The acute toxicity of phenol and unionized ammonia, separately and together, to the ephemeropteran Baetis rhodani (Pictet)

The acute toxicity of phenol and ammonia, singly and in combination, to larvae of the ephemeropteran, Baetis rhodani, was examined using a computerized continuous flow system in the laboratory. The 24 h LC50 values (with 95% confidence intervals) were calculated to be 29.9 (17.3-51.5) mg phenol litre(-1) and 8.2 (2.0-33.0) mg un-ionized ammonia litre(-1). When phenol and ammonia were together in low concentration (< 20 mg litre(-1) and < 3 mg litre(-1) [un-ionized], respectively), they expressed their toxicity additively, but at higher concentrations they behaved in a greater-than-additive manner. When the 24 h LC50 values were used to predict the toxicity of a coking plant effluent, containing principally ammonia and phenol, it was found that the B. rhodani larvae died quicker than expected indicating the presence of other toxic chemicals. This exemplifies the value of using direct toxicity assessments to detect the presence of unknown toxicants.     

Liming of River Audna,Southern Norway: a large-scale experiment of benthic invertebrate recovery

This study describes the recovery of sensitive invertebrates after liming of the anadromous part of River Audna in 1985. The river lost its salmon population during 1960-1970. The aim of the liming was to produce a water quality with pH > 6.0 and ANC > 20 microg L(-1) and to reduce the content of labile aluminum. Highly sensitive invertebrates like the mayfly Baetis rhodani were not found in the river before liming. Two years after liming, several sensitive invertebrate species showed a positive response. B. rhodani was then recorded at 2 sites in the lower part of the river. In the following 5 years several species of sensitive invertebrates recolonized the whole limed reach of the river and became numerous. Ten years after liming the snail Lymnaea peregra was recorded in the river. The dispersa of this species was also very fast and after 5 years it was found at all investigated sites in the limed main river covering a reach of 40 km. Reduced sulfur deposition in the area also resulted in water-quality improvements in th unlimed stretches of River Audna. Comparisons between limed and unlimed localities indicated that the water quality and the critical limits of sensitive species are the ma factors determining the fauna composition in River Audna independent of the reason for the change in water quality.     

Mitigation of peroxidative stress for barley exposed to cadmium in the presence of water-extractable organic matter from compost-like materials

The effects of water-extractable organic matter (WEOM) from compost-like materials on peroxidative stress were investigated for hydroponic culture of barley exposed to Cd. In the presence of WEOM, lipoxygenase activity and malondialdehyde, indices of peroxidative stress in barley, were significantly reduced, compared to those with Cd alone (5 μM) for a 30-d culture (p < 0.05). In addition, Cd uptake in the presence of WEOM samples was significantly lower than that in their absence (p < 0.05). These results indicate that the addition of WEOM can be effective in mitigating the peroxidative stress in barley exposed to Cd. Of the total Cd in the solution, 7–8% was complexed with WEOM, indicating that the complexation of Cd with WEOM is a minor factor in reducing Cd-induced stress in barley. The WEOM sample was purified by cation-exchange column and ultrafiltration to remove the nutrient minerals, such as Ca, Mg and Fe. When the purified WEOM was employed for hydroponic culture in the presence of Cd, significant decreases in peroxidative stress and Cd uptake were observed (p < 0.05). These results show that the organic components in WEOM contribute to the mitigation of peroxidative stress in barley exposed to Cd.     

Cadmium uptake by tobacco as affected by liming, N form, and year of cultivation

Tobacco is able to accumulate cadmium and reduction of cadmium content can reduce health hazards to smokers. Soil pH and form of N fertilizers are among the factors affecting Cd uptake by tobacco. This hypothesis was tested in an acid soil in northern Greece by a four year field experiment. The variability of Cd uptake by tobacco was attributed to the variation of soil Cd availability as affected by soil pH. Liming with 3000 kg Ca(OH)(2) ha(-1) increased soil pH by 0.8 units and decreased extractable with DTPA soil and leaf Cd by 40% and 35%, respectively. The ammonium fertilizer caused the opposite, but weaker, effects. Liming reduced soil Cd more in the ammonium treatment than in nitrate or combined N treatments. The year of cultivation strongly affected soil and leaf Cd. Four years after tobacco cultivation, soil pH was reduced by 0.5 units, whereas soil and leaf Cd reduction was more than 60% in the limed treatments. Liming affected Cd uptake only in the first three years of cultivation.     

