Leachates from solid wastes: chemical and eco(geno)toxicological differences between leachates obtained from fresh and stabilized industrial organic sludge

The chemical and ecotoxicological characteristics of fresh and stabilized industrial organic sludge leachates were compared to obtain information regarding how the stabilization process can influence the ecotoxic potential of this industrial waste, which could be used for the amendment of degraded soil. Physicochemical analysis of the sludge leachates, as well as a battery of eco(geno)toxicity tests on bacteria, algae, daphnids, and higher plants (including Vicia faba genotoxicity test) and the determination of hydrolytic enzyme activity, was performed according to standard methods. The chemical comparison of the two types of leachate showed that the samples obtained from stabilized sludge had a lower organic content and higher metal content than leachates of the fresh sludge. The eco(geno)toxicological results obtained with aquatic organisms showed that the stabilized sludge leachate was more toxic than the fresh sludge leachate, both originating from the same industrial organic sludge sample. Nevertheless, phytotoxicity tests carried out with a reference peat soil irrigated with stabilized sludge leachate showed the same toxicity as the fresh sludge leachate. In the case of the industrial solid organic sludge studied, stabilization through a biodegradation process promoted a higher metal mobility/bioavailability/eco(geno)toxicity in the stabilized sludge leachate compared to the fresh sludge leachate.     

A comparative study of the toxicity of 1,1,2-trichloroethane,dieldrin, pentachlorophenol and 3,4 dichloroaniline for marine and fresh water organisms

The aquatic toxicity of 1,1,2-trichloroethane, dieldrin, pentachlorophenol and 3,4-dichloroaniline was determined for about 15 marine and fresh water animals and several unicellular algae. Acute, subchronic and chronic tests including reproduction studies, were carried out. The results are summarized in five tables.     

Effects of the parasiticide ivermectin on the cladoceran Daphnia magna and the green alga Pseudokirchneriella subcapitata

Although widely used for the treatment of endo- and ectoparasites in livestock and pets, very few data on chronic effects on aquatic organisms are available for the parasiticide ivermectin. In the present study, toxicity of ivermectin to two freshwater organisms, the cladoceran Daphnia magna and the green alga Pseudokirchneriella subcapitata was investigated. For D. magna, a mean LC(50) 48 h of 5.7 ngl(-1) was derived from 10 acute tests. Chronic toxicity of ivermectin to D. magna was extremely high: with 0.001 and 0.0003 ngl(-1), respectively, nominal LOEC and NOEC based on growth and reproduction were far below the analytical limit of detection for this compound. P. subcapitata was considerably less sensitive to ivermectin than D. magna. For both growth rate and yield, EC(50) was >4,000 microgl(-1), LOEC was 1,250 microgl(-1) and NOEC 391microgl(-1). In view of the high toxicity to D. magna, the use of ivermectin might pose a risk to local aquatic ecosystems. Further studies should be carried out to investigate the effects of ivermectin and its degradation products on pelagic and benthic freshwater invertebrates.     

Toxicity of methyl tert-butyl ether to marine organisms: ambient water quality criteria calculation

In response to increasing concerns over the detection of methyl tert-butyl ether (MTBE) in groundwater and surface water and its potential effects in aquatic ecosystems, industry and the United States Environmental Protection Agency (USEPA) began to collaborate in 1997 to develop aquatic toxicity databases sufficient to derive ambient water quality criteria for MTBE consistent with USEPA requirements. Acute toxicity data for seven marine species, chronic toxicity data for an invertebrate, and plant toxicity data were developed to complete the saltwater database. The species tested were Cyprinodon variegatus, Gasterosteus aculeatus, Callinectes sapidus, Mytilus galloprovincialis, Palaemonetes pugio, Rhepoxynius abronius, Americamysis bahia, and Skeletonema costatum. The toxicity tests were conducted in accordance with USEPA and American Society for Testing and Materials testing procedures and Good Laboratory Practice guidelines. Data developed from this study were consistent with existing data and showed that MTBE has low acute and chronic toxicity to the marine species tested. Based upon measured MTBE concentrations, acute effects were found to range from 166 mg MTBE/l for the grass shrimp to 1950 mg MTBE/l for marine mussel. The no-observed effect concentration for the reproduction and growth of mysids was 26 mg MTBE/l during the life cycle test. The toxicity of MTBE to saltwater organisms is comparable to its toxicity to the freshwater species tested. Reported MTBE concentrations in coastal waters are several orders of magnitude lower than concentrations observed to cause effects in marine organisms.     

