Fate, behavior and effects of surfactants and their degradation products in the environment

Surfactants are widely used in household and industrial products. After use, surfactants as well as their products are mainly discharged into sewage treatment plants and then dispersed into the environment through effluent discharge into surface waters and sludge disposal on lands. Surfactants have different behavior and fate in the environment. Nonionic and cationic surfactants had much higher sorption on soil and sediment than anionic surfactants such as LAS. Most surfactants can be degraded by microbes in the environment although some surfactants such as LAS and DTDMAC as well as alkylphenols may be persistent under anaerobic conditions. LAS were found to degrade in sludge amended soils with a half-lives of 7 to 33 days. Most surfactants are not acutely toxic to organisms at environmental concentrations and aquatic chronic toxicity of surfactants occurred at concentrations usually greater than 0.1 mg/L. However, alkylphenols have shown to be capable of inducing the production of vitellogenin in male fish at a concentration as low as 5 microg/L. More toxicity data are needed to assess the effects on terrestrial organisms such as plants.     

A probabilistic approach to obtaining limiting estimates of radionuclide concentration in biota

The US Department of Energy has developed a graded approach for evaluating radiation doses to biota. Limiting concentrations of radionuclides in water, soil, and sediment were derived for twenty-three radionuclides. Four organism types (aquatic animals, riparian animals, terrestrial animals, and terrestrial plants) were selected as the basis for method development. While environmental transfer data needed for deriving biota tissue concentrations are available for aquatic animals and terrestrial plants, less information is available for terrestrial and riparian organisms. Two methods were applied and examined for their ability to provide estimates of organism:soil or organism:water concentration factors in lieu of measured data. The kinetic/allometric approach combined with a parameter uncertainty analysis provides a needed method to estimate concentration factors across multiple species with limited input data.     

Impact of arbuscular mycorrhizal fungi on uranium accumulation by plants

Contamination by uranium (U) occurs principally at U mining and processing sites. Uranium can have tremendous environmental consequences, as it is highly toxic to a broad range of organisms and can be dispersed in both terrestrial and aquatic environments. Remediation strategies of U-contaminated soils have included physical and chemical procedures, which may be beneficial, but are costly and can lead to further environmental damage. Phytoremediation has been proposed as a promising alternative, which relies on the capacity of plants and their associated microorganisms to stabilize or extract contaminants from soils. In this paper, we review the role of a group of plant symbiotic fungi, i.e. arbuscular mycorrhizal fungi, which constitute an essential link between the soil and the roots. These fungi participate in U immobilization in soils and within plant roots and they can reduce root-to-shoot translocation of U. However, there is a need to evaluate these observations in terms of their importance for phytostabilization strategies.     

Diclofenac and its transformation products: Environmental occurrence and toxicity - A review

Diclofenac (DCF) is a prevalent anti-inflammatory drug used throughout the world. Intensive researches carried out in the past few decades have confirmed the global ubiquity of DCF in various environmental compartments. Its frequent occurrence in freshwater environments and its potential toxicity towards several organisms such as fish and mussels makes DCF an emerging environmental contaminant. At typical detected environmental concentrations, the drug does not exhibit toxic effects towards living organisms, albeit chronic exposure may lead to severe effects. For DCF, about 30–70% removal has been obtained through the conventional treatment system in wastewater treatment plant being the major primary sink. Thus, the untreated DCF will pass to surface water. DCF can interact with other inorganic contaminants in the environment particularly in wastewater treatment plant, such as metals, organic contaminants and even with DCF metabolites. This process may lead to the creation of another possible emerging contaminant. In the present context, environmental fate of DCF in different compartments such as soil and water has been addressed with an overview of current treatment methods. In addition, the toxicity concerns regarding DCF in aquatic as well as terrestrial environment along with an introduction to the metabolites of DCF through consumption as well as abiotic degradation routes are also discussed. Further studies are required to better assess the fate and toxicological effects of DCF and its metabolites and must consider the possible interaction of DCF with other contaminants to develop an effective treatment method for DCF and its traces.     

