jones, 1973). The pH-value of the culture media was usually pH=5, except for one of the test series. Tested concentrations ranged from c=4 to 220 micromol litre(-1). The isolated strains of green algae were highly sensitive to increased Al-concentrations. The strain isolated from the Püttlach river was more sensitive than the Eger river algae. A total growth inhibition occurs at Al-concentrations of c=4 micromol litre(-1) if the whole Al was added at once. If Al was added gradually into the growth media the response of the algae was delayed. This is due to Al-enrichment in cells. In our long term toxicity studies, growth inhibition occurs even at nearly neutral pH-conditions (pH=6.5) although Al toxicity is expected at pH-values less than pH=5.5. This new result confirms the need of long-term studies in continuous cultures under simulated natural conditions. This might be the only way to achieve valid conclusions about the fate and the toxicity of environmental pollutants.     

Biochemical responses of the mycorrhizae in Pinus massoniana to combined effects of Al, Ca and low pH

Biochemical responses of Pinus massoniana, with and without the inoculation mycorrhizal fungus Pisolithus tinctorius at the root, to artificial acid rain (pH 2.0) and various Ca/Al ratios were investigated. Some enzymes associated with the nutritive metabolism, such as acid phosphatase, alkaline phosphatase, nitrate reductase, mannitol dehydrogenase and trehalase, in the roots, stems and leaves of plant were obviously inhibited by the artificial acid rain and Al. After treatment with pH 2.0 + Ca/Al (0/1 or 1/10) artificial acid rain, the protein content in the organs was decreased. However, the activities of superoxide dismutase (SOD) and peroxidase (POD) and glutathione (GSH) concentrations were induced. It demonstrated that acid rain and Al could induce oxygen radicals in plant. Compared with the treatments with lower pH or Al, respectively, the combination of lower pH and Al concentration was more toxic to P. massoniana. Al toxicity could be ameliorated by the addition of Ca and the amelioration was the most when the ratio was 1/1 among the various Ca/Al ratio. Infection with mycorrhizal fungus P. tinctorius at the root of P. massoniana increased the ability of the plant to resist the toxicity of artificial acid rain and Al stress.     

Chronic toxicity of ammonia to the amphipod Hyalella azteca; Importance of ammonium ion and water hardness

Ammonia toxicity resulted in the continuous mortality of Hyalella azteca for up to 10 weeks with similar mortality rates for adults and young. Growth was not reduced at concentrations below those causing chronic mortality (1 mM total ammonia in Lake Ontario water), but reproduction was reduced at concentrations as low as 0.32 mM. Chronic mortality was a function of total ammonia (or ammonium ion), and not un-ionized ammonia, when the pH was adjusted by addition of acid. However, a 1 in 10 dilution of Lake Ontario water in distilled water resulted in a 10-fold reduction in the 4 week LC50. In contrast to common practice, ammonia toxicity to Hyalella is best defined on a total ammonia basis, but variations in hardness and other ions must be taken into account.