Toxicity of selected chlorobenzenes to aquatic organisms

Acute toxicity tests with six chlorobenzenes were performed on several aquatic organisms at different trophic levels. Fertility impairment on Daphnia and photosynthesis inhibition on Selenastrum were also carried on. Results are discussed together with physico-chemical properties of the molecules in order to identify structure-activity relationships and to predict environmental distribution. A hazard ranking procedure is also applied.     

Transformation and Ecotoxicity of Carbamic Pesticides in Water (5 pp)

Background N-methylcarbamate insecticides are widely used chemicals for crop protection. This study examines the hydrolytic and photolytic cleavage of benfuracarb, carbosulfan and carbofuran under natural conditions. Their toxicity and that of the corresponding main degradation products toward aquatic organisms were evaluated. Methods Suspensions of benfuracarb, carbosulfan and carbofuran in water were exposed to sunlight, with one set of dark controls, for 6 days, and analyzed by 1H-NMR and HPLC. Acute toxicity tests were performed on Brachionus calyciflorus, Daphnia magna, and Thamnocefalus platyurus. Chronic tests were performed on Pseudokirchneriella subcapitata, and Ceriodaphnia dubia. Results and Discussion Under sunlight irradiation, benfuracarb and carbosulfan gave off carbofuran and carbofuran-phenol, while only carbofuran was detected in the dark experiments. The latter was degraded to phenol by exposure to sunlight. Effects of pH, humic acid and KNO3 were evaluated by kinetics on dilute solutions in the dark and by UV irradiation, which evidenced the lability of the pesticide at pH 9. All three pesticides and phenol exhibited acute and higher chronic toxicity towards the aquatic organisms tested. Conclusion Investigation on the hydrolysis and photolysis of benfuracarb and carbosulfan under natural conditions provides evidence concerning the selective decay to carbofuran and/or phenol. Carbofuran is found to be more persistent and toxic. Recommendations and Outlook The decay of benfuracarb and carbosulfan to carbofuran and the relative stability of this latter pesticide account for many papers that report the detection of carbofuran in water, fruits and vegetables.     

Comparative study on the susceptibility of freshwater species to copper-based pesticides

Copper compounds have been intentionally introduced into water bodies as aquatic plant herbicides, algicides and molluscicides. Copper-based fertilizers and fungicides have been widely used in agriculture as well. Despite the fact that copper is an essential element for all biota, elevated concentrations of this metal have been shown to affect a variety of aquatic organisms. Nonetheless, comparative studies on the susceptibility of different freshwater species to copper compounds have seldom been performed. This study was conducted to compare toxicity of copper-based pesticides (copper oxychloride, cuprous oxide and copper sulfate) to different freshwater target (Raphidocelis subcapitata, a planktonic alga and Biomphalaria glabrata, a snail) and non-target (Daphnia similis, a planktonic crustacean and Danio rerio, a fish) organisms. Test water parameters were as follows: pH = 7.4 +/- 0.1; hardness 44 +/- 1 mg/l as CaCO3; DO 8-9 mg/l at the beginning and > 4 mg/l at the end; temperature, fish and snails 25 +/- 1 degrees C, Daphnia 20 +/- 2 degrees C, algae 24 +/- 1 degrees C. D. similis (immobilization), 48-h EC50s (95% CLs) ranging from 0.013 (0.011-0.016) to 0.043 (0.033-0.057) mg Cu/l, and R. subcapitata (growth inhibition), 96-h IC50s from 0.071 (0.045-0.099) to 0.137 (0.090-0.174) mg Cu/l, were the most susceptible species. B. glabrata (lethality), 48-h LC50s from 0.179 (0.102-0.270) to 0.854 (0.553-1.457) mg Cu/l, and D. rerio (lethality), 48-h LC50s 0.063 (0.045-0.089), 0.192 (0.133-0.272) and 0.714 (0.494-1.016) mg Cu/l, were less susceptible than Daphnia to copper-based pesticides. Findings from the present study therefore suggest that increased levels of copper in water bodies is likely to adversely affect a variety of aquatic species.     

