CeO2 nanoparticle fate in environmental conditions and toxicity on a freshwater predator species: a microcosm study

Environmental Science and Pollution Research - We studied the fate and toxicity of two types of CeO2 NPs (bare or citrate-coated) in environmentally relevant conditions, using large indoor...     

The study of distribution and fate of nitrobenzene in a water/sediment microcosm

In November 2005, an explosion occurred at a petrochemical plant of the Jilin Petrochemical Corporation in Jilin Province, China. A nearby water body was seriously polluted with a large spill of toxic substances made up of a mixture of benzene, aniline, and nitrobenzene (NB). To understand the long term impact of NB on public health and ecosystem around the Songhua River, it was necessary to investigate its fate in the environment. In this study, a microcosm was used to mimic the polluted water system and to study the transport and fate of NB in the river water body. The volatility and biodegradation of NB was investigated and a Markov model was applied to predict the fate of NB in the environment. The simulated results matched very well with the results obtained from the microcosm experiment. The model indicated that at room temperature and after around 500 h, there was only residual NB in the water and sediment. Most of the NB (around 82%) evaporated into the air and 18% was degraded by microorganisms.     

Copper toxicity to Lemna minor modelled using humic acid as a surrogate for the plant root

Humic acids are chemically analogous to plant root cell walls in that their surface sites are principally comprised of carboxylic and phenolic acids which bind both metals and protons. Based on this analogy, we developed a biotic-ligand type of model to predict Cu toxicity to Lemna minor, using particulate humic acid (HA(part)) of the Windermere Humic Aqueous Model (WHAM), and 7d static-renewal exposures with five surface waters and one nutrient media which varied in DOC (1-10 mg L(-1)), pH (6.9-8.7), and water hardness (35-236 mg equivalent CaCO(3)L(-1)). Although the range of waters tested resulted in a 36-fold variation in 50% inhibitory concentration (IC50) values, the calculated concentration of Cu bound to HA(part) using this framework was highly correlated with pooled percent net root elongation (%NRE) (R(2)=0.95). Ten and fifty percent IC values based on [Cu-HA(part)] were additionally within a factor of ±1.5 and ±1.4, respectively, inclusive of 95% confidence limits. This model construct, which defines the free metal ion and the first hydrolysis product (but not metal carbonate complexes) as being bioavailable, provides an alternative means of defining the binding surface in bioavailability models, whereby a heterogeneous mixture of ligands collectively influence root-metal sorption and toxicity.     

Growth rate effects, responses of antioxidant enzymes and metabolic fate of the herbicide Propanil in the aquatic plant Lemna minor

Propanil (3,4-dichloropropionanilide) is a selective contact pesticide, recommended for post-emergence use in rice. This herbicide may end up in surface waters and present potential risk for aquatic vascular plants. Therefore, its toxicity was evaluated on Lemna minor L., an aquatic plant regularly used for toxicological studies, during time- and concentration-dependent exposure. Toxicity assessments were based on inhibition of growth of L. minor cultures after 24 days. The obtained results showed that the growth of Lemna was affected by the herbicide. The responses of the guaiacol peroxidase (G-POD) and glutathione S-transferase (GST) involved in the xenobiotic metabolism and antioxidative system were also investigated following Propanil exposure. Our results showed that Propanil has not induced enzymatic antioxidative defenses of L. minor. Both 3,4-dichloroaniline (3,4-DCA) and 3,4-dichloroacetanilide are the major metabolites in this plant. On the contrary, only 3,4-DCA was found in culture media after 4 days. Probably, the enzymatic hydrolysis by acyl acylamidase and the acetylation by acetyl-CoA are the major pathways for these transformation products, respectively. The results of this study showed that the selected aquatic plant has the potential to accumulate and metabolize rice herbicide, like Propanil. Based on these toxicity data this herbicide should impair the establishment of non-target aquatic plants.     