Mayfly larvae (Baetis rhodani and B. vernus) as biomonitors of trace metal pollution in streams of a catchment draining a zinc and lead mining area of Upper Silesia,Poland

Larvae of two Baetis species were used to investigate spatial and temporal variability in the bioavailabilities of cadmium, copper, lead, zinc and iron in the river Biala Przemsza and its tributaries draining an area of lead and zinc mining in Upper Silesia, Poland. Accumulated metal concentrations were measured in April, May, August and November 2000. Both species indicated significant local geographical variability in availabilities of zinc, iron, lead and cadmium, but not copper. Accumulated concentrations of lead, zinc and cadmium confirmed the high general contamination of the Biala Przemsza system by these three trace metals. Larvae showed little seasonal variation in concentrations of cadmium, copper, lead and iron. Accumulated zinc concentrations were low in Baetis rhodani in August, perhaps as a result of insufficient time for high concentrations to accumulate since hatching of the larvae. Samples collected in August most nearly matched criteria of the greatest availability of larvae for collection and their size homogeneity, minimising the possibilities of any effect of differential larval size and/or age on accumulated metal concentrations. Mayfly larvae are members of a suite of potential stream biomonitors in Central Europe, which together can provide information on the different sources of bioavailable trace metals present in aquatic ecosystems.     

Accumulation of Al, Mn, Fe, Cu, Zn, Cd and Pb by the bryophyte Scapania undulata in three upland waters of different pH.

Measurements were made of the contents of Al, Mn, Fe, Cu, Zn, Cd and Pb in Scapania undulata in three streams (D2, D5, D11) in the English Lake District. The stream waters had average pH values of 5.35 (D2), 5.81 (D5) and 7.26 (D11), the main differences in other major chemical components being in Mg, Al, Ca and alkalinity. There was generally more metal accumulation in the older parts of the plants, but this was not significant in all cases. Extents of accumulation varied with stream pH and dissolved metal concentration. For Al, accumulation was greatest in streams D2 and D5. Mn accumulated most in D5 and Fe was without preference. Cu, Zn and Cd accumulated mostly in the plants in stream D11 and Pb accumulated more in D5 and D11. In terms of enrichment factors (amount of metal in the plants divided by stream water concentration) the sequence was Zn < Cd < Cu < Mn < Pb < Al < Fe. Laboratory experiments supported the findings of the field data, providing evidence that uptake increases with pH at constant total metal concentration. The results are interpreted qualitatively in terms of the chemical speciation of the metals in the stream water and competition between metal ions and protons at the plant-water interface. It is suggested that Al, Cu, Zn, Cd and Pb behave according to chemical complexation, whereas redox processes and/or colloidal interactions may be significant for Mn and Fe.     

Effect of soil characteristics on Cd uptake by the hyperaccumulator Thlaspi caerulescens

The influence of soil characteristics on the phytoremediation potential of Thlaspi caerulescens is not well understood. We investigated the effect of soil pH and Cd concentration on plant Cd uptake on one soil type, and the variation in Cd uptake using a range of field contaminated soils. On soils with total Cd concentrations of 0.6-3.7 mg kg(-1), T. caerulescens (the Ganges ecotype) produced greater biomass in the pH range 5.1-7.6 than at pH 4.4. The highest plant Cd concentration (236 mg kg(-1)) and Cd uptake (228 microg pot(-1)) were observed at pH 5.1. On soils with total Cd concentrations of 2.6-314.8 mg kg(-1), shoot Cd concentrations were 10.9-1,196 mg kg(-1). Multiple regression analysis indicated that higher Cd in soil, low pH (within the range of >5) and coarser texture were associated with higher Cd concentration and Cd uptake by T. caerulescens.     