Ecotoxicological and chemical evaluation of phenolic compounds in industrial effluents

The aim of this paper was to evaluate the ecotoxicological response of industrial effluents containing phenolic compounds. All complex effluents collected from a chemical plant and then after both a chemical–physical and biological treatment were characterised with chemical analysis, biodegradability tests and four ecotoxicological tests (Daphnia magna, Artemia salina, Brachionus plicatilis and Vibrio fisheri with Microtox^®). The evaluation of the chemical and ecotoxicological data was useful for predicting the effect of the raw effluent on the treatment plant and the impact of the final treated effluent on the receiving water. Besides the toxicity of the effluent from the chemical plants, the acute toxicity of its main components was also determined. The results of the tests and toxicity data from literature were transformed in Toxic Units (TUs). Effluent toxicity was under- or over-estimated by calculating the sum of the TUs of the individual components, depending on which toxicity data and test organisms were used.     

The water-soluble fraction of potentially toxic elements in contaminated soils: relationships between ecotoxicity, solubility and geochemical reactivity

To better understand the impacts posed by soil contamination to aquatic ecosystems it is crucial to characterise the links between ecotoxicity, chemical availability and geochemical reactivity of potentially toxic elements (PTE’s) in soils. We evaluated the adverse effects of water extracts obtained from soils contaminated by chemical industry and mining, using a test battery including organisms from different trophic levels (bacteria, algae and daphnids). These tests provided a quick assessment of the ecotoxicity of soils with respect to possible adverse effects on aquatic organisms although the ecotoxicological responses could be related to the solubility of PTE’s only to a limited extent.The analysis of results of bioassays together with the chemical characterisation of water extracts provided additional relevant insight into the role of conductivity, pH, Al, Fe, and Mn of soil extracts on toxicity to organisms. Furthermore, an important conclusion of this study was that the toxicity of extracts to the aquatic organisms could also be related to the soil properties (pH, Org C and Fe_ox) and to the reactivity of PTE’s in soils which in fact control the soluble fraction of the contaminants.The combined assessment of ecotoxicity in water fractions, solubility and geochemical reactivity of PTE’s in soils provided a more comprehensive understanding of the bioavailability of inorganic contaminants than ecotoxicological or chemical studies alone and can therefore be most useful for environmental risks assessment of contaminated soils.     

Deriving freshwater quality criteria for 2,4-dichlorophenol for protection of aquatic life in China

Freshwater quality criteria for 2,4-dichlorophenol (2,4-DCP) were developed with particular reference to the aquatic biota in China, and based on USEPA's guidelines. Acute toxicity tests were performed on nine different domestic species indigenous to China to determine 48-h LC50 and 96-h LC50 values for 2,4-DCP. In addition, 21 day survival-reproduction tests with Daphnia magna, 30-day embryo-larval tests with Carassius auratus, 60 day fry-juvenile test with Ctenopharyngodon idellus, 30 d early life stage tests with Bufo bufo gargarizans and 96 h growth inhibition tests with Scenedesms obliqaus were conducted, to estimate lower chronic limit (LCL) and upper chronic limit (UCL) values. The final acute value (FAV) was 2.49 mg/l 2,4-DCP. Acute-to-chronic ratios (ACR) ranged from 3.74 to 22.5. The final chronic value (FCV) and the final plant value (FPV) of 2.4-DCP were 0.212 mg/l and 7.07 mg/l respectively. Based on FAV, FCV, and FPV, a criteria maximum concentration (CMC) of 1.25 mg/l and a criterion continuous concentration (CCC) of 0.212 mg/l were derived. The results of this study provide useful data for deriving national or local water quality criteria for 2,4-DCP based on aquatic biota in China.     

