Effects of zinc on the structure and growth dynamics of a natural freshwater phytoplankton assemblage reared in the laboratory

The response of a natural phytoplankton assemblage to different concentrations of Zn(2+) was evaluated by means of a static laboratory bioassay. Aliquots of surface water, taken in autumn from a non-polluted point of the Reconquista River (Buenos Aires, Argentia), were incubated in mineral nutrient media containing 2.5, 10 or 25 mg litre(-1) of Zn(2+) (as zinc chloride). The comparative structure and dynamics of the communities were followed through periodic physico-chemical and biological analyses of samples taken during 24 days of incubation. Under the experimental conditions of the bioassays, the existence of several Zn(2+) tolerant algal species was shown: the most important of them were Chlorella vulgaris Beij. (Chlorophyceae, Chlorococcales), Nitzschia palea (Kütz.) Smith and Gomphonema parvulum (Kütz.) Kütz. (Bacillariophyceae). It was also demonstrated that the algal responses to Zn(2+) were selectively concentration dependent: at 2.5 and 10 mg litre(-1) a stimulatory effect was observed in the diatoms; at 25 mg litre(-1), diatom toxicity occurred. In contrast, Chlorophyceae growth was stimulated at the maximal Zn level. In general, the diversity, richness and equitability of the community were adversely affected by Zn in a concentration-dependent fashion.     

Effects of pH, organic acids, and inorganic ions on lead desorption from soils

The desorption characteristics of lead in two variable charge soils (one developed from Arenaceous rock (RAR) and the other derived from Quaternary red earths (REQ)) were studied, and the effects of pH value, organic acid, and competitive ions were examined. Desorption of Pb(2+) decreased from nearly 100.0 to 20.0% within pH 1.0-4.0 in both soils, and then the decrease diminished at pH > 4.0. Organic ligands at relatively low concentrations (< or =10(-3) mol L(-1)) slightly inhibited Pb(2+) desorption, but enhanced Pb(2+) desorption at higher concentrations. In this study, citric acid or acetic acid at higher concentrations (>10(-3) mol L(-1)) had the greatest improvement of Pb(2+) desorption, followed by malic acid; and the smallest was oxalic acid. Desorption of the adsorbed Pb(2+) increased greatly with increasing concentrations of added Cu(2+) or Zn(2+). Applied Cu(2+) increased Pb(2+) desorption more than Zn(2+) at the same loading.     

Comparative studies on the biokinetics of Cd, Cr, and Zn in the green mussel Perna viridis and the Manila clam Ruditapes philippinarum

A kinetic approach was employed to determine the rates of metal uptake (Cd, Cr and Zn) from the dissolved phase and the rate constants of metal depuration in the mussel Perna viridis and the clam Ruditapes philippinarum. The effects of ambient metal concentration, salinity, and body size on the metal influx rate were examined. A linear positive relationship was observed between the metal influx rate and the metal concentration in ambient seawater. There was some evidence that Zn uptake was regulated by the bivalves in response to an increase in ambient Zn concentration. The uptake rate constant was highest for Zn and lowest for Cr in both bivalves, and was higher in mussels than in clams. The metal influx rate decreased by 1.6-1.8 times for the three metals when the salinity was increased from 15 ppt to 30 ppt. However, the effect of salinity on Zn influx in mussels was not statistically significant. A negative relationship of Cd and Zn influx rates with tissue dry weight was also found in both bivalves. Cr uptake in mussels was not significantly correlated with body size, but its uptake in clams was significantly correlated with body size. Metal concentration in ambient seawater appeared to be the most determining factor on metal uptake from the dissolved phase in both bivalves. The efflux rate constants of the three metals were within the range of 0.01-0.03 d-1, and were comparable between the mussels and the clams. Using a simple bioenergetic-based kinetic model, it was shown that both dissolved uptake and food ingestion can contribute to metal accumulation in the bivalves. However, Zn accumulation in the clam R. philippinarum was dominated by uptake from food ingestion. Metal partitioning in ingested food was found to be critical in affecting the relative importance of metal uptake from the dissolved phase and food source, primarily because of the large variability of this parameter in natural environments.     