A freshwater shrimp (Paratya compressa improvisa) as a sensitive test organism to pesticides

The susceptibility of 2-week-old individuals of the freshwater shrimp, Paratya compressa improvisa, to five kinds of insecticide and five kinds of herbicide was examined in comparison with that of two species of Cladocera, Daphnia magna and Moina macrocopa. The shrimp was especially sensitive to two organophosphorus insecticides. The 48-h LC50 values for fenitrothion and fenthion to the shrimp were 1.15 and 1.04 microg litre(-1) (mean value, n=2), in contrast with 37.8 and 35.3 microg litre(-1) in the case of M. macrocopa, and more than 50 microg litre(-1) with D. magna. The shrimp also showed the higher susceptibility to other insecticides, diazinon, carbaryl (NAC) and BPMC, apart from D. magna to diazinon and NAC. The shrimp also showed higher susceptibility to herbicides. The 48-h LC50 values of CNP, benthiocarb, oxadiazon, butachlor, and symetryne to the shrimp were two to eight times lower than those of two species of Cladocera, except for the LC50 value of oxadiazon to M. macrocopa, which was very slightly higher. However, the shrimp showed a somewhat lower susceptibility to heavy metals than the two species of Cladocera, especially to copper, and to cadmium and zinc in comparison with D. magna. A bioassay using the shrimp with river water, collected from the river adjacent to the paddy field, showed clearly the high mortality of the shrimp following the aerial spraying with pesticides.     

Modular containers for microcosm and process model studies on the fate and effects of aquatic contaminants

Container modules are described for the laboratory simulation of selected processes and ecosystems that are representative of lentic environments. Emphasis is placed on design features permitting mass balance accountability of contaminant residues and procedural cautions required for the proper use of the described systems in environmental simulations. Experiments on the efficiency of container modules for microbial mineralization studies were conducted using ¹⁴CNaHCO₃, and acidification resulted in a ¹⁴CCO₂ recovery of $\text{97.3 ± 4.7\% (}\text{x}\text{?}\text{± SD}\text{)}$. The trapping efficiency of pesticides volatilized from water and glass surfaces was investigated using the same module and the mean recoveries of ¹⁴C-fonofos and ¹⁴C-trifluralin were 114.2 ± 3.2% and 95.2 ± 3.5%, respectively. The mass balance capabilities of the system was also demonstrated for extended microcosm exposures to ¹⁴C-trifluralin.     

Effects of the phenylurea herbicide isoproturon on periphytic diatom communities in freshwater indoor microcosms

The toxic effects of the phenylurea herbicide Isoproturon -IPU: (3-(4-isopropylphenyl)-1, 1-dimethylurea)-were studied on the colonization of periphytic diatom communities, within indoor microcosms consisting of a mixed biotope (water column and natural sediment) and two biological species-rooted macrophyte cuttings (Elodea densa) and benthic bivalve molluscs (Corbicula fluminea). The periphyton, essentially composed of diatoms, was collected on artificial substrata (glass slides) in the upper layers of the water column, after two periods of exposure (34 and 71 days). IPU was initially added in the water or in the sediment compartment, at two nominal concentrations (L1 and L2 levels) for each contamination source-5 and 20 microg litre(-1) and 100 and 400 microg kg(-1) in sediment (w/w) respectively. The effects of IPU on the density and community structure of periphytic diatoms are described. A marked reduction in the diatom density was observed after 34 days exposure to the lower concentration of IPU in the water (5 microg litre(-1)). For the L2 levels, the very small number of live cells present did not permit quantification of the diatom density. After 71 days, recovery in community parameters occurred for the two contamination levels of the sediment and water column sources. Samples collected in the experimental units contaminated with the L2 levels were dominated by heterotrophic and smaller diatom species, such as Sellaphora seminulum. Data treatment based on factorial discriminant analysis enabled us to distinguish the different contamination conditions, with only 11 species from the 130 taxa identified.     

Phytotoxicity of diuron alone and in combination with copper or folpet on duckweed (Lemna minor)

The photosystem II-herbicide diuron is widely used for weed control in Champagne's vineyards. Its important use and its relative persistence make it of particular interest for ecotoxicological studies. Toxicity of diuron was assessed on Lemna minor L., a representative aquatic macrophyte regularly used for toxicological studies. Toxicity assessments were based on inhibition of growth and total chlorophyll content of L. minor cultures after 7 days. Growth was inhibited and IC(50) and IC(90) were, respectively, 25 and 60 microg l(-1), but chlorophyll content of L. minor increased in response to the herbicide. When diuron was combined with copper, growth inhibition of L. minor depended on the concentrations of both chemicals. For some concentrations, combination of these chemicals resulted in a slight (but non-significant) antagonism. Additivity was observed for all other mixtures. When diuron was combined with folpet, growth and chlorophyll content of L. minor only depended on the concentration of the herbicide. Diuron was also found to prevent the copper-induced decrease of chlorophyll content when it was combined with this metal. A multifactorial model was found more appropriate to characterize interactions between pesticides than Abott's model.     