Statistical evaluation of chronic toxicity data on aquatic organisms for the hazard identification: the chemicals toxicity distribution approach

Presently, in the Globally Harmonised System of Classification and Labelling of Chemicals the classification of substances for long-term effects to aquatic life is based on acute toxicity in combination with degradation and/or bioaccumulation potential. Recently an OECD Working Group was created to develop the classification scheme to accommodate chronic toxicity data related to aquatic organisms for assigning a chronic hazard category. This study focuses on a new approach for setting chronic toxicity cut-off values based on Chemicals Toxicity Distributions (CTDs). A CTD is obtained through statistical fitting of the data used by regulatory bodies for setting hazard-based classifications. The CTDs were made using the lowest aquatic NOEC value of each chemical. A review of different toxicological sources reporting acute aquatic toxicities was carried out. Initially, the data were arranged according to the specific source and distributions for key taxonomic groups (i.e. fishes, crustaceans and algae) were evaluated separately. In most cases, no significant departures from normality were observed. Thereafter, a compiled database containing >900 values was developed and the CTDs were constructed for each taxonomic group. Significant deviation from normality (P < 0.05) was observed in the fishes and crustaceans' CTDs. However, this deviation was apparently produced by the presence of only seven values with NOECs <1 x 10(-5) mg l(-1), while high correlation between the data and the normal scores (r-values>or= 0.989) indicated that the data were samples from normal distributions. From these observations, potential cut-off values would allow quantitative estimations of the percentage of chemicals falling into each specific category. This approach results in a simple classification hazard scheme where most chemicals are covered in one of the categories, allowing a clear distribution of the chemicals among three categories for chronic toxicity.     

Occurrence,elimination, and risk of anticoagulant rodenticides and drugs during wastewater treatment

Anticoagulants are biocides widely used as pest control agents in agriculture, urban infrastructures, and domestic applications for the control of rodents. Other anticoagulants such as warfarin and acenocoumarol are also used as drugs against thrombosis. After use, anticoagulants are discharged to sewage grids and enter wastewater treatment plants (WWTPs). Our hypothesis is that WWTP effluents can be a source of anticoagulants to receiving waters and that these can affect aquatic organisms and other nontarget species. Therefore, the objective of the present study was to determine the occurrence of 11 anticoagulants in WWTPs receiving urban and agricultural wastewaters. Warfarin was the most ubiquitous compound detected in influent waters and was partially eliminated during the activated sludge treatment, and low nanograms per liter concentration were found in the effluents. Other detected compounds were coumatetralyl, ferulenol, acenocoumarol, flocoumafen, brodifacoum, bromadiolone, and difenacoum at concentrations of 0.86–87.0 ng L^?1. Considering water volumes of each WWTP, daily emissions were estimated to be 0.02 to 21.8 g day^?1, and thus, WWTPs contribute to the loads of anticoagulants to receiving waters. However, low aquatic toxicity was observed using Daphnia magna as a model aquatic organism.     