Photochemistry in the mixed aqueous solution of nitrobenzene and nitrous acid as initiated by the 355 nm UV light

The 355 nm photon-initiated microscopic reaction mechanisms of the mixed aqueous solution of nitrobenzene and nitrous acid in the presence or absence of O(2) were studied by the laser flash photolysis technique. The main transient absorption peaks in the recorded spectra were assigned and the growth/decay trends of several transient species were investigated. It was found that the OH radical formed from the photolysis of nitrous acid triggered most of the subsequent radical reactions. The rate constant of the reaction between OH radical and nitrobenzene was measured to be (3.4 +/- 0.1) x 10(9) l mol(-1) s(-1). The product from this reaction, namely C(6)H(5)NO(2)-OH adduct, was found to react with O(2) to yield C(6)H(5)NO(2)-OHO(2) adduct with a rate constant of (1.6 +/- 0.2) x 10(9) l mol(-1) s(-1). Final steady-state products were identified by GC/MS analysis and were in accordance with the transient spectroscopic results. The possible reaction pathways were proposed.     

Acceleration of catalase and peroxidase activities in Lemna minor L. and Allium cepa L. in response to low levels of aquatic mercury

The purpose of this study was to assess certain physiological responses of Lemna minor L. (duckweed) and Allium cepa L. (onion) to aquatic mercury at low concentrations. Following a 96-h exposure of plants to nutrient medium contaminated with known levels of mercuric chloride (HgCl(2)), 0.001 to 4 mg litre(-1) (0.0007 to 2.95 mg Hg litre(-1)) or methyl mercuric chloride (MeHgCl(2)), 0.0001 to 0.1 mg litre(-1) (0.0007 to 0.07 mg Hg litre(-1)), the physiological endpoints measured were the growth of fronds (Lemna minor) or roots (Allium cepa), and catalase and peroxidase activities in both plant assays. The EC(50) for HgCl(2) on the basis of the growth curve of Lemna minor was found to be 2.1 mg litre(-1). HgCl(2) and MeHgCl(2) were lethal to L. minor at concentrations of 4 and 0.01 mg litre(-1), respectively. The range of low concentrations that accelerated growth as well as enzymic activities in L. minor was 0.004 to 0.04 mg litre(-1) for HgCl(2) and 0.001 mg litre(-1) for MeHgCl(2). HgCl(2) and MeHgCl(2) induced maximum enzymic activity in Lemna fronds at concentrations of 0.008 and 0.0005 mg litre(-1), respectively. In Allium roots, catalase activity was accelerated at all the concentrations of HgCl(2) (0.001-2 mg litre(-1)) and MeHgCl(2) (0.0001-0.1 mg litre(-1)) tested. The activity of peroxidase was, however, accelerated by HgCl(2) at concentration range 0.01-1.0 mg litre(-1), or by MeHgCl(2) at 0.001 mg litre(-1). The concentrations of HgCl(2) and MeHgCl(2) that induced the highest enzymic activity in Allium roots were 0.05 mg litre(-1) and 0.001 mg litre(-1), respectively.     

Survival, growth and reproduction of Daphnia carinata (Crustacea: Cladocera) exposed to chronic cadmium stress at different food (Chlorella) levels

In nature, organisms have to respond to a diversity of factors acting simultaneously. The present investigation was conducted to study whether changes in food (Chlorella) levels could modify the chronic toxicity of cadmium on the various life-history parameters, such as survivorship, longevity, life expectancy, fecundity, age at first reproduction, R(0), T, r and growth rates of the cladoceran Daphnia carinata. The study indicated that at low food levels (0.5 x 10(6) cells ml(-1) Chlorella), cadmium concentrations in the range of 27-162 microg litre(-1) reduced these life-history parameters by 50% (EC(50)). At medium food levels (1.5 x 10(6) ml(-1) Chlorella) the EC(50) of cadmium was in the range of 51-127 microg litre(-1). At high food levels (4.5 x 10(6) cells ml(-1) Chlorella), the toxic effect of cadmium was greatly reduced. The decreases in survival, growth and reproduction of D. carinata at high cadmium-low food levels affected the fitness parameter 'r'. The study emphasises the need to include reproductive parameters other than mere survival in toxicity bioassays. The study also stresses the need to incorporate in laboratory tests other relevant factors that might modify pollutant toxicity.     