Derivation of a screening methodology for evaluating radiation dose to aquatic and terrestrial biota

The United States Department of Energy (DOE) currently has in place a radiation dose standard for the protection of aquatic animals, and is considering additional dose standards for terrestrial biota. These standards are: 10 mGy/d for aquatic animals, 10 mGy/d for terrestrial plants, and, 1 mGy/d for terrestrial animals. Guidance on suitable approaches to the implementation of these standards is needed. A screening methodology, developed through DOE's Biota Dose Assessment Committee (BDAC), serves as the principal element of DOE's graded approach for evaluating radiation doses to aquatic and terrestrial biota. Limiting concentrations of radionuclides in water, soil, and sediment were derived for 23 radionuclides. Four organism types (aquatic animals; riparian animals; terrestrial animals; and terrestrial plants) were selected as the basis for development of the screening method. Internal doses for each organism type were calculated as the product of contaminant concentration, bioaccumulation factor(s) and dose conversion factors. External doses were calculated based on the assumption of immersion of the organism in soil, sediment, or water. The assumptions and default parameters used provide for conservative screening values. The screening methodology within DOE's graded approach should prove useful in demonstrating compliance with biota dose limits and for conducting screening assessments of radioecological impact. It provides a needed evaluation tool that can be employed within a framework for protection of the environment.     

Toxic and genotoxic impact of fibrates and their photoproducts on non-target organisms

Lipid regulators have been detected in effluents from sewage treatment plants and surface waters from humans via excretion. This study was designed to assess the ecotoxicity of fibrates, lipid regulating agents. The following compounds were investigated: Bezafibrate, Fenofibrate and Gemfibrozil and their derivatives obtained by solar simulator irradiation. Bioassays were performed on bacteria, algae, rotifers and microcrustaceans to assess acute and chronic toxicity, while SOS Chromotest and Ames test were utilized to detect the genotoxic potential of the investigated compounds. The photoproducts were identified by their physical features and for the first risk evaluation, the environmental impact of parental compounds was calculated by Measured Environmental Concentrations (MEC) using the available data from the literature regarding drug occurrence in the aquatic environment and the Predicted No Effect Concentrations (PNEC) based on our toxicity data. The results showed that acute toxicity was in the order of dozens of mg/L for all the trophic levels utilized in bioassays (bacteria, rotifers, crustaceans). Chronic exposure to these compounds caused inhibition of growth population on rotifers and crustaceans while the algae seemed to be slightly affected by this class of pharmaceuticals. Genotoxic and mutagenic effects were especially found for the Gemfibrozil photoproduct suggesting that also byproducts have to be considered in the environmental risk of drugs.     

Occurrence,fate and effects of azoxystrobin in aquatic ecosystems: A review

The use of pesticides for crop protection may result in the presence of toxic residues in environmental matrices. In the aquatic environment, pesticides might freely dissolve in the water or bind to suspended matter and to the sediments, and might be transferred to the organisms' tissues during bioaccumulation processes, resulting in adverse consequences to non-target species. One such group of synthetic organic pesticides widely used worldwide to combat pathogenic fungi affecting plants is the strobilurin chemical group. Whereas they are designed to control fungal pathogens, their general modes of action are not specific to fungi. Consequently, they can be potentially toxic to a wide range of non-target organisms. The present work had the intent to conduct an extensive literature review to find relevant research on the occurrence, fate and effects of azoxystrobin, the first patent of the strobilurin compounds, in aquatic ecosystems in order to identify strengths and gaps in the scientific database. Analytical procedures and existing legislation and regulations were also assessed. Data gathered in the present review revealed that analytical reference standards for the most relevant environmental metabolites of azoxystrobin are needed. Validated confirmatory methods for complex matrices, like sediment and aquatic organisms' tissues, are very limited. Important knowledge of base-line values of azoxystrobin and its metabolites in natural tropical and estuarine/marine ecosystems is lacking. Moreover, some environmental concentrations of azoxystrobin found in the present review are above the Regulatory Acceptable Concentration (RAC) in what concerns risk to aquatic invertebrates and the No Observed Ecologically Adverse Effect Concentration (NOEAEC) reported for freshwater communities. The present review also showed that there are very few data on azoxystrobin toxicity to different aquatic organisms, especially in what concerns estuarine/marine organisms. Besides, toxicity studies mostly address azoxystrobin and usually neglect the more relevant environmental metabolites. Further work is also required in what concerns effects of exposure to multi-stressors, e.g. pesticide mixtures. Even though Log K_ow for azoxystrobin and R234886, the main metabolite of azoxystrobin in water, are below 3, the bio-concentration factor and the bioaccumulation potential for azoxystrobin are absent in the literature. Moreover, no single study on bioaccumulation and biomagnification processes was found in the present review.     