Acute, chronic and sublethal effects of the herbicide propanil on Daphnia magna

Acute and chronic toxicity tests with propanil were conducted on Daphnia magna. The 24 and 48 h LC50 were 43.74 and 5.01 mg/l respectively. Chronic toxicity tests were carried out using sublethal propanil concentrations (0.07, 0.10, 0.21 and 0.55 mg/l) during 21 days. The effect of propanil on survival, reproduction and growth of D. magna organisms was monitored. The parameters used to evaluate herbicide effect on reproduction were: mean total young ones per female, mean brood size, time to first reproduction, mean number broods per female and intrinsic rate of natural increase (r). Survival and growth (body length) were also determined after 21 days of exposure to the herbicide. Reproduction was significantly reduced when propanil concentration increased in the medium. The intrinsic rate of natural increase (r) decreased with increasing concentrations of propanil especially in those animals exposed to 0.55 mg/l. However, growth as well as survival of the exposed organisms only decreased in daphnids exposed to the highest propanil concentration tested. The maximum acceptable toxicant concentration (MATC) was calculated for D. magna exposed to the herbicide using as parameter of evaluation the intrinsic rate of natural increase (r). The interpolation of these results gave MATC values of 0.08 mg/l herbicide. We have derived the EC50 values for some selected parameters on D. magna exposed to propanil. EC50 values indicated that reproductive parameters were very sensitive of the effect of propanil on daphnids. Finally, the daphnids were exposed to the same sublethal herbicide concentrations as in the chronic study and the effect of the toxicant on filtration and ingestion rates was determined. Feeding rates of D. magna declined with increasing propanil concentrations. The effective propanil concentrations at which feeding rates were reduced to 50% of that in controls (EC50) were also calculated.     

Fate, effects and potential environmental risks of ethylene glycol: a review

The fate, effects, and potential environmental risks of ethylene glycol (EG) in the environment were examined. EG undergoes rapid biodegradation in aerobic and anaerobic environments (approximately 100% removal of EG within 24 h to 28 days). In air, EG reacts with photo-chemically produced hydroxyl radicals with a resulting atmospheric half-life of 2 days. Acute toxicity values (LC(50)s and EC(50)s) were generally >10,000 mg/l for fish and aquatic invertebrates. The data collectively show that EG is not persistent in air, surface water, soil, or groundwater, is practically non-toxic to aquatic organisms, and does not bioaccumulate in aquatic organisms. Potential long-term, quasi-steady state regional concentrations of EG estimated with a multi-media model for air, water, soil, and sediment were all less than predicted no effect concentrations (PNECs).     

Potential impacts of water injection dredging on water quality and ecotoxicity in Limehouse Basin, River Thames, SE England, UK

The use of water injection dredging (WID) is increasing in the UK's inland waterways and marinas. Jets of water are injected under low pressure directly into bottom sediment creating a turbulent water-sediment mixture that flows under the influence of gravity. Many of these sediments are highly contaminated and little is known of the effects of contaminant release on water quality or the risk to biota living in both the sediment and the water column. Sediment cores were collected from Limehouse Basin, a proposed WID site in SE England and current sediment toxicity was assessed using a number of techniques. Comparison of metal data to US sediment quality guidelines indicated intermediate levels of toxicity while, calculation of acid volatile sulphide to simultaneously extracted metal ratios underestimated the potential toxicity to sediment dwelling organisms. In contrast, porewater ammonia concentrations were in excess of all published ecotoxicological guidelines and indicate serious risk to biota. Re-suspension experiments were used to mimic the effects of WID on overlying water quality and ecotoxicity tests were carried out on elutriates using Daphnia magna to examine the impacts on biota. Concentrations of a range of metals in the elutriates predict that adverse biological effects would be observed during WID, however only 10% of the elutriate samples caused an adverse effect on Daphnia. Limehouse Basin is a complex aquatic environment receiving predominantly fresh waters while the sediments have high porewater chloride concentrations reminiscent of previous tidal inputs to the basin, making the choice of test organism problematic.     

