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.     

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.     

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.     

Factors affecting metal toxicity to (and accumulation by) aquatic organisms — Overview

This literature review encompasses aquatic environmental toxicities of metals and metalloids. The emphasis is on the influencing factors on metal toxicity to aquatic organisms. The effects of environmental factors on metal uptake are also discussed. The factors can be divided into biotic and abiotic. The biotic factors include tolerance, size and life stages, species, and nutrition related to the test organisms. The abiotic factors include organic substances, pH, temperature, alkalinity and hardness, inorganic ligands, interactions, sediments, and others. These factors can alter metal toxicity in the aquatic environment substantially, mostly causing attenuating effect. The literature shows divergent results. For example, the interactions between Cd and Zn were reported to be synergistic by some researchers and antagonistic by others. It is recommended that environmental hazard assessment takes into consideration the results of standard toxicity tests and site-specific conditions which can moderate metal toxicity considerably.     

The ecological effects of trichloroacetic acid in the environment

Trichloroacetic acid (TCAA) is a member of the family of compounds known as chloroacetic acids, which includes mono-, di- and trichloroacetic acid. The significant property these compounds share is that they are all phytotoxic. TCAA once was widely used as a potent herbicide. However, long after TCAA's use as a herbicide was discontinued, its presence is still detected in the environment in various compartments. Methods for quantifying TCAA in aqueous and solid samples are summarized. Concentrations in various environmental compartments are presented, with a discussion of the possible formation of TCAA through natural processes. Concentrations of TCAA found to be toxic to aquatic and terrestrial organisms in laboratory and field studies were compiled and used to estimate risk quotients for soil and surface waters. TCAA levels in most water bodies not directly affected by point sources appear to be well below toxicity levels for the most sensitive aquatic organisms. Given the phytotoxicity of TCAA, aquatic plants and phytoplankton would be the aquatic species to monitor for potential effects. Given the concentrations of TCAA measured in various soils, there appears to be a risk to terrestrial organisms. Soil uptake of TCAA by plants has been shown to be rapid. Also, combined uptake of TCAA from soil and directly from the atmosphere has been shown. Therefore, risk quotients derived from soil exposure may underestimate the risk TCAA poses to plants. Moreover, TCE and TCA have been shown to be taken up by plants and converted to TCAA, thus leading to an additional exposure route. Mono- and di-chloroacetic acids can co-occur with TCAA in the atmosphere and soil and are more phytotoxic than TCAA. The cumulative effects of TCAA and compounds with similar toxic effects found in air and soil must be considered in subsequent terrestrial ecosystem risk assessments.     

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.     

Assays with Daphnia magna and Danio rerio as alert systems in aquatic toxicology

For the evaluation and monitoring of the water quality, a series of methodologies, which have as basis an ample variety of bioindicators, may be applied. The aim of this research was to evaluate the use of ecotoxicity assays with Daphnia magna and Danio rerio as alert systems in water contaminated with toxic substances. Using two toxicity databases, the sensibility of those aquatic organisms to a wide variety of chemical products and elements and to some chemical categories was investigated. The relation between the reference dose for human oral chronic exposure (RfD) of all chemical products and the acute toxicity values for both bioindicators was also studied. Acute toxicity tests with D. magna respond to a larger variety of chemicals with a higher sensitivity than those with D. rerio. Although mammals, crustaceans and fish have different routes of exposure, target organs and toxic mechanisms, acute toxicity essays with fish and Daphnia may be used as an initial screening before mammal models are used.     

Biological activity and environmental impact of anionic surfactants

The newest results concerning the biological activity and environmental fate of anionic surfactants are collected and critically evaluated. The chemical and physicochemical parameters related to the biological activity and the field of application are briefly discussed. Examples on the effect of anionic surfactants on the cell membranes, on the activity of enzymes, on the binding to various proteins and to other cell components and on their human toxicity are presented and the possible mode of action is elucidated. The sources of environmental pollution caused by anionic surfactants are listed and the methods developed for their removal from liquid, semiliquid and solid matrices are collected. Both the beneficial and adversary effects of anionic surfactants on the environment are reported and critically discussed. It was concluded that the role of anionic surfactants in the environment is ambiguous: they can cause serous environmental pollution with toxic effect on living organisms; otherwise, they can promote the decomposition and/or removal of other inorganic and organic pollutants from the environment. The relationship between their chemical structure, physicochemical parameters, biological activity and environmental impact is notwell understood. A considerable number of data are needed for the development of new anionic surfactants and for the successful application of the existing ones to reduce the adversary and to promote beneficial effects.     