The solid-solution partitioning of heavy metals (Cu,Zn, Cd,Pb) in upland soils of England and Wales

Ninety-eight surface soils were sampled from the uplands of England and Wales, and analysed for loss-on-ignition (LOI), and total and dissolved base cations, Al, Fe, and trace heavy metals (Cu, Zn, Cd, Pb). The samples covered wide ranges of pH (3.4-8.3) and LOI (9-98%). Soil metal contents measured by extraction with 0.43 mol l-1 HNO3 and 0.1 mol l-1 EDTA were very similar, and generally lower than values obtained by extraction with a mixture of concentrated nitric and perchloric acids. Total heavy metal concentrations in soil solution depend positively upon soil metal content and [DOC], and negatively upon pH and LOI, values of r2 ranging from 0.39 (Cu) to 0.81 (Pb). Stronger correlations (r2=0.76-0.95) were obtained by multiple regression analysis involving free metal ion (Cu2+, Zn2+, Cd2+, Pb2+) concentrations calculated with the equilibrium speciation model WHAM/Model VI. The free metal ion concentrations depend positively upon MHNO3 and negatively upon pH and LOI. The data were also analysed by using WHAM/Model VI to describe solid-solution interactions as well as solution speciation; this involved calibrating each soil sample by adjusting the content of "active" humic matter to match the observed soil pH. The calibrated model provided fair predictions of total heavy metal concentrations in soil solution, and predicted free metal ion concentrations were in reasonable agreement with the values obtained from solution-only speciation calculations.     

Biokinetics of cadmium, selenium, and zinc in freshwater alga Scenedesmus obliquus under different phosphorus and nitrogen conditions and metal transfer to Daphnia magna

The uptake of Cd, Se(IV) and Zn by the freshwater alga Scenedesmus obliquus and the subsequent transfer and release budget in Daphnia magna were investigated under different nutrient additions and cell incubation conditions. An increase in ambient phosphate concentrations from 0.5 micromol l(-1) to 50 micromol l(-1) significantly increased the intracellular accumulation of Cd (by 18x) and Zn (by 5x), but decreased the accumulation of Se (by 126x) in the alga. The percentage of these metals distributing in the intracellular pool of algae also increased substantially with increasing ambient P concentrations. Nitrate addition from 5.0 to 200 micromol l(-1) did not influence the uptake of any of the three metals, although a significant decrease in the intracellular Se distribution was observed. Radiolabeled algae under different nutrient manipulations (semi-continuous culture, starvation, and P-pulse treatments) were used to measure trophic transfer assimilation efficiency (AE) in Daphnia. When the algal cells were grown in a semi-continuous culture, starved for N and P, or were treated with P-pulse, the AEs of Cd and Zn were generally independent of the nutritional conditions, but the Se AE was significantly affected by different P levels. The efflux rate constants, determined during 10 d depuration following 7 days of dietary uptake, decreased significantly for Cd and Zn, but were relatively constant for Se with increasing P concentration. N-addition caused no effect on the metal efflux rate constants. P- or N-additions did not influence the release budget (including molting, neonates, excretion and feces) for all three elements in Daphnia. Our study indicated that phosphate enrichment may substantially increase metal uptake in green alga S. obliquus. Responses of trophic transfer in Daphnia to nutrient enrichment were metal specific. P-enrichment can possibly lead to considerable decrease on Se transfer from algae to zooplankton.     