Human health risk assessment of pharmaceuticals and personal care products in plant tissue due to biosolids and manure amendments,and wastewater irrigation

Amending soil with biosolids or livestock manure provides essential nutrients in agriculture. Irrigation with wastewater allows for agriculture in regions where water resources are limited. However, biosolids, manure and wastewater have all been shown to contain pharmaceuticals and personal care products (PPCPs). Studies have shown that PPCPs can accumulate in the tissues of plants but the risk that accumulated residues may pose to humans via consumption of edible portions is not well documented. This study reviewed the literature for studies that reported residues of PPCPs in the edible tissue of plants grown in biosolids- or manure-amended soils or irrigated with wastewater. These residues were used to determine the estimated daily intake of PPCPs for an adult and toddler. Estimated daily intake values were compared to acceptable daily intakes to determine whether PPCPs in plant tissue pose a hazard to human health. For all three amendment practices, the majority of reported residues resulted in hazard quotients < 0.1. Amendment with biosolids or manure resulted in hazard quotients ≥ 0.1 for carbamazepine, diphenhydramine, salbutamol, triclosan, and sulfamethazine. Irrigation with wastewater resulted in hazard quotients of ≥ 0.1 for flunixin, ketoprofen, lamotrigine, metoprolol, and sildenafil. Many of the residues that resulted in hazard quotients ≥ 0.1 were due to exposing plants to concentrations of PPCPs that would not be considered relevant based on concentrations reported in biosolids and manure or unrealistic methods of exposure, which lead to artificially elevated plant residues. Our assessment indicates that the majority of individual PPCPs in the edible tissue of plants due to biosolids or manure amendment or wastewater irrigation represent a de minimis risk to human health. Assuming additivity, the mixture of PPCPs could potentially present a hazard. Further work needs to be done to assess the risk of the mixture of PPCPs that may be present in edible tissue of plants grown under these three amendment practices.     

Occurrence,fate and ecological risk of five typical azole fungicides as therapeutic and personal care products in the environment: A review

Azole fungicides are widely used to treat fungal infection in human. After application, these chemicals may reach to the receiving environment via direct or indirect discharge of wastewaters, thus posing potential risks to non-target organisms. We aimed to review the occurrence, fate and toxicological effects of some representative household azole fungicides in the environment. Azole fungicides were widely detected in surface water and sediment of the aquatic environment due to their incomplete removal in wastewater treatment plants. These chemicals are found resistant to microbial degradation, but can undergo photolysis under UV irradiation. Due to different physiochemical properties, azole fungicides showed different environmental behaviors. The residues of azole fungicides could cause toxic effects on aquatic organisms such as algae and fish. The reported effects include regulation changes in expression of cytochrome P450-related genes and alteration in CYP450-regulated steroidogenesis causing endocrine disruption in fish. Further studies are essential to investigate the removal of azole fungicides by advanced treatment technologies, environmental fate such as natural photolysis, and toxic pathways in aquatic organisms.     