Underlying mechanisms and effects of hydrated lime and selenium application on cadmium uptake by rice (<Emphasis Type="Italic">Oryza sativa</Emphasis> L.) seedlings

A pot experiment was conducted to investigate the effects of selenium (Se) and hydrated lime (Lime), applied alone or simultaneously (Se+Lime), on growth and cadmium (Cd) uptake and translocation in rice seedlings grown in an acid soil with three levels of Cd (slight, mild, and moderate contamination). In the soil with 0.41 mg kg^?1 Cd (slight Cd contamination), Se addition alone significantly decreased Cd accumulation in the root and shoot by 35.3 and 40.1%, respectively, but this tendency weakened when Cd level in the soil increased. However, Se+Lime treatment effectively reduced Cd accumulation in rice seedlings in the soil with higher Cd levels. The results also showed that Se application alone strongly increased Cd concentration in the iron plaque under slight Cd contamination, which was suggested as the main reason underlying the inhibition of Cd accumulation in rice seedlings. Se+Lime treatment also increased the ability of the iron plaques to restrict Cd uptake by rice seedlings across all Cd levels and dramatically decreased the available Cd concentration in the soil. These results suggest that Se application alone would be useful in the soil with low levels of Cd, and the effect would be enhanced when Se application is combined with hydrated lime at higher Cd levels.     

Bioaccumulation of cadmium by the freshwater isopod Asellus aquaticus (L.) from aqueous and dietary sources

Experiments were conducted to determine the kinetics and relative importance of aqueous and dietary uptake of cadmium by the freshwater isopod Asellus aquaticus (L.). Test animals were exposed during 30 days to aqueous Cd in a continuous flow system (exposure levels: 0.2 - 10 microg litre(-1)) and kept on a diet of previously contaminated Elodea sp. (range of Cd concentrations: 2-350 microg g(-1), dry weight). Preceding semi-static experiments on dosage-control of the dietary factor revealed a rapid uptake of Cd by Elodea, with relatively high concentration factors (CF), which ranged from 4.8 to 5.5 (dry weight log (CF) after 16 days). For Asellus uptake from water appeared to be the predominant route. Highly significant bioconcentration of cadmium from water was observed in the animals, even at exposure levels below 1.0 microg litre(-1). In the various treatments, direct uptake from water accounted for 50-98% of the body burdens after 30 days exposure. The experimental results were described with a first order one-compartment bioaccumulation model. Model parameter estimates (mean +/- standard error) were obtained for rate constant of uptake (560 +/- 110 day(-1)), rate constant of elimination (0.032 +/- 0.017 day(-1)) and assimilation efficiency of Cd uptake from food (1.1 +/- 0.7%). The (dry weight) bioconcentration factor (BCF) and bioaccumulation factor (BAF) for extrapolated steady state conditions were estimated at 18 000 (BCF) and 0.08 (BAF). Experiments conducted at two different pH levels (5.9 versus 7.6) revealed no significant effects of pH on the uptake of aqueous Cd by the isopods. The results are discussed in relation to their potential significance to the field situation.     

Contrasting effects of silicates on cadmium uptake by three dicotyledonous crops grown in contaminated soil