Fate and effect of monoalkyl quaternary ammonium surfactants in the aquatic environment

The effect of the alkyl chain of quaternary ammonium-based surfactants on their aquatic toxicity and aerobic biodegradability has been studied. Two families of monoalkylquats surfactants were selected: alkyl trimethyl ammonium and alkyl benzyl dimethyl ammonium halides. Acute toxicity tests on Daphnia magna and Photobacterium phosphoreum were carried out and EC50 values in the range of 0.1-1 mg/l were obtained for the two series of cationic surfactants. Although the substitution of a benzyl group for a methyl group increases the toxicity, an incremental difference in toxicity between homologs of different chain length were not observed. Biodegradability of the different homologs was determined not only in standard conditions but also in coastal water, both tests yielding similar results. An increase in the alkyl chain length or the substitution of a benzyl group for a methyl group reduces the biodegradation rate. The degradation of these compounds in coastal waters was associated with an increase in bacterioplankton density, suggesting that the degradation takes place because the compound is used as a growth substrate.     

Biodegradation in laboratory activated sludge plants and aquatic toxicity of herbicides

The biodegradation and the aquatic toxicity of four herbicides (isoproturon, terbuthylazine, mecoprop, metamitron) were investigated. Laboratory activated sludge plants were used for biodegradation experiments. The biodegradation of mecoprop reached nearly 100%, the other herbicides were not eliminated by biodegradation. The acute Daphnia magna 24-h assay, the algal 72-h inhibition test, and the recently developed lemna growth inhibition 7-d test were applied to evaluate the biological effects of herbicides as original substances. EC 50 and EC 10 values were determined. Algal and lemna test show that isoproturon and terbuthylazine are both much more toxic than mecoprop and metamitron. Daphnids are generally less sensitive against herbicides than plants. Biodegradation and toxicity test were coupled for mecoprop to assess biological long-term effects of possible biodegradation products of this herbicide. The effluents of the laboratory activated sludge units were used in toxicity tests (Daphnia magna 21-d reproduction test, lemna growth inhibition 7-d test). No inhibiting effect on the tested organisms was observed.     

Combined effects of soil moisture and carbaryl to earthworms and plants: simulation of flood and drought scenarios

Studying tolerance limits in organisms exposed to climatic variations is key to understanding effects on behaviour and physiology. The presence of pollutants may influence these tolerance limits, by altering the toxicity or bioavailability of the chemical. In this work, the plant species Brassica rapa and Triticum aestivum and the earthworm Eisenia andrei were exposed to different levels of soil moisture and carbaryl, as natural and chemical stressors, respectively. Both stress factors were tested individually, as well as in combination. Acute and chronic tests were performed and results were discussed in order to evaluate the responses of organisms to the combination of stressors. When possible, data was fitted to widely employed models for describing chemical mixture responses. Synergistic interactions were observed in earthworms exposed to carbaryl and drought conditions, while antagonistic interactions were more representative for plants, especially in relation to biomass loss under flood-simulation conditions.     

Deriving freshwater quality criteria for 2,4,6-trichlorophenol for protection of aquatic life in China

Freshwater quality criteria of 2,4,6-trichlorophenol (2,4,6-TCP) were developed with particular reference to the aquatic biota in China, and based on USEPA's guidelines. Acute toxicity tests were performed on nine different domestic species indigenous to China to determine 48 h LC(50) and 96 h LC(50) values for 2,4,6-TCP. In addition, 21 d survival-reproduction test with Daphnia magna, 30 d embryo-larval test with Carassius auratus, 60 d fry-juvenile test with Ctenopharyngodon idellus, 30 d early life stage test with Bufo bufo gargarizans and 96 h growth inhibition test with Scenedesmus obliqaus were also conducted to estimate lower chronic limit and upper chronic limit values. The final acute value (FAV) was 2.01 mg/l 2,4,6-TCP. Acute-to-chronic ratios ranged from 5.01 to 12.2. The final chronic value (FCV) and the final plant value (FPV) of 2,4,6-TCP were 0.226 and 2.24 mg/l respectively. Based on FAV, FCV and FPV for 2,4,6-TCP, a criteria maximum concentration of 1.01 mg/l and a criterion continuous concentration of 0.226 mg/l were derived. The results of this study provide useful data for deriving national or local water quality criteria for 2,4,6-TCP based on aquatic biota in China.