A dynamic model for assessing radiological consequences of tritium routinely released in rivers. Application to the Loire River

A dynamic model for assessing the transfer of tritium in a food chain was applied to the Loire River, where 14 nuclear power plants situated on five different sites operate. The model considers several potential exposure pathways in the aquatic and terrestrial ecosystems: transfer of tritium through the aquatic food chain (especially fish); use of river water for agricultural purposes (irrigation) and transfer of radionuclides through the terrestrial food chain (vegetables, meat, milk); subsequent internal exposure of humans due to ingestion of contaminated foodstuffs. For biological environmental compartments, the transfer of tritium to organic matter (i.e. OBT) was simulated. For each of the parameters introduced in this model, a probability density function, allowing further uncertainty and sensitivity analyses, was proposed. Uncertainty/sensitivity analyses were performed to determine a confidence interval for the mean annual dose to critical groups and to identify the parameters responsible for the uncertainty and subsequent research priorities.     

Nonylphenol in the environment: a critical review on occurrence, fate, toxicity and treatment in wastewaters

Nonylphenol is a toxic xenobiotic compound classified as an endocrine disrupter capable of interfering with the hormonal system of numerous organisms. It originates principally from the degradation of nonylphenol ethoxylates which are widely used as industrial surfactants. Nonylphenol ethoxylates reach sewage treatment works in substantial quantities where they biodegrade into several by-products including nonylphenol. Due to its physical-chemical characteristics, such as low solubility and high hydrophobicity, nonylphenol accumulates in environmental compartments that are characterised by high organic content, typically sewage sludge and river sediments, where it persists. The occurrence of nonylphenol in the environment is clearly correlated with anthropogenic activities such as wastewater treatment, landfilling and sewage sludge recycling. Nonylphenol is found often in matrices such as sewage sludge, effluents from sewage treatment works, river water and sediments, soil and groundwater. The impacts of nonylphenol in the environment include feminization of aquatic organisms, decrease in male fertility and the survival of juveniles at concentrations as low as 8.2 mug/l. Due to the harmful effects of the degradation products of nonylphenol ethoxylates in the environment, the use and production of such compounds have been banned in EU countries and strictly monitored in many other countries such as Canada and Japan. Although it has been shown that the concentration of nonylphenol in the environment is decreasing, it is still found at concentrations of 4.1 mug/l in river waters and 1 mg/kg in sediments. Nonylphenol has been referred to in the list of priority substances in the Water Frame Directive and in the 3rd draft Working Document on Sludge of the EU. Consequently there is currently a concern within some industries about the possibility of future regulations that may impose the removal of trace contaminants from contaminated effluents. The significance of upgrading sewage treatment works with advanced treatment technologies for removal of trace contaminants is discussed.     

Toxic risk of surface water pollution--six years of experience

Assessment of an ecological quality of surface water is necessary for effective protection, abatement and successive revitalisation of river ecosystems. This quality is primarily given by biological impact of surface water pollution. Substances contained in pollution are frequently toxic to aquatic organisms. Risk of chronic impact of surface water pollution is very often underestimated due to hidden long time action of pollutants. Proper estimation of the risk is not possible from results of chemical analyses and data of substances' toxicity. Chemical analyses are not able to detect all substances presented in water including the products of reactions between them. In addition, a simultaneous presence of substances can modify their final effect on aquatic organisms. Therefore, a complex method of assessment of toxic risk of surface water pollution based on ecotoxicological approach was developed. The toxic risk of surface water pollution is determined from results of evaluation of toxic risk of organic part and inorganic part of surface water pollution. Resultant degree of toxic risk of total pollution is given by the highest degree detected in any part of the water pollution. Presented method, which is routinely used for monitoring in the Czech part of the Odra river basin, was fully standardised and published in the form of the Czech branch technical norm of water management (TNV) in the year 2000.     