The effects of several silicates (talcum powder (TP), calcium silicate (CS), sodium silicate (SS), and potassium silicate (PS)), in comparison with other amendments (quicklime (QL) and potassium dihydrogen phosphate (PDP)) on cadmium (Cd) uptake by three dicotyledonous crops (Amaranthus hypochondriacus L. Cv. ‘K112’, Amaranthus tricolor L., and Brassica oleracea var. albiflora Kuntze) were investigated in Cd–contaminated soil. The effects of both application methods of amendments (singly and combined) and timing of application were also evaluated. Sodium silicate was the most effective in reducing crop Cd uptake and translocation, which was diminished by 51 % in roots, 53 % in stems, and 72 % in leaves on average. Application of CS amendment showed greater efficiency than PDP amendment in decreasing Cd uptake by crops and resulted in increased biomass. Potassium silicate only slightly decreased shoot Cd concentration. Combination of PDP and SS was able to overcome the inhibitory effect of SS on crop yield while decreasing Cd concentrations in roots, stems and leaves of the tested crops by average rates of 52, 65, and 68 % respectively. Applications of SS and PS significantly reduced the root-to-shoot Cd transfer factor. We found that Si accumulation in crops was not associated with lower Cd concentration, indicating that Si in crops may play a major role in alleviating metal stress rather than inhibiting crop Cd accumulation. We suggested that the inhibitive effect of silicates on crops Cd uptake was majorly attributed to the properties of the silicates, those were their specific effects on soil pH and cations, which increased Cd adsorption by soil and suppressed Cd uptake from soil solution by increasing the relative dissolved concentrations of competing cations.     

Effect of arsenate on adsorption of Cd(II) by two variable charge soils

The effect of arsenate on Cd(II) adsorption in two variable charge soils and the desorption of Cd(II) pre-adsorbed in the presence of arsenate were studied. The batch type experiments showed, the presence of arsenate led to increase in Cd(II) adsorption and the desorption of pre-adsorbed Cd(II). Further it was observed that the extent of adsorption and desorption of Cd(II) was greatly influenced by the initial concentrations of arsenate and Cd(II), the solution pH, and the nature of the soils. In general the increase in arsenate concentration and pH favored the uptake of Cd(II). Moreover, the arsenate concentration influenced more in Hyper-Rhodic Ferralsol than Rhodic Ferralsol at least for the Cd(II) adsorption/desorption. This may be due to the content of Fe/Al oxides in these soils. The larger the content of Fe/Al oxides, the more the adsorption of arsenate by the soil, hence greater the uptake of Cd(II). It can be assumed that the enhanced Cd(II) adsorption was mainly due to the increase in net negative surface charge of the soil induced by the adsorption of arsenate, because the presence of arsenate led to the decrease in zeta potential of these soil suspensions. The increase of electrostatically adsorbed Cd(II) was responsible for the increase in the desorption of Cd(II) pre-adsorbed in the presence of arsenate.     

Soil Cd availability to Indian mustard and environmental risk following EDTA addition to Cd-contaminated soil

A pot experiment was conducted to investigate the influence of EDTA on the extractability of Cd in the soil and uptake of Cd by Indian mustard (Brassica juncea). Twenty levels of soil Cd concentration ranging from 10 to 200 mg kg(-1) were produced by spiking aliquots of a clay loam paddy soil with Cd(NO3)2. One week before the plants were harvested EDTA was applied to pots in which the soil had been spiked with 20, 40, 60...200 mg Cd kg(-1). The EDTA was added at the rate calculated to complex with all of the Cd added at the 200 mg kg(-1) level. Control pots spiked with 10, 30, 50... 190 mg Cd kg(-1) received no EDTA. The plants were harvested after 42 days' growth. Soil water- and NH4NO3-extractable Cd fractions increased rapidly following EDTA application. Root Cd concentrations decreased after EDTA application, but shoot concentrations increased when the soil Cd levels were >130 mg kg(-1) and Cd toxicity symptoms were observed. The increases in soil solution Cd induced by EDTA did not increase plant total Cd uptake but appeared to stimulate the translocation of the metal from roots to shoots when the plants appeared to be under Cd toxicity stress. The results are discussed in relation to the possible mechanisms by which EDTA may change the solubility and bioavailability of Cd in the soil and the potential for plant uptake and environmental risk due to leaching losses to groundwater.     