The effect of soil organic matter on fate of polycyclic aromatic hydrocarbons in soil: A microcosm study

A microcosm study was conducted to address the influences of air-soil partition and sequestration on the fate of polycyclic aromatic hydrocarbons (PAHs) in soil. Sterilized and unsterilized soils with soil organic carbon (SOC) content ranging from 0.23 to 7.06% were incubated in a chamber with six PAHs supplied through air. After 100 d of incubation when the system approached pseudo-steady state, the PAHs concentrations in the unsterilized soils still correlated with SOC significantly, while the association did not exist for those sterilized. The lower degradation rate in the soil with higher SOC was likely the major reason for the association between SOC and PAHs concentrations, while the decreased surface porosity likely suppressed such correlation for the sterilized samples. The results indicated that the sequestration was likely the major mechanism for the accumulation of PAHs in soils, while both of the soil porosity and PAHs properties had observed influences.     

Effect of photosensitizer riboflavin on the fate of 2,4,6-trinitrotoluene in a freshwater environment

The effect of riboflavin (1 microM) on the fate of TNT (20 mg/l) in a natural water environment was studied. The relative contribution of photolysis, microbial assemblages and freshwater matrix to TNT degradation was examined. The rates, extent and products of TNT and riboflavin transformation were compared under different experimental conditions. It was found that riboflavin significantly enhanced the degradation of TNT in natural water environment. Thus it is a potentially useful photosensitizing agent for the treatment of TNT-contaminated surface water. Furthermore, in the presence of riboflavin, two new intermediates with max. absorption wavelength of 230 nm were found, demonstrating that transformation of TNT in the presence of riboflavin undergoes different pathways.     

Pesticide fate in tropical wetlands of Brazil: an aquatic microcosm study under semi-field conditions

A contamination of off-site aquatic environments with pesticides has been observed in the tropics, yet only sparse information exists about pesticide fate in such ecosystems. The objective of our semi-field study was to elucidate the fate of alachlor, atrazine, chlorpyrifos, endosulfan, metolachlor, profenofos, simazine, and trifluralin in the aqueous environment of the Pantanal wetland (MT, Brazil). To this aim, water and water/sediment microcosms of two sizes (0.78 and 202 l) were installed in the outskirts of this freshwater lagoon environment and pesticide dissipation was monitored for up to 50 d after application. The physical-chemical water conditions that developed in the microcosms were reproducible among field replicates for both system sizes. Pesticide dissipation was substantially enhanced for most pesticides in small microcosms relative to the large ones (reduced DT(50) by a factor of up to 5.3). The presence of sediment in microcosms led to increased persistence of chlorpyrifos, endosulfan, and trifluralin in the test systems, while for polar pesticides (alachlor, atrazine, metolachlor, profenofos, and simazine) a lesser persistence was observed. Atrazine, simazine, metolachlor, and alachlor were identified as the most persistent pesticides in large water microcosms (DT(50) > or = 47 d); in large water/sediment systems endosulfan beta, atrazine, metolachlor, and simazine showed the slowest dissipation (DT(50) > or = 44 d). A medium-term accumulation in the sediment of tropical ecosystems can be expected for chlorpyrifos and endosulfan isomers (11-35% of applied amount still extractable at 50 d after application). We conclude that the persistence of the studied pesticides in aquatic ecosystems of the tropics is not substantially lower than during summer in temperate regions.     

The toxicity of phthalocyanines to the aquatic plant Lemna minor (duckweed) - testing of 31 compounds

Phthalocyanines are prospective chemicals that have applications in industry, medicine and biology due especially to their architectural flexibility and production of reactive oxygen species. Although they are used in so many areas of human activities nowadays, there is still little knowledge of their ecotoxicity. Here we present the first observation of their toxic effects on representatives of the aquatic plants Lemna minor. The tested phthalocyanines possess a wide spectrum of phytotoxicity ranging from seldom (>50 mg L⁻¹) to highly toxic 0.11 mg L⁻¹. Moreover, the potential of phthalocyanines to be used as selective cyanocides or herbicides is discussed as well.     