Thallium: a review of public health and environmental concerns

Thallium (Tl) is a rare but widely dispersed element. All forms of thallium are soluble enough to be toxic to living organisms. Thallium is more toxic to humans than mercury, cadmium, lead, copper or zinc and has been responsible for many accidental, occupational, deliberate, and therapeutic poisonings since its discovery in 1861. Its chemical behavior resembles the heavy metals (lead, gold and silver) on the one hand and the alkali metals (K, Rb, Cs) on the other. It occurs almost exclusively in natural waters as monovalent thallous cation. The solubility of thallous compounds is relatively high so that monovalent thallium is readily transported through aqueous routes into the environment. Tl can be transferred from soils to crops readily and accrues in food crops. The fascinating chemistry and high toxicity potential make thallium and its compounds of particular scientific interest and environmental concern. Thallium was detected in base-metal mining effluents. The conventional removal of heavy metals from wastewater has little effect on thallium. In this review, various treatment options and removal technologies are enumerated in order to protect the environment from thallium toxicity.     

Polybrominated diphenyl ether flame retardants in the U.S. marine environment: A review

Polybrominated diphenyl ethers (PBDEs) are used as flame retardants in polymeric materials such as furnishing foam, rigid plastics and textiles. The U.S. has historically led the world production of these man-made chemicals and was responsible for about 50% of the total global demand in 2001. Paradoxically, scientific studies addressing sources, behavior and fate of PBDEs in the U.S. environment are limited when compared to those in Europe. This paper reviews the distribution of PBDEs in marine and estuarine matrices of the three U.S. coasts (Atlantic, Pacific and Gulf of Mexico) and Alaska. PBDEs are ubiquitous in all compartments including water, sediment and biota. Contamination is higher in urbanized regions such as the coast of California. In numerous cases, concentrations of PBDEs in U.S. marine matrices are among the highest in the world. Higher PBDE levels in the U.S. marine environment reflect that over 90% of the Penta-BDE global production has been utilized in the United States. BDEs 47, 99 and 100 typically dominate the composition of PBDEs in most samples and exhibit high concentrations in several matrices. BDEs 17, 28, 33, 49, 153, 154 and 155 are also of concern since they are known to be present in a minor proportion in the Penta-BDE products. BDEs 206, 207, 208 and 209 which occur in Deca-BDE products do not appear to accumulate in most marine organisms although they may be debrominated into more toxic congeners. There is still no regulation addressing PBDEs contamination in the U.S. aquatic environments. Thus, efforts to understand the cycling of PBDEs in the environment as well as toxic effects in organisms are needed to support the development of quality criteria. Some PBDE congeners fulfill the criteria to be recognized as persistent organic pollutants (POPs). The addition of PBDEs to the list of POPs established by the United Nations Stockholm Convention will be important in elevating environmental concerns regarding these chemicals to an appropriate level of awareness.     

Prediction of environmental concentrations of glucocorticoids: The River Thames,UK, as an example

Synthetic glucocorticoids (GCs) are consumed in large amounts as anti-inflammatory and immunosuppressive drugs worldwide. Based on what has been learnt from studies of other human pharmaceuticals, they are likely to be present in the aquatic environment. However, to date, information on the environmental concentrations of GCs is very limited. The situation is complicated by the fact that a considerable number of GCs are in everyday use in most developed countries. Hence, obtaining a full picture of GC concentrations in the aquatic environment using the traditional analytical chemistry approach would be time-consuming and expensive. Thus, we took a modelling approach to predict the total environmental concentration of all synthetic GCs (consisting of 28 individual GCs) in the River Thames, as a first step in risk assessment of these drugs. Using reliable data on consumption, the LF2000-WQX model predicts mean concentrations up to 30 ng/L of total GCs in surface water as a best case scenario when the lowest excretion and highest removal rates in sewage treatment works were used, whereas mean concentrations up to 850 ng/L were predicted when the highest excretion and lowest removal rates are considered. We also present the 10th and 90th percentile concentrations (which indicate the likely range of concentrations seen from high flow to low flow conditions in the river) of the highest and lowest consumed GCs, to show the spatial and temporal variations of the concentrations of individual GCs. These data probably provide reliable estimates of the likely range of concentrations of GCs in a typical river impacted by effluent from many sewage treatment plants. Results also identify the hot spots where field studies on fish could be focused. To determine if aquatic organisms face any threat from GCs, laboratory toxicity studies should be conducted using concentrations similar to those reported here.     