Effects of short-term pH fluctuations on cadmium, nickel, lead, and zinc availability to ryegrass in a sewage sludge-amended field

In this field experiment, sewage sludge was applied at 0, 5, 10, and 50tha(-1), and the availability of Cd, Ni, Pb, and Zn was assessed both by ryegrass uptake and by DTPA extractions. The aim was to investigate the role of important soil parameters, particularly pH, on heavy metal availability. It was found that metal uptake and extractability increased significantly in the 50tha(-1) treatment. In the 16th week of the experiment there was a significant, although temporary, increase in DTPA-extractable Cd, Ni, and Zn concentrations. Metal concentrations in ryegrass were also significantly elevated in week 20 compared to the subsequent cuttings. These fluctuations in both DTPA and ryegrass uptake occurred only at 50tha(-1) and were probably induced by a sudden pH decrease measured in the same treatment in week 16. This suggests that soils which have received high applications of sewage sludge may be prone to fluctuations in metal availability.     

Aseptic hydroponics to assess rhamnolipid-Cd and rhamnolipid-Zn bioavailability for sunflower (<Emphasis Type="Italic">Helianthus annuus</Emphasis>): a phytoextraction mechanism study

The availability of cadmium (Cd) and zinc (Zn) to sunflower (Helianthus annuus) was investigated in rhamnolipid- and ethylenediaminetetraacetic acid (EDTA)-buffered solutions in order to evaluate the influence of aqueous speciation of the metals on their uptake by the plant, in relation to predictions of uptake by the free ion activity model (FIAM). Free metal ion activity was estimated using the chemical equilibrium program MINTEQ or measured by Donnan dialysis. The uptake of Cd followed the FIAM for the EDTA-buffered solution at EDTA concentrations below 0.4 μM; for the rhamnolipid-buffered solution, the uptake of both metals in roots was not markedly affected by increasing rhamnolipid concentrations in solution. This suggests rhamnolipid enhanced metal accumulation in plant roots (per unit free metal in solution) possibly through formation and uptake of lipophilic complexes. The addition of normal Ca concentrations (low millimetre range) to the rhamnolipid uptake solutions reduced Cd accumulation in shoots by inhibiting Cd translocation, whereas it significantly increased Zn accumulation in shoots. This study confirms that although rhamnolipid could enhance accumulation of Cd in plants roots at low Ca supply, it is not suitable for Cd phytoextraction in contaminated soil environments where Ca concentrations in soil solution are orders of magnitude greater than those of Cd.     

Effect of chemical amendments on the concentration of cadmium and lead in long-term contaminated soils

The availability of metal in contaminated soil can be reduced by the addition of soil amendments. The objectives of this study are to study the effects of applying different soil amendments on the concentration of Cd and Pb in soil solution, DTPA or EDTA extractable Cd and Pb, and the uptake of Cd and Pb by wheat (Triticum vulgare) when growing in long-term Cd and Pb-contaminated soils, more than 20 years. The soil amendments, including check, compost, zinc oxide, calcium carbonate, calcium carbonate mixed with zinc oxide, and calcium carbonate mixed with compost, were conducted in a four replicates pot cultural study. The amended soils were incubated for six months under 60% of water holding capacity. Following incubation, wheat was grown for four months in greenhouse. Analyses of Cd concentration demonstrated a significant decrease in soil solution concentration and DTPA or EDTA extractable in soils amended with calcium carbonate or calcium carbonate mixed with ZnO (or compost) (p<0.01). These amendments can significantly reduce the Cd concentration in the grain, leaf and stem, or reduce the total Cd uptake in all parts of wheat species grown in highly contaminated soil amended with calcium carbonate or calcium carbonate mixed with ZnO (or compost) (p<0.01). The concentration of Cd in soil solution and extracted with DTPA or EDTA can predict the Cd concentration in wheat, especially for soil solution.     

Cadmium in cereal grain and herbage from long-term experimental plots at Rothamsted, UK