Dose-response studies with ethylenediurea (EDU) and radish

There is some concern that the antiozonant ethylenediurea (EDU), used for crop loss assessment due to ambient ozone (O3) may per se affect plant growth and yield. In view of this, and to provide knowledge for later field experiments, dose-response studies with EDU and O3 were carried out in greenhouses in winter and spring 1989, using radish (Raphanus sativus L.) cv. 'Cherry Belle' and 'Red Prince', grown in two different substrates. EDU was applied as a single or repeated soil drench in concentrations ranging from 300 to 800 mg litre(-1) in the first, and from 100 to 400 mg litre(-1) in the second trial. In the second experiment, plants were exposed to a chronic level of O3, mimicking ambient patterns, or to filtered air after the EDU-treatment. When applied in concentrations above 300 mg litre(-1), EDU reduced growth, thereby affecting the development of the thickened hypocotyl far more than the shoot growth that was partially stimulated by lower doses of EDU. Phytotoxic symptoms on the leaves, attributable to EDU, were observed at concentrations above 200 mg litre(-1), but complete protection from visible O3-injury was provided by a single application of EDU at a concentration as low as 100 mg litre(-1). Significant interactions on growth characters measured between O3-exposure and EDU application were observed only in one of the substrates. While these results demonstrate the need for careful dose-response studies prior to field assessments, they also provide evidence of a dosage that is effective in protecting radish from O3 damage without interfering with plant growth itself.     

Short-term effects of metals on the filtration rate of the zebra mussel Dreissena polymorpha

In order to study the short-term ecotoxicity of metals to the freshwater mussel Dreissena polymorpha, the effects of Cu, Zn and Cd on the filtration rate of this mussel were determined in laboratory experiments. Filtration rate was chosen as the endpoint, because it is a sensitive sublethal parameter compared to mortality and it is an important parameter given the ecological role D. polymorpha fulfills. The filtration rate was calculated from the decrease in algal concentration, fed to mussels in aquaria, containing different metal concentrations. The EC50 for Cu (41 microg litre(-1)) was lower than for Cd (388 microg litre(-1)) and Zn (1350 microg litre(-1)). The NOEC(accumulation) for the essential metal Zn was higher than for the essential metal Cu. Cadmium, a non-essential metal, was accumulated at all elevated water concentrations, so the NOEC(accumulation) was the concentration in the control water (<0.2 microg litre(-1)). All (no) effect concentrations found in this study were above the quality criteria set for metal concentrations in Dutch surface water, suggesting that the zebra mussel is sufficiently protected by these quality criteria.     

TNT and 4-amino-2,6-dinitrotoluene influence on germination and early seedling development of tall fescue

Cost-effective and environmentally acceptable methods are needed to remediate munitions-contaminated soil. Some perennial grass species are tolerant of soil contaminants and may promote remediation because of their high water use and extensive fibrous root systems. The effects of 2,4,6-trinitrotoluene (TNT) and its reduction product, 4-amino-2,6-dinitrotoluene (4ADNT), on germination and early seedling development of tall fescue (Festuca arundinacea Schreb.) were determined. Tall fescue seeds were germinated in nutrient-free agar containing 0-60 mg TNT litre(-1) or 0-15 mg 4ADNT litre(-1). Germination decreased linearly as TNT concentration increased but was not significantly affected by 4ADNT at these concentrations. Concentrations less than 30 mg TNT litre(-1) or 7.5 mg 4ADNT litre(-1) had little effect on seedling growth and development. Higher TNT or 4ADNT concentrations substantially delayed seedling development, caused abnormal radicle tissue development, and reduced secondary root and shoot growth. Seedling respiration rates decreased linearly with increasing TNT concentration. Experiments indicate that tall fescue may be grown in soils that maintain soil solution concentrations of 30 mg TNT litre(-1) or less.     

Evidence for a seasonal fluctuation of arsenic in New Zealand's longest river and the effect of treatment on concentrations in drinking water

A year-long survey, with samples collected weekly, was conducted to estimate long-term average concentrations of arsenic in treated and untreated drinking water for the city of Hamilton, New Zealand. The average concentration of arsenic in Waikato River water at Hamilton before processing was found to be (32.1 +/- 3.7) microg litre(-1), about three times above the new WHO limit of 10 microg litre(-1). However, full conventional water treatment effects a five-fold reduction in arsenic concentrations in drinking water to a level which meets the new standards of (6.2 +/- 0.8) microg litre(-1). The results of both this study and retrospective analysis of archived data suggest that total arsenic concentrations in the Waikato River are likely to follow a regular seasonal variation, being about 10-25 microg litre(-1) higher in the summer months. Changes in river flow rates have an almost negligible effect on the summer peak and winter trough; it is proposed that most of the variation in total arsenic concentrations may be due to the seasonal conversion of arsenic in the river sediments to more soluble forms.     