Occurrence,fate and ecological risk of chlorinated paraffins in Asia: A review

Chlorinated paraffins (CPs), complex mixtures of polychlorinated alkanes, are widely used in various industries and are thus ubiquitous in the receiving environment. The present study comprehensively reviewed the occurrence, fate and ecological risk of CPs in various environmental matrices in Asia. Releases from the production and consumption of CPs or CP-containing materials, wastewater discharge and irrigation, sewage sludge application, long-range atmospheric transport and aerial deposition have been found to be most likely sources and transport mechanisms for the dispersion of CPs in various environmental matrices, such as air, water, sediment, soil and biota. CPs can be bioaccumulated in biota and biomagnified through food webs, likely causing toxic ecological effects in organisms and posing health risks to humans. Inhalation, dust ingestion and dietary intake are strongly suggested as the major routes of human exposure. Research gaps are discussed to highlight the perspectives of future research to improve future efforts regarding the analysis of CPs, the environmental occurrence and elimination of CPs, the total environmental pressure, and the risks to organisms and populations.     

Fate of glutaraldehyde in hospital wastewater and combined effects of glutaraldehyde and surfactants on aquatic organisms

Glutaraldehyde (GA), an aliphatic dialdehyde disinfectant, and surfactants, one of the major components of detergents, are widely used in hospitals in order to eliminate pathogenic organisms causing nosocomial infectious diseases. After their use, disinfectants and surfactants reach the wastewater network together. The discharge of chemical compounds from hospital activities into wastewater is also a well-known problem, causing pollution of water resources and constituting an ecological risk for aquatic organisms. In this study, the chemistry and toxicology of GA and surfactant mixtures were reviewed in order to estimate their fate in aquatic ecosystems. Furthermore, their joint effects on aquatic organisms were experimentally assessed in the laboratory. A simple model of the additive joint action of toxicants was used to determine combined acute toxicity effects on the bacteria luminescence and Daphnia mobility of three mixtures containing GA at 1.5 x EC50 24 h [in mg/L] on Daphnia and anionic, cationic and nonionic surfactants at twice their critical micellar concentration (CMC). The mixture of GA and a cationic surfactant gave an EC50 30 min on Vibrio fischeri of 0.158%, with a concentration of 0.04 mg GA/L and 1.04 mg CTAB/L, which provided an additive action. The interaction between GA and an anionic surfactant on V. fischeri produced an antagonistic joint action with an EC50 30 min of 3.95%, containing 1.06 mg GA/L and 33.2 mg SDS/L. A synergistic action with an EC50 30 min of 8.4% on V. fischeri was observed for the mixture containing GA and a nonionic surfactant. Antagonistic interactions were observed for the joint action between GA and the surfactants studied on Daphnia. The mixture of GA and CTAB was more toxic (EC50 24 h=0.02%) than the two other mixtures (EC50 24 h GA+SDS=6%; EC50 24 h GA+TX 100=10%). This study provides new data on the toxicity of certain hospital pollutants entering the aquatic environment and detected in surface and groundwaters. It is necessary to study the joint effects of GA and surfactant mixtures following chronic and sublethal standard bioassays in order to estimate the contribution of the additive joint action models in assessing the environmental risk of hospital wastewater (HW).     

Removal of trace organic contaminants from domestic wastewater: A meta-analysis comparison of sewage treatment technologies

Trace organic contaminants (TrOCs), such as endocrine disrupting compounds (EDCs) and pharmaceuticals and personal care products (PPCPs), represent global threats to aquatic animals and ecosystems. A major source of TrOCs in the aquatic environment is via the discharge of treated sewage, so there is an urgent need to evaluate the comparative efficiencies of the most widely used sewage treatment technologies as regards elimination of these compounds from wastewater. To address this need, 976 published articles were compiled focusing on estimates of removal (%) for 20 common environmental TrOCs, from five major sewage treatment technologies: conventional activated sludge (CAS), oxidation ditch (OD), membrane bioreactor (MBR), ponds and constructed wetlands (PCW), and trickling biological filters (TBF). A quantitative meta-analysis was performed to compare standardized relative removal efficiencies (SREs) of the compounds amongst these technologies, and where possible potential sources of heterogeneity were considered (e.g., flow rates and chemical sorption potential). The results indicate that the most widely used CAS treatment and the less common TBF provide comparatively poor overall removal of common organic micropollutants. Membrane bioreactors appear to be capable of achieving the greatest overall removal efficiencies, but the sustainability and economic viability of this option has been questioned. Treatment with OD systems may be more economical while still achieving comparatively high removal efficiencies, and the analysis revealed OD to be the best option for targeting highly potent estrogenic EDCs. This study offers a unique global assessment of TrOC removal via leading sewage treatment technologies, and is an important step in the identification of effective options for treating municipal sewage.     