Crop samples harvested and stored from three long-term agricultural experiments started in the 1840-1850s at Rothamsted Experimental Station (UK) have been analysed recently for Cd. Increased Cd burden in the soils of the experiments, which have had a range of treatments, originates mainly from atmospheric deposition. Soils treated with farmyard manure (FYM) or, in some cases, applications of phosphate fertilisers, have increased Cd levels. Herbage, wheat and barley grain from the three experiments were analysed by neutron activation analysis (NAA) and graphite furnace atomic absorption spectrometry (GFAAS). Samples were bulked for groups of years between 1860 and 1986, from variously treated plots in each experiment (control or 'nil' treatment, P-fertilised, FYM-amended, NPK-fertilised-limed and unlimed). There were marked differences in Cd concentrations between treatments. For example, uptake of Cd into herbage was greater where P fertiliser had been applied than not, and was greater from unlimed than limed soils. Offtake of Cd (mg ha(-1) year(-1)) was affected by large differences in yield and probably also by other factors. These include changes in botanical composition in the permanent grassland experiment; cultivar changes in the wheat and barley experiments; changes in soil organic matter and soil pH of some plots; changes in atmospheric deposition of Cd through time. All of these potentially confounding factors make the interpretation of results complicated. It is concluded, however, that, with one exception, there is little evidence of a long-term increase in crop Cd concentrations at Rothamsted.     

Biomass-derived materials in the remediation of heavy-metal contaminated water: removal of Cadmium(II) and copper(II) from aqueous solutions

Manganese-coated activated carbon (MCAC) and activated carbon were used in batch experiments for the removal of cadmium(II) and copper(II). Results showed that uptake of Cd(II) and Cu(II) was unaffected by increases in pH (3.0 to 8.5) or concentration (1 to 20 mg/L). Increased ionic strength (from 0.001 to 1 M NaNO3), however, significantly affected the uptake of Cd(II); adsorption of Cu(II) was not affected. Freundlich adsorption isotherm results indicated that MCAC possessed higher sorption capacity than activated carbon. Second-order rate constants were found to be 0.0386 for activated carbon and 0.0633 g/mg x min for MCAC for Cd(II) and 0.0774 for AC and 0.1223 g/mg x min for MCAC for Cu(II). Column experiments showed that maximum sorption capacity of MCAC was 39.48 mg/g for Cu(II) and 12.21 mg/g for Cd(II).     

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.     

Chemical methods and phytoremediation of soil contaminated with heavy metals

The effects of chemical amendments (calcium carbonate (CC), steel sludge (SS) and furnace slag (FS)) on the growth and uptake of cadmium (Cd) by wetland rice, Chinese cabbage and wheat grown in a red soil contaminated with Cd were investigated using a pot experiment. The phytoremediation of heavy metal contaminated soil with vetiver grass was also studied in a field plot experiment. Results showed that treatments with CC, SS and FS decreased Cd uptake by wetland rice, Chinese cabbage and wheat by 23-95% compared with the unamended control. Among the three amendments, FS was the most efficient at suppressing Cd uptake by the plants, probably due to its higher content of available silicon (Si). The concentrations of zinc (Zn), lead (Pb) and Cd in the shoots of vetiver grass were 42-67%, 500-1200% and 120-260% higher in contaminated plots than in control, respectively. Cadmium accumulation by vetiver shoots was 218 g Cd/ha at a soil Cd concentration of 0.33 mg Cd/kg. It is suggested that heavy metal-contaminated soil could be remediated with a combination of chemical treatments and plants.     

Chronic effects of Cd on reproduction of Polypedilum nubifer (Chironomidae) through water and food

Chronic effects of Cd on reproduction of Polypedilum nubifer (Chironomidae) were investigated by Cd-exposure from the egg stage using a flow-through aquarium. No significant effect of Cd on reproduction was observed in the midge larvae which had been exposed to 10 or 20 microg Cd litre(-1). Emergence of the Cd-exposed larvae peaked several days before that of the control, although growth was impaired in 1st and/or 2nd instars. The percentage emergence success decreased to about 46% of the control at 40 microg Cd litre(-1). However, other reproductive processes (adult sex ratio, oviposition success and egg hatchability) were not impaired. The emergence success decreased to less than 3% of the control at 80 microg Cd litre(-1). The emergence success of midge larvae which had been fed Cd-contaminated food with 220 or 1800 microg Cd g(-1) decreased to nearly 60% of the control. However, other reproductive processes were not impaired. Emergence success of larvae exposed to food containing 22 microg Cd g(-1) was unaffected.