Henry's law constants of phenol and mononitrophenols in water and aqueous sulfuric acid

Phenols are widely present in the atmosphere and nitration probably in the aerosol phase leads to nitrophenols. Nitration by nitric acid in sulfuric acid can be rapid, but little is known of the process under atmospheric conditions. The Henry's law constants K(H)(dagger) of phenol and 2-, 3- and 4-nitrophenol were all measured by a bubble stripping method as: 2820mol kg(-1) atm(-1) (at 298K), 147mol kg(-1) atm(-1) (at 298K), 1.6x10(4)mol kg(-1)atm(-1) (at 308K) and 2.1x10(4)mol kg(-1) atm(-1) (at 308K), respectively. The Henry's law constant of phenol in sulfuric acid systems is lower by more than a factor of two at 1020mol kg(-1) atm(-1) (at 298K) in 40wt% sulfuric acid, which is in line with salting-out of oxygen-containing aromatic compounds in water-sulfuric acid systems. The Henry's law constants of 2- and 4-nitrophenol behave differently and are almost independent of sulfuric acid concentration. The variation of K(H)(dagger) with temperature (T) described in terms of -dln(K(H)(dagger))/d(1/T) does not to vary with sulfuric acid concentration, suggesting enthalpy of dissolution for phenol is independent of sulfuric acid. The series of Henry's law constants measured here can describe the equilibrium situation for phenols in careful determinations of phase partitioning in the atmosphere.     

Chemistry of soil solutions under different kinds of vegetation in the vicinity of a thermal power station

The influence of atmospheric deposition on the chemical characteristics of soil solutions in a small catchment area in NW Spain was studied. The soils, developed from slates, were sampled from seven sites supporting different forms of vegetation (deciduous and pine forest and heath). Soil solutions were extracted, by the column displacement method, from soil samples collected monthly from March 1992 until November 1993. The solutions were acidic with a low content of basic cations. The most common ions in all horizons were Cl(-) and Na(+), due to marine influence. In the surface horizons (0-10 cm), relatively high concentrations of SO(2-)4 (150-380 micromol litre(-1)) and Zn (approximately 2 micromol litre(-1)) were obtained, with good correlation between the two ions. These results, along with the prevalence of inorganic forms of Al (50-90% of total Al), were related to the effects of acidic deposition in the catchment area. The more rapid breakdown of litter in the soils under deciduous forest explains the greater ionic concentrations obtained in these solutions.     

Trout farm effluents: characterization and impact on the receiving streams

Effluents from three rainbow trout (Oncorhynchus mykiss) farms located in Northern Portugal were characterized and their impact on the receiving streams was evaluated. Mean fish productions in the studied fish farms were 15, 55 and 500 t of trout per year, respectively. The feeding water was abstracted from Fornelo, Inha and Coura Rivers, at flow rates ranging from 1.2 (15 t year(-1) fish farm) to 4.8 litre s(-1) per ton annual fish production (500 t year(-1) fish farm). As the water flows through the farms, net variations in the chemical characteristics were observed: a mean reduction in the dissolved oxygen (DO) concentration between 0.7 and 2.4 mg litre(-1); mean increases between 1.9 and 3.2 mg CaCO3 litre(-1) for total alkalinity, between 0.9 and 14 mg litre(-1) for BOD5, between 0.27 and 1.46 mg litre(-1) for ammonia nitrogen (NH4-N), between 0.060 and 0.579 mg litre(-1) for soluble phosphorus (PO4-P) and less than 16 mg litre(-1) for suspended solids; variations in the pH value and nitrate nitrogen concentration were not statistically significant (p<0.05). At the 500 t year(-1) fish farm it was also possible to detect net increases of total hardness (3.2 mg CaCO3 litre(-1)), electric conductivity (19 mS cm(-1)) and permanganate value (3.6 mgO2 litre(-1)). At the other farms net variations in these parameters were not significant. Net mass flow variations reported to the annual fish production are presented. The DO mass flow decreased, on average, between 255 and 549 g t(-1) of fish per day. The mean daily BOD5 increase ranged from 353 to 1510 g t(-1) of fish. The corresponding ranges for the other parameters were 105-157 g t(-1) for NH4-N, 24-62 g t(-1) for PO4-P, 348-1035 g CaCO3 t(-1) for total alkalinity and 224 x 10(6)-506 x 10(6) t(-1) for mesophilic bacteria. Daily net variations of suspended solids, total hardness, electric conductivity and permanganate value were below 1753 g t(-1), 342 g CaCO3 t(-1), 2081 mS cm t(-1) and 392 gO2 t(-1), respectively. Longitudinal concentration profiles for the most relevant parameters show the impact of the effluent discharges on the physico-chemical and bacteriological river water quality downstream from the trout farms. Analyzing the situations from a purely chemical point of view, the polluted stretches were 3, 5 and 12 km long downstream from the effluent discharges, respectively. The microbiological contamination extended over longer distances.     