Aquatic arsenic: Toxicity,speciation, transformations,and remediation

This paper reviews the current knowledge on the toxicity, speciation and biogeochemistry of arsenic in aquatic environmental systems. The toxicity of arsenic is highly dependent on the chemical speciation. The effects of pH, E_h, adsorbing surfaces, biological mediation, organic matter, and key inorganic substances such as sulfide and phosphate combine in a complex and interwoven dynamic fashion to produce unique assemblages of arsenic species. The number of different arsenic species found in environmental samples and an understanding of the transformations between arsenic species has increased over the past few decades as a result of new and refined analytical methods. Changes in arsenic speciation and in total arsenic content of foods upon processing have suggested possible risks associated with processed and unprocessed food. Arsenic removal from water using adsorbents, chemical oxidation, photolysis and photocatalytic oxidation techniques is also reviewed.     

Effects of acidification on aquatic ecosystems

Effects of acidification on aquatic ecosystems are analyzed on the basis of an analytical synopsis of relevant data. Major active agents influencing aquatic organisms and main trends in the reorganization of microbial, phyto- and zooplanktonic, benthic, and fish communities in an acidified environment are described. A generalized concept of changes in ecosystems caused by acid precipitation and accompanying factors is formulated. These changes include the reduction of biodiversity of all structural elements due to the disappearance of species sensitive to acidification, modification of trophic structure, and decrease of fish stock.Translated from Ekologiya, No. 2, 2005, pp. 110–119.Original Russian Text Copyright © 2005 by Moiseenko.     

Trace metal bioaccumulation: models, metabolic availability and toxicity

Aquatic invertebrates take up and accumulate trace metals whether essential or non-essential, all of which have the potential to cause toxic effects. Subsequent tissue and body concentrations of accumulated trace metals show enormous variability across metals and invertebrate taxa. Accumulated metal concentrations are interpreted in terms of different trace metal accumulation patterns, dividing accumulated metals into two components - metabolically available metal and stored detoxified metal. Examples of different accumulation patterns are described from crustaceans but have a general applicability to all aquatic invertebrates. Toxicity does not depend on total accumulated metal concentration but is related to a threshold concentration of internal metabolically available metal. Toxicity ensues when the rate of metal uptake from all sources exceeds the combined rates of detoxification and excretion (if present) of the metal concerned. The biodynamic model of trace metal bioaccumulation allows the prediction and explanation of widely differing accumulated trace metal concentrations in organisms, combining geochemical analyses of environmental metal concentrations with the measurement of key physiological parameters for a species from the site under consideration. The combination of the biodynamic model as a unified explanation of metal bioaccumulation with an understanding of the relationship between accumulation and toxicity sets the stage for a realistic understanding of the significance of trace metal concentrations in aquatic invertebrates.     

Do nanoparticles present ecotoxicological risks for the health of the aquatic environment?

Nanotechnology is a major innovative scientific and economic growth area, which may present a variety of hazards for environmental and human health. The surface properties and very small size of nanoparticles and nanotubes provide surfaces that may bind and transport toxic chemical pollutants, as well as possibly being toxic in their own right by generating reactive radicals. There is a wealth of evidence for the harmful effects of nanoscale combustion-derived particulates (ultrafines), which when inhaled can cause a number of pulmonary pathologies in mammals and humans. However, release of manufactured nanoparticles into the aquatic environment is largely an unknown. This review addresses the possible hazards associated with nanomaterials and harmful effects that may result from exposure of aquatic animals to nanoparticles. Possible nanoparticle association with naturally occurring colloids and particles is considered together with how this could affect their bioavailability and uptake into cells and organisms. Uptake by endocytotic routes are identified as probable major mechanisms of entry into cells; potentially leading to various types of toxic cell injury. The higher level consequences for damage to animal health, ecological risk and possible food chain risks for humans are also considered based on known behaviours and toxicities for inhaled and ingested nanoparticles in the terrestrial environment. It is concluded that a precautionary approach is required with individual evaluation of new nanomaterials for risk to the health of the environment. Although current toxicity testing protocols should be generally applicable to identify harmful effects associated with nanoparticles, research into new methods is required to address the special properties of nanomaterials.