Impacts of atrazine in aquatic ecosystems

A portion of all herbicides applied to forests, croplands, road sides, and gardens are inevitably lost to water bodies either directly through runoff or indirectly by leaching through groundwater into ephemeral streams and lakes. Once in the aquatic environment, herbicides may cause stress within aquatic communities and radically alter community structure. Atrazine is one of the most effective and inexpensive herbicides in the world and is consequently used more frequently than any other herbicide. Atrazine is frequently detected in aquatic waters, and has been known to affect reproduction of aquatic flora and fauna, which in turn impacts on the community structure as a whole. This paper presents a summary of the reported direct and indirect impacts of atrazine on aquatic organisms and community structure. The information can be used for developing improved management guidelines and legislation. It is concluded that a single universal maximum limit on the atrazine application in catchments, as suggested by many regulatory authorities, does not provide adequate protection of the aquatic environment. Rather, it is advocated that flexible limits on the application of atrazine be developed in line with the potential risk of contamination to surface and subsurface water and fragility of the aquatic environment.     

Assessment of ecotoxicological risks related to depositing dredged materials from canals in northern France on soil

The implementation of an ecological risk assessment framework is presented for dredged material deposits on soil close to a canal and groundwater, and tested with sediment samples from canals in northern France. This framework includes two steps: a simplified risk assessment based on contaminant concentrations and a detailed risk assessment based on toxicity bioassays and column leaching tests. The tested framework includes three related assumptions: (a) effects on plants (Lolium perenne L.), (b) effects on aquatic organisms (Escherichia coli, Pseudokirchneriella subcapitata, Ceriodaphnia dubia, and Xenopus laevis) and (c) effects on groundwater contamination. Several exposure conditions were tested using standardised bioassays. According to the specific dredged material tested, the three assumptions were more or less discriminatory, soil and groundwater pollution being the most sensitive. Several aspects of the assessment procedure must now be improved, in particular assessment endpoint design for risks to ecosystems (e.g., integration of pollutant bioaccumulation), bioassay protocols and column leaching test design.     

Toxicology and detection methods of the alkaloid neurotoxin produced by cyanobacteria, anatoxin-a

Freshwater resources are under stress due to naturally occurring conditions and human impacts. One of the consequences is the proliferation of cyanobacteria, microphytoplankton organisms that are capable to produce toxins called cyanotoxins. Anatoxin-a is one of the main cyanotoxins. It is a very potent neurotoxin that was already responsible for some animal fatalities. In this review we endeavor to divulgate much of the internationally published information about toxicology, occurrence and detection methods of anatoxin-a. Cyanobacteria generalities, anatoxin-a occurrence and production as well as anatoxin-a toxicology and its methods of detection are the aspects focused in this review. Remediation of anatoxin-a occurrence will be addressed with a public health perspective. Final remarks call the attention for some important gaps in the knowledge about this neurotoxin and its implication to public health. Alterations of aquatic ecosystems caused by anatoxin-a is also addressed. Although anatoxin-a is not the more frequent cyanotoxin worldwide, it has to be regarded as a health risk that can be fatal to terrestrial and aquatic organisms because of its high toxicity.     

Observations and modelling of thoron and its progeny in the soil-atmosphere-plant system

Samples of pasture vegetation, mainly Trifolium pratensis, were collected at the Botanic Garden of the University of Bologna during the period 1998-2000 and measured by gamma-spectrometry for determining thoron progeny. Concentrations of ²¹²Pb were between 1.5 and 20 Bq m⁻², with individual peaks up to 70 Bq m⁻². Soil samples were collected at the same location and physically characterised. Their chemical composition (particularly Th and U) was determined by X-ray fluorescence spectroscopy. Lead-212 on plants mainly originates from dry and wet deposition of this isotope generated in the lower atmosphere by the decay of its short-lived precursor ²²⁰Rn, which is produced in the upper soil layers as a member of the natural thorium decay chain and exhales into the atmosphere. Concentrations of ²²⁰Rn in the atmosphere depend on (1) the amount of Th present in soil, (2) the radon fraction which escapes from the soil minerals into the soil pore space, (3) its transport into the atmosphere, and (4) its redistribution within the atmosphere. The mobility of radon in soil pore space can vary by orders of magnitude depending on the soil water content, thus being the main factor for varying concentrations of ²²⁰Rn and ²¹²Pb in the atmosphere. We present a simple model to predict concentrations of thoron in air and its progeny deposited from the atmosphere, which takes into account varying soil moisture contents calculated by the OPUS code. Results of this model show close agreement with our observations.     