Adsorption of aluminium by stream particulates

An experimental study was made of the adsorption of aluminium by fine particulates from Whitray Beck, a hill stream in NW England. Adsorption increased with Al(3) activity, pH and concentration of particles, and could be quantitatively described by the empirical equation: [Formula: see text] [particles] where square brackets indicate concentrations, curly brackets, activities, and alpha, beta and gamma are constants with values of 5.14x10(-10) (mol litre(-1))(2.015) (g particles litre(-1))(-1), 0.457, and 1.472, respectively. For the experimental data, the equation gave a correlation ratio of 0.99. The equation accounts reasonably well for the adsorption of Al by particulates from seven other streams. In applying the equation, it must be borne in mind that the desorption kinetics of Al depend on pH, and rapid reversibility (<15min) can only be assumed for pHor=10%) of total monomeric Al.     

Unavailability of polynuclear aromatic hydrocarbons from coal particles to the eastern oyster

The accumulation by oysters of polycyclic aromatic hydrocarbons (PAH) from coal dust entering the estuarine environment has been postulated in the vicinity of coal transfer operations. Oysters Crassostrea virginica were exposed to coal dust plus 15 day leachate at concentrations of 10 mg litre(-1) and 1 mg litre(-1) coal dust for 28 days in a flow-through test system. Potential effects of the exposures were measured by comparing the uptake of PAH and the growth of the exposed animals versus control groups. Oysters sampled at 7, 14 and 28 days did not exhibit an increase in PAH body burden over control animals provided the guts were first purged of particulates. Even at the high test concentrations (10 mg litre(-1)), no effect of the exposure on shell growth was observed.     

Physiological effects of metal toxicity on the tropical freshwater shrimp Microbrachium carcinus (Linneo, 1758)

Pilot tests were performed to determine the level at which Zn(++) and Cu(++) ceased to be acutely toxic in Macrobrachium carcinus. The data indicated that the static 96h-LC(50) values for Zn(++) and Cu(++) were 0.2 and 0.1 mg litre(-1) respectively. A differential reduction in respiration and ammonia excretion rates was noted with increasing concentrations of these metals in the water. These levels may in a toxic body burden and a progressive deterioration of gill efficiency. A decrease in respiration and ammonia excretion rates resulted in a decrease in O:N ratios, upon exposure to Zn(++) and Cu(++) concentrations. The ratios obtained indicate that these metals, also increased dependence on carbohydrate or lipid reserves.     

Ozone flux to Picea sitchensis (Bong) Carr and Picea abies (L) Karst during short episodes and the effects of these on transpiration and photosynthesis

Sitka spruce and Norway spruce were grown in controlled environments and then exposed to ozone (O3) for short periods as in mid-afternoon episodes experienced in the forest. For concentrations of between 20 and 300 nl litre(-1) there were linear relationships between exposure concentration and O3 uptake rates. Increasing photon flux densities increased rates of photosynthesis and transpiration, the increases being larger in actively growing than dormant seedlings. Physiological condition (dormancy or active growth), species and photon flux density were found to influence O3 flux via their effects on stomatal conductance. Exposure to 80 nl litre(-1) O3 resulted in consistent increases of stomatal conductance and there were also indications that water-use efficiency was decreased.