Evaluation of aquatic environmental fate of 2,4,6-trichlorophenol with a mathematical model

A mathematical model, Simplified Approach for Fate Evaluation of Chemicals in Aquatic Systems (SAFECAS), was applied to evaluate fate of 2,4,6-trichlorophenol(TCP) in three types of aquatic environments; a river, an oligotrophic lake, and an eutrophic lake.Since phenols are dissociative substances, equilibrium constants and rate constants for transfer and transformation processes were measured or estimated as a function of pH.Results suggest that most of TCP is distributed to the water phase in aquatic environments, and is almost removed by the advective outflow in the river and by the photodegradation in lakes.     

Comparison of different physiological parameter responses in Lemna minor and Scenedesmus obliquus exposed to herbicide flumioxazin

The sensitivity of different physiological parameters in Scenedesmus obliquus and Lemna minor exposed to herbicide (flumioxazin) was investigated to indicate the most convenient and sensitive parameter. To assess toxicity of flumioxazin, we used a panel of biomarkers: pigment contents, chlorophyll fluorescence parameters and antioxidative enzyme activities. Algae and duckweed were exposed to 48-h IC50 for growth rate. In L. minor, the sensitivity of the parameters was as follows: QN > Oxygen emmision > phiS(PSII) > QP > phi(PSII) > CAT, GR > Pigment> APO > Growth. For S. obliquus, this ranking was as follows: CAT > Oxygen emission > QP > APO > GR > Pigment > phiS(PSII) > Growth > phi(PSII) > QN (from the greatest to the least sensitive). The results demonstrated that the observed toxicity is related not only to interspecific variations but also to the selected parameter.     

The effect of thallium on the growth of Lemna minor and plant tissue concentrations in relation to both exposure and toxicity

The effect of thallium on frond production and the rates of increase in surface area and fresh weight in Lemna minor were examined in terms of concentrations of the element in the growth medium and in the plant. The toxicity indices, EC(50) and threshold concentration, indicate that curtailment of frond expansion occurs at a lower thallium exposure than inhibition of frond multiplication. Production of smaller fronds, rather than chlorosis, was the most notable initial response to thallium stress and, below the threshold of toxicity, enhanced multiplication rates were recorded. Subsequent recovery in thallium-free medium was significant in the region of EC(50) exposures and below, but very little recovery occurred at higher exposures. Lemna minor has a remarkable capacity to accumulate thallium, and accumulation factors of 88 x 10(3) at low exposures, and 6 x 10(3) at high exposures, were recorded, which would suggest some form of active uptake.     

Toxicity of uranium and copper individually, and in combination, to a tropical freshwater macrophyte (Lemna aequinoctialis)

Copper (Cu) and uranium (U) are of potential ecotoxicological concern to tropical freshwater biota in northern Australia, as a result of mining activities. Few data are available on the toxicity of U, and no data are available on the toxic interaction of Cu and U, to freshwater biota. This study determined the toxicity of Cu and U individually, and in combination, to a tropical freshwater macrophyte, Lemna aequinoctialis (duckweed), in a synthetic soft water (27 degrees C; pH, 6.5; hardness, 40 mg CaCO3 l-1, alkalinity, 16 mg CaCO3 l-1), typical of many fresh surface waters in coastal northern Australia. The growth rate of L. aequinoctialis decreased with increasing Cu or U concentrations, with the concentration of Cu inhibiting growth by 50% (EC50) being 16+/-1.0 microg l-1, with a minimum detectable effect concentration (MDEC) of 3.2 microg l-1. The concentration of U inhibiting growth by 50% (EC50) was 758+/-35 microg l-1 with a MDEC of 112 microg l-1. The EC50 value for the exposure of L. aequinoctialis to equitoxic mixtures of Cu and U was significantly (P0.05) higher than one toxic unit (1.35; 95% confidence interval, 1.18-1.52), indicating that the combined effects of Cu and U are less than additive (antagonistic). Therefore, inhibition of the growth rate of L. aequinoctialis was reduced when Cu and U were present in equitoxic mixtures, relative to individual metal exposures. Since non-additive (e.g. antagonistic) interactions of metal mixtures cannot be predicted using current mixture models, these results have important potential implications for the protection of freshwater ecosystems through the derivation of national water quality guidelines.     

Environmental fate of rice paddy pesticides in a model ecosystem.

The distribution and metabolic fate of several rice paddy pesticides were evaluated in a modified model ecosystem. Among the three BHC isomers, beta-isomer was the most stable and bioconcentrated in all of the organisms. Alpha- and gamma-isomers were moderately persistent and degraded to some extent during the 33 day period. Disulfoton was relatively persistent due to the transformation to its oxidation products. Pyridaphenthion was fairly biodegradable. N-Phenyl maleic hydrazide derived from the hydrolysis of pyridaphenthion was not detected in the organisms though it was found in the aquarium water after 33 days. Cartap and edifenphos were considerably biodegradable, and the ratio of the conversion to water soluble metabolites was very high. There was a distinct difference in the persistence of Kitazin P and edifenphos in the aquarium water. It appeared that the hydrolysis rate of the pesticides affected their fate in the organisms. PCP appeared to be moderately biodegradable. CNP was considerably stable and stored in the organisms though the concentration in the aquarium water was relatively low. The persistence and distribution of the pesticides in the model ecosystem were dependent on their chemical structures. In spite of the limitation derived from short experimental period, the model ecosystem may be applicable for predicting the environmental fate of pesticides.     

Distribution of the herbicide atrazine in a microcosm with riparian forest plants

Pesticides applied on sugarcane reach the subsoil of riparian forests and probably contaminate the river water. This work was conducted to learn about the phytoremediation of atrazine and subsoil contamination using the common riparian forest species of Cecropia hololeuca Miq. and Trema micranta (L.) Blum. These plants were grown in soil microcosms where ¹⁴C-atrazine at 1/10 of the field-recommended dose was applied at the bottom of the microcosm simulating the movement from contaminated ground water to the upper soil layers and into plants. Residues of ¹⁴C-atrazine were detected in all parts of the microcosm including soil, rhizosphere and the roots in different layers of the microcosm, stem and leaves. Atrazine mineralization was higher (10.2%) in the microcosms with plants than the control microcosms without plants (1.2%). The upward movement of this pesticide from deeper to more superficial soil layers occurred in all the microcosms with plants, powered by evapotranspiration process. From the atrazine applied in this study about 45% was taken up by C. hololeuca and 35% by T. micrantha. The highest amount of radioactivity (%) was found in the fine roots and the specific radioactivity (% g^?1) showed that thick, fine roots and leaves bioaccumulate atrazine. The enhanced mineralization of atrazine as well the phytostabilization effect of the tree biomass will reduce the bioavailability of these residues and consequently decrease the hazardous effects on the environment.     

Distribution of the herbicide atrazine in a microcosm with riparian forest plants

Pesticides applied on sugarcane reach the subsoil of riparian forests and probably contaminate the river water. This work was conducted to learn about the phytoremediation of atrazine and subsoil contamination using the common riparian forest species of Cecropia hololeuca Miq. and Trema micranta (L.) Blum. These plants were grown in soil microcosms where (14)C-atrazine at 1/10 of the field-recommended dose was applied at the bottom of the microcosm simulating the movement from contaminated ground water to the upper soil layers and into plants. Residues of (14)C-atrazine were detected in all parts of the microcosm including soil, rhizosphere and the roots in different layers of the microcosm, stem and leaves. Atrazine mineralization was higher (10.2%) in the microcosms with plants than the control microcosms without plants (1.2%). The upward movement of this pesticide from deeper to more superficial soil layers occurred in all the microcosms with plants, powered by evapotranspiration process. From the atrazine applied in this study about 45% was taken up by C. hololeuca and 35% by T. micrantha. The highest amount of radioactivity (%) was found in the fine roots and the specific radioactivity (% g(-1)) showed that thick, fine roots and leaves bioaccumulate atrazine. The enhanced mineralization of atrazine as well the phytostabilization effect of the tree biomass will reduce the bioavailability of these residues and consequently decrease the hazardous effects on the environment.