The distribution of tritium in the terrestrial and aquatic environments of the Creys-Malville nuclear power plant (2002-2005)

The Creys-Malville nuclear plant, located on the left bank of the Rh?ne, was shut down in 1998. The facilities are currently in their initial stage of dismantling. In order to establish a baseline for tritium in the vicinity of the site prior to the main dismantling phase, we carried out a monitoring program between 2002 and 2005 in the main terrestrial and aquatic compartments of the local environment. Tritium levels in the groundwaters and in the Rh?ne waters correspond to the regional tritium concentration in precipitation. The data obtained for the terrestrial environment are also in good agreement with the regional background and do not show any specific signature linked to the nuclear plant. The various aquatic compartments of the Rh?ne (fish, plant, sediment) are significantly enriched in tritium both upstream and downstream of the power plant: although Tissue-Free Water Tritium concentrations are in equilibrium with the river water, the non-exchangeable fraction of organic bound tritium in plants and fishes shows values which outpace the river water background by one to two orders of magnitude, and up to four to five orders of magnitude in the sediments. This tritium anomaly is not related to the nuclear plant, as it is already present at the Swiss border 100km upstream of the site. Although fine particles of tritiated polystyrene entering the composition of the luminous paints used by the clock industry have been suspected on several occasions, the exact nature and the origin of this tritium source remain unknown and require further investigations.     

Effects of seven organic pollutants on soil nematode Caenorhabditis elegans

Caenorhabditis elegans is a free-living soil nematode that is commonly used as a model for toxicity tests. The aim of this study was to investigate the toxicity of seven organic pollutants: four azaarenes (quinoline, acridine, phenazine, and 1,10-phenanthroline), short-chain chlorinated paraffins, and two organochlorinated pesticides (toxaphene and hexachlorobenzene). The exposure to all chemicals was carried out in three test media (soil, agar, and aquatic medium), and adult mortality was evaluated after 24 and 48 h. Toxaphene was the most toxic substance with LC(50) (48 h) of 379 mg/kg in the soil and 0.2 mg/L in the aquatic medium. Quinoline was the most toxic chemical in agar test with LC(50) (48 h) of 10 mg/L. HCB showed a very low toxicity in all tests, maybe due to its very low water solubility. Longer than 24-h test duration was found necessary for getting more correct data on toxicity. In comparison with other studies, C. elegans was less sensitive than other soil invertebrates. Different response might be attributed to different exposure routes and shorter test duration. Equilibrium partitioning theory was used to calculate K(oc) from results of soil and aquatic tests but this approach was found not working. Our results suggest that the tests with nematode C. elegans should be included to the battery of tests for risk assessment of POPs in soil.     

Spatially explicit prioritization of human antibiotics and antineoplastics in Europe

This paper presents a screening tool for the location-specific prioritization of human pharmaceutical emissions in Europe, based on risk quotients for the aquatic environment and human health. The tool provides direction towards either monitoring activities or additional research. Its application is illustrated for a set of 11 human antibiotics and 7 antineoplastics. Risk quotients for the aquatic environment were highest for levofloxacin, doxycycline and ciprofloxacin, located in Northern Italy (Milan region; particularly levofloxacin) and other densely populated areas in Europe (e.g. London, Krakow and the Ruhr area). Risk quotients for human health not only depend on pharmaceutical and location, but also on behavioral characteristics, such as consumption patterns. Infants in eastern Spain that consume locally produced food and conventionally treated drinking water were predicted to run the highest risks. A limited comparison with measured concentrations in surface water showed that predicted and measured concentrations are approximately within one order